JP2018189898A - Laminate structure and molded body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate structure and a molded body comprising a hue (especially, a blue color), and exhibiting a lacquer-state black color with high blackness.SOLUTION: A laminate structure comprises: a base material; and a laminate membrane arranged on the base material. The laminate membrane comprises: a light absorption layer which has an average extinction coefficient of being 0.01 or higher in whole area of a wavelength region of 400-700 nm; and an optical adjustment layer comprising a laminate formed by contacting and laminating a low refraction index dielectric layer having two or more dielectric layers arranged adjacently to the light absorption layer on an opposite side of the base material in view from the light absorption layer, and whose refraction indexes are different each other and exhibiting a relatively low refraction index between the two or more dielectric layers, and a high refraction index dielectric layer exhibiting a relatively high refraction index between two or more dielectric layers. In the laminate structure, R1>R2>R3, 4.0%<R1, R2, R3<6.0% are satisfied (average reflection ratio to incident light parallel to a lamination direction of a laminate in R1:400-500nm, R2:500-600nm and R3:600-700nm).SELECTED DRAWING: Figure 1

Description

  The present disclosure relates to a laminated structure and a molded body.

  In recent years, products in fields such as automobiles or electronic products such as smartphones or watches may not only be excellent in the density and hue of colored colors, but may also be required to have a texture that appeals to the human sense of depth. .

  The texture as described above often comes from the design imparted to the product, greatly affects the visual impression of the product, and affects the commercial value of the product itself. The appearance texture of the product varies depending on the type of the product, and may vary greatly depending on, for example, the hue or the degree of light reflection.

As a technique related to the above, for example, an antiglare hard coat film in which fine particles are included in the hard coat layer and the surface of the antireflection layer has an uneven shape is disclosed, which is excellent in antiglare property and improves the darkness of black. (For example, refer to Patent Document 1).
In addition, a colored product including a reflectance attenuation layer formed of a dielectric material, a light absorption film formed of a metal material, and a concealing film is disclosed as a vapor deposition optical porous layer (see, for example, Patent Document 2). . Furthermore, from the viewpoint of thermal conductivity and insulating properties, a composite sheet having a exfoliated graphite layer containing exfoliated graphite, and a light absorption part having a surface reflectance and a back surface reflectance of 1% or less at a wavelength of 400 nm to 700 nm, The light absorption member which consists of a light-shielding part and a light absorption part is disclosed (for example, refer patent documents 3-4).

JP 2013-178534 A JP 2013-37040 A JP 2011-189700 A JP 2006-201697 A

  As described above, conventionally, a technique for improving the antiglare property, a technique for suppressing reflection of light or providing concealment, or imparting a black tone has been studied. However, it is hard to say that any of these documents is a technique that considers enhancing the black texture.

  In particular, with regard to the black texture, in addition to the black hue, in order to give a texture with a sense of depth in the case of a three-dimensional molded product, it is not just a dark black, but a black with high blackness and added color. Therefore, there is a demand for a so-called lacquer-like black color that has a surface gloss that gives a reflected image sharp, but has anti-glare properties and reduced reflected light.

For example, materials, decorations or paints used for interior and exterior of automobiles and the like are often aimed at protecting the vehicle body and improving durability, but recently, appearance quality appealing to human sensitivity (for example, interiors) In the case of materials, there is a high demand for improvement in appearance, or in the case of paints, the coating texture. In order to improve the appearance of the painted product, it is important to increase the depth perceived when the product is observed.
A lacquered product has been known as a representative example of a product having a good texture for a long time. In particular, black lacquering is said to give the product a sense of depth and give it a high-class feel. However, black lacquer coating has a problem that is not suitable for industrial production because it is a traditional craft technique by craftsmen.

However, simply applying carbon materials such as carbon black and carbon nanotubes that have been widely used as black materials in the past can achieve black density, but as described above, the blackness is high and the color tone is high. It is difficult to reproduce a lacquer-like black color that has a black hue with the addition of and has a surface gloss that gives a sharp reflected image, but has anti-glare properties and reduced reflected light.
Reproduction of lacquer-like black color with materials other than lacquer is considered to meet recent demand.

The present disclosure has been made in view of the above. That is,
The problem to be solved by an embodiment of the present invention is to provide a laminated structure that has a color (particularly bluish) and exhibits a lacquer-like black color with high blackness.
The problem to be solved by another embodiment of the present invention is to provide a molded article having a color (particularly bluish) and exhibiting a lacquer-like black color with high blackness.

Specific means for solving the above problems include the following aspects.
<1> A substrate and a laminated film disposed on the substrate,
A light absorption layer having an average extinction coefficient of 0.01 or more in the entire wavelength range of 400 nm to 700 nm, a light absorption layer disposed adjacent to the light absorption layer on the side opposite to the substrate, and refraction A low refractive index dielectric layer having two or more dielectric layers having different rates and having a relatively low refractive index between the two or more dielectric layers, and a relative relationship between the two or more dielectric layers; A high refractive index dielectric layer having a high refractive index, and an optical adjustment layer including a laminate laminated in contact with each other, and the following formulas a, b1, b2, and A black-toned laminated structure satisfying the formula b3.
R1>R2> R3 Formula a
4.0% <R1 <6.0% Formula b1
4.0% <R2 <6.0% Formula b2
4.0% <R3 <6.0% Formula b3
R1 represents an average reflectance with respect to incident light parallel to the stacking direction of the laminate in the wavelength range of 400 nm to 500 nm, and R2 is incident parallel to the stacking direction of the stack in the wavelength range of 500 nm to 600 nm. The average reflectance with respect to light is represented, and R3 represents the average reflectance with respect to incident light parallel to the stacking direction of the stacked body in a wavelength range of 600 nm to 700 nm.

<2> The refractive index of the low refractive index dielectric layer is lower than the refractive index of the light absorbing layer, and the refractive index of the high refractive index dielectric layer is higher than the refractive index of the light absorbing layer. It is a laminated structure.
<3> The laminated structure according to <1> or <2>, wherein the refractive index of the low refractive index dielectric layer is 1.55 or less.
<4> The laminated structure according to any one of <1> to <3>, wherein the refractive index of the high refractive index dielectric layer is 1.70 or more.
<5> The absolute value of the difference between the refractive index of the high refractive index dielectric layer and the refractive index of the low refractive index dielectric layer is 0.3 or more, and is described in any one of <1> to <4> It is a laminated structure.
<6> The laminated structure according to any one of <1> to <5>, in which the reflectance Rs with respect to S-polarized light satisfies the following formula.

  In the formula, θ represents an incident angle of light incident in the stacking direction of the stacked film, satisfies 0 radian ≦ θ ≦ π / 3 radian, and Rs (θ) and f (θ) are represented by the following equations.

In the formula, θ represents an incident angle of light incident in the stacking direction of the stacked film, and satisfies 0 radian ≦ θ ≦ π / 3 radian. λ is the wavelength of incident light, and its unit is nm. A, B, C, D, and E are respectively A = 4.813 × 10 ⁻¹³ , B = −1.606 × 10 ⁻⁹ , C = 2.049 × 10 ⁻⁶ , and D = −1.212. × 10 ⁻³ , E = 1.847.
Λ ² represents the square of λ, λ ³ represents the third power of λ, and λ ⁴ represents the fourth power of λ.

<7> The laminated structure according to any one of <1> to <6>, in which the light absorption layer satisfies the following formula c and formula d.
N1>N2>N3> 1.55 formula c
K1>K2>K3> 0.01 Formula d
In the above, N1 represents the average refractive index in the wavelength range of 400 nm to 500 nm, N2 represents the average refractive index in the wavelength range of 500 nm to 600 nm, and N3 represents the average refractive index in the wavelength range of 600 nm to 700 nm. It is. K1 represents an average extinction coefficient in a wavelength range of 400 nm to 500 nm, K2 represents an average extinction coefficient in a wavelength range of 500 nm to 600 nm, and K3 represents an average extinction coefficient in a wavelength range of 600 nm to 700 nm. It is.
<8> The laminated structure according to any one of <1> to <7>, wherein the light absorption layer has a thickness of 2 μm or more.
<9> The laminated structure according to any one of <1> to <8>, in which the optical adjustment layer includes at least one compound selected from SiO ₂ , SiN, and Al ₂ O ₃ .
<10> The laminate in the optical adjustment layer includes at least two low refractive index dielectric layers and at least two high refractive index dielectric layers, the low refractive index dielectric layer and the high refractive index dielectric layer. Is a laminated structure according to any one of <1> to <9>, which is a laminate of four or more layers alternately stacked.
<11> The laminated structure according to any one of <1> to <10>, wherein the arithmetic average value of the surface roughness Ra on the side where the laminated film is disposed with respect to the substrate is 30 nm or less. .
<12> The arithmetic average value of the interface roughness at the interface between the light absorption layer and the laminate and the arithmetic average value of the interface roughness at the interface between the low refractive index dielectric layer and the high refractive index dielectric layer of the laminated film are The laminated structure according to any one of <1> to <11>, which is 30 nm or less.
<13> A molded body obtained by molding the laminated structure according to any one of <1> to <12> in two dimensions or three dimensions.

According to one embodiment of the present invention, there is provided a laminated structure having a color (particularly bluish) and exhibiting lacquer black with high blackness.
According to other embodiment of this invention, the molded object which has color (especially bluishness) and exhibits lacquer-like black with high blackness is provided.

It is a schematic sectional drawing which shows an example of the laminated structure of this indication. It is a reflection spectrum which shows the reflectance in the wavelength range of 400 nm-700 nm of the laminated structure of an Example and a comparative example. FIG. 3 is a partially enlarged view of FIG. 2. It is a graph which shows the incident angle dependence of the reflectance in wavelength 450nm of the laminated structure of Examples 1-2. It is a graph which shows the incident angle dependence of the reflectance in wavelength 550nm of the laminated structure of Examples 1-2. It is a graph which shows the incident angle dependence of the reflectance in wavelength 650nm of the laminated structure of Examples 1-2. It is a graph which shows the optical characteristic of Ni moth-eye structure film.

  Hereinafter, the laminated structure and the molded body of the present disclosure will be described in detail.

  In the present specification, a numerical range indicated using “to” means a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively. In a numerical range described in stages in the present disclosure, an upper limit value or a lower limit value described in a numerical range may be replaced with an upper limit value or a lower limit value in another numerical range. Further, in the numerical ranges described in the present disclosure, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the values shown in the examples.

In this specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. means.
In this specification, the term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. It is.

In this specification, the refractive index and the extinction coefficient are values measured by a spectroscopic ellipsometry method at a wavelength of 550 nm unless otherwise specified.
The average refractive index and the average extinction coefficient are average values obtained by dividing the measured values measured at equal intervals of 10 nm or less by a spectroscopic ellipsometry method by the number of measurement points in a specific wavelength region.

<Laminated structure>
The multilayer structure of the present disclosure includes a base material and a multilayer film disposed on the base material, and the multilayer film has an average extinction coefficient of 0.01 or more in the entire wavelength range of 400 nm to 700 nm. A light-absorbing layer, and an optical adjustment layer disposed adjacent to the light-absorbing layer on the side opposite to the substrate as viewed from the light-absorbing layer, and a formula a shown below, and , Expression b1, Expression b2, and Expression b3 are satisfied.
R1>R2> R3 Formula a
4.0% <R1 <6.0% Formula b1
4.0% <R2 <6.0% Formula b2
4.0% <R3 <6.0% Formula b3
The optical adjustment layer in the present disclosure includes two or more dielectric layers having different refractive indexes, a low refractive index dielectric layer having a relatively low refractive index between the two or more dielectric layers, and two or more dielectric layers. A high refractive index dielectric layer having a relatively high refractive index between the dielectric layers is brought into contact with each other (for example, in the case of three or more layers, a low refractive index dielectric layer and a high refractive index dielectric layer (Including alternating layers).
Here, R1, R2 and R3 in the above formula are as follows.
R1 represents an average reflectance with respect to incident light (perpendicular incident light with respect to the surface of the dielectric layer) parallel to the stacking direction of the stacked body in a wavelength range of 400 nm to 500 nm.
R2 represents an average reflectance with respect to incident light (perpendicular incident light with respect to the surface of the dielectric layer) parallel to the stacking direction of the stacked body in a wavelength range of 500 nm to 600 nm.
R3 represents an average reflectance with respect to incident light (perpendicular incident light with respect to the surface of the dielectric layer) parallel to the stacking direction of the stacked body in a wavelength region of 600 nm to 700 nm.

  In the present disclosure, “having a relatively low refractive index between two or more dielectric layers” or “having a relatively high refractive index between two or more dielectric layers” forms a laminate. The relationship between the low-refractive index dielectric layer and the high-refractive index dielectric layer is a relative magnitude relationship of the refractive index when the refractive indexes between a plurality of dielectrics are compared. That is, when comparing the refractive indexes of a plurality of dielectric layers included in a laminate, it means that a specific dielectric layer has a higher or lower refractive index than other dielectric layers. doing.

Conventionally, a technique for suppressing or preventing absorption of incident light, a technique for imparting anti-glare properties, or a technique for obtaining a dark black color by attenuating reflected light so that the reflected light does not look metallic. Various studies have been made.
However, for example, as in Patent Document 1, if fine particles are used or an uneven shape is imparted to the surface in order to obtain antiglare properties, the antiglare effect can be expected, but the surface properties become matte and glossy. The feeling is significantly impaired, and as a result, the visual depth is likely to be lowered. Also, the inventions described in Patent Documents 2 to 4 are considered to obtain an attenuation effect on the reflected light, but even if the reflected light is simply attenuated, the luster is lost and a sense of depth cannot be obtained.
As described above, when incident light is likely to be scattered on the surface due to the presence of particles on the surface or the formation of irregularities, it is considered that not only the gloss is lowered but also the feeling of depth is lowered. The technology that has been proposed in the past reproduces the glossy luster and does not depend on the shade of black, but has a black hue with a tint that has a lacquer-like black color, and has a sense of depth. The reality is that no technology to achieve the color tone has been provided.

For example, in the case of black lacquer coating, it is considered that a glossy surface property is expressed due to an appropriate glossiness, and thereby a sense of depth is obtained. Furthermore, when black is given a color, in addition to an increase in the sense of depth, it is considered that the hue becomes black with a hue and a high-grade hue.
In view of the above, the present disclosure provides a light absorption layer and an optical adjustment layer including a plurality of dielectric layers having different refractive indexes when providing a laminated film on a substrate, and an average wavelength range of 400 nm to 500 nm. The reflectance R1, the average reflectance R2 in the wavelength region 500 nm to 600 nm, and the average reflectance R3 in the wavelength region 600 nm to 700 nm satisfy the relationship R1>R2> R3, and all of R1, R2, and R3 are 4.0. % To 6.0%. As a result, unlike black, which is simply dark and glossy, black has a black tone with a tint (for example, bluish), and the reflected image is sharp but reflected to the extent that an anti-glare effect is obtained. The rate is suppressed and appears as a color with a sense of depth. Therefore, there is an effect that a high-class feeling close to a so-called lacquered product can be obtained.
Thus, the laminated structure of the present disclosure has a high blackness and a lacquer-like black color.

The laminated structure of the present disclosure satisfies the following formula a, and formulas b1, b2, and b3.
R1>R2> R3 Formula a
4.0% <R1 <6.0% Formula b1
4.0% <R2 <6.0% Formula b2
4.0% <R3 <6.0% Formula b3
In each formula, details of R1, R2, and R3 are as follows.
R1 represents an average reflectance with respect to incident light (perpendicular incident light with respect to the surface of the dielectric layer) parallel to the stacking direction of the stacked body in a wavelength range of 400 nm to 500 nm.
R2 represents an average reflectance with respect to incident light (perpendicular incident light with respect to the surface of the dielectric layer) parallel to the stacking direction of the stacked body in a wavelength range of 500 nm to 600 nm.
R3 represents an average reflectance with respect to incident light (perpendicular incident light with respect to the surface of the dielectric layer) parallel to the stacking direction of the stacked body in a wavelength region of 600 nm to 700 nm.

  In the laminated structure of the present disclosure, R1, R2, and R3 satisfy the relationship of formula a, and the average reflectance increases as the wavelength becomes shorter in the wavelength range of 400 nm to 700 nm. Therefore, the laminated structure according to the present disclosure has strong black color tone with strong reflection on the side close to 400 nm to 500 nm and a bluish color added to black. Thereby, the color tone similar to the shade of lacquer tone black is exhibited.

R1, R2 and R3 satisfy the formulas b1 to b3, and all are in the range of more than 4.0% and less than 6.0%. In other words, when the average reflectance in the wavelength range of 400 nm to 700 nm exceeds 4.0%, a matte black tone is obtained instead of a matte black tone. In addition, when the average reflectance in the wavelength range of 400 nm to 700 nm is less than 6.0%, the reflected image is sharply reflected but the reflectance is suppressed to such an extent that an antiglare effect is obtained, and a hue with a feeling of depth is obtained. can get.
For the same reason as described above, it is more preferable that R1, R2, and R3 satisfy the following formulas b4, b5, and b6.
5.0% <R1 <6.0% formula b4
4.0% <R2 <5.0% formula b5
4.0% <R3 <5.0% formula b6

The average reflectance of the laminated structure of the present disclosure is measured by the following method.
Using a reflection spectral film thickness meter (Otsuka Electronics Co., Ltd.) with respect to the surface of the dielectric layer that forms the outermost layer arranged at the position farthest from the base material of the laminated body, the laminated structure is 400 nm to 500 nm. The average reflectance R1 in the wavelength region, the average reflectance R2 in the wavelength region of 500 nm to 600 nm, and the average reflectance R3 in the wavelength region of 600 nm to 700 nm are measured. Each average reflectance is calculated | required as a value which remove | divided the total of the reflectance measured for every 1 nm within each wavelength range by the number of the measurement points.

The laminated structure of the present disclosure may have, for example, the laminated structure shown in FIG. FIG. 1 is a schematic cross-sectional view illustrating an example of a laminated structure according to the present disclosure.
As shown in FIG. 1, the laminated structure 100 is provided with a laminated film 20 having a laminated structure including an optical adjustment layer 22 and a light absorption layer 24 on a base material 30, and further the optical adjustment layer 22. Are a high refractive index dielectric layer 12, a low refractive index dielectric layer 14, a high refractive index dielectric layer 16, and a low refractive index, in which high refractive index dielectric layers and low refractive index dielectric layers are alternately arranged. The dielectric constant layer 18 is formed of a laminate composed of four dielectric layers.

-Laminated film-
The laminated film in the present disclosure has a light absorption layer having an average extinction coefficient of 0.01 or more in the entire wavelength range of 400 nm to 700 nm, and a light absorption layer on the side opposite to the side having the base material of the light absorption layer. A laminated structure having an optical adjustment layer disposed adjacent to each other, and has a contact interface between the light absorption layer and the optical adjustment layer.

  The laminated film only needs to have at least one light absorption layer, and two or more light absorption layers may be provided as necessary. In this case, each of the two or more light absorption layers may be a light absorption layer having different average extinction coefficients in the wavelength region of 400 nm to 700 nm.

(Light absorption layer)
The laminated film in the present disclosure has a light absorption layer having an average extinction coefficient of 0.01 or more in the entire wavelength range of 400 nm to 700 nm. An average extinction coefficient of 0.01 or more indicates that the light absorption layer is a light absorbing layer and not a transparent layer, and the light absorption layer in the present disclosure has a wavelength range of 400 nm to 700 nm. It has absorption over the whole area.

The extinction coefficient is an imaginary component other than the refractive index in the complex refractive index, and the average refractive index N _i and the average extinction coefficient K _i in the wavelengths λ ₁ to λ ₂ are defined as follows.
The average refractive index and the average extinction coefficient are obtained as average values at wavelengths λ _{1 to} λ ₂ .
Specifically, the average refractive index and the average extinction coefficient are measured by spectroscopic ellipsometry, for example, by measuring 300 refractive indexes or extinction coefficients every 1 nm in the wavelength range of 400 nm to 700 nm, and averaging the measured values. Is required. Alternatively, the average refractive index and the average extinction coefficient are calculated based on the following formula by obtaining an approximate curve (refractive index dispersion curve) n (λ) from the values measured as described above.

  The light absorption layer is preferably not a layer containing a material containing metal as a main component. Here, the main component means that the content ratio of the metal element in the layer is 50% by mass or more.

  The light absorption layer can be formed using a material having an average extinction coefficient of 0.01 or more. As the material having an average extinction coefficient of 0.01 or more, for example, a black paint such as an anti-reflection black paint for optical elements or a black ink material for lenses can be used. As a material having an average extinction coefficient of 0.01 or more, a commercially available product may be used, and examples of the commercially available product include optical black ink GT-1000 (Canon Kasei Co., Ltd.).

The light-absorbing layer preferably has an aspect that satisfies the following formulas c and d.
N1>N2>N3> 1.55 formula c
K1>K2>K3> 0.01 Formula d
N1 represents an average refractive index in a wavelength range of 400 nm to 500 nm, N2 represents an average refractive index in a wavelength range of 500 nm to 600 nm, and N3 represents an average refractive index in a wavelength range of 600 nm to 700 nm. K1 represents an average extinction coefficient in a wavelength range of 400 nm to 500 nm, K2 represents an average extinction coefficient in a wavelength range of 500 nm to 600 nm, and K3 represents an average extinction coefficient in a wavelength range of 600 nm to 700 nm. .

  By satisfy | filling said Formula c and Formula d, the black tone with a favorable depth feeling is easy to be obtained, reducing the lamination number of the below-mentioned optical adjustment layer. Therefore, the manufacturing suitability is also improved.

In the laminated structure of the present disclosure, it is preferable that N1, N2, and N3 satisfy the relationship of formula c, and that the average refractive index is larger toward the shorter wavelength side in the wavelength range of 400 nm to 700 nm. That is, the laminated structure of the present disclosure satisfies the formula c and realizes a black tone with a tint in which bluish color is added to black by adjusting the refractive index on the side close to 400 nm to 500 nm. Cheap. Thereby, adjustment of the refractive index in an optical adjustment layer becomes easy, and it becomes easy to adjust to the color tone similar to the lacquer-like black hue as a result.
For the same reason as described above, it is more preferable that N1, N2, and N3 satisfy the following expression c1.
N1>N2>N3> 1.60 Formula c1

In the laminated structure of the present disclosure, it is preferable that K1, K2, and K3 satisfy the relationship of formula d, and that the average extinction coefficient is larger toward the shorter wavelength side in the wavelength range of 400 nm to 700 nm. That is, the multilayer structure of the present disclosure satisfies the formula d, and is adjusted so that the average extinction coefficient becomes higher toward the side closer to 400 nm to 500 nm, so that a black tone with a tint in which bluish color is added to black is obtained. It is easy to realize. Thereby, adjustment of the refractive index in an optical adjustment layer becomes easy, and it becomes easy to adjust to the color tone similar to the lacquer-like black hue as a result.
For the same reason as described above, it is more preferable that K1, K2, and K3 satisfy the following formula d1.
K1>K2>K3> 0.02 Formula d1

The thickness of the light absorption layer is preferably in the range of 2 μm or more.
When the thickness of the light absorption layer is 2 μm or more, not only a black hue can be secured, but also the light absorption can be further improved.
The thickness of the light absorption layer is more preferably 4 μm or more. Moreover, the upper limit of the thickness of the light absorption layer is not particularly limited, and may be, for example, 200 μm or less.

(Optical adjustment layer)
The laminated film in the present disclosure has an optical adjustment layer disposed adjacent to the light absorption layer on the side opposite to the side having the base material of the light absorption layer described above.
The optical adjustment layer in the present disclosure includes two or more dielectric layers having different refractive indexes, a low refractive index dielectric layer having a relatively low refractive index between the two or more dielectric layers, and two or more dielectric layers. A high refractive index dielectric layer having a relatively high refractive index between the dielectric layers is laminated.

The optical adjustment layer is preferably a layer having an average extinction coefficient of less than 0.01 in a wavelength range of 400 nm to 700 nm.
The optical adjustment layer is preferably included in two or more layers, and more preferably in three or more layers. The optical adjustment layer has a laminated structure having a laminated body, and plays a role of adjusting the reflection spectrum of the laminated structure to express a sense of depth.
Adjustment of the reflection spectrum by the optical adjustment layer can be performed by optimizing the film thickness and refractive index of the plurality of dielectric layers forming the laminate.

Each of the low refractive index dielectric layer and the high refractive index dielectric layer may have at least one layer. The optical adjustment layer is a laminate including four or more dielectric layers each having two or more low refractive index dielectric layers and high refractive index dielectric layers, or a low refractive index dielectric layer and a high refractive index dielectric. It may be a laminated body having one body layer, the other being composed of two or more layers, and including three or more dielectric layers as a whole.
Further, the number of the low-refractive index dielectric layers and the high-refractive index dielectric layers in the laminate may be an even layer or an odd layer, respectively. The number of the low-refractive index dielectric layers and the high-refractive index dielectric layers in the stacked body may be the same or different numbers.

A preferred optical adjustment layer is an embodiment having a laminate including four or more dielectric layers.
In particular, the optical adjustment layer includes at least two low refractive index dielectric layers and at least two high refractive index dielectric layers, and the low refractive index dielectric layers and the high refractive index dielectric layers are alternately stacked. The aspect made into the laminated body of four or more layers made is preferable.
In the above aspect, the depth is excellent, and the manufacturing is easy.

Preferably, the refractive index of the low refractive index dielectric layer is lower than the refractive index of the light absorbing layer, and the refractive index of the high refractive index dielectric layer is higher than the refractive index of the light absorbing layer.
The low refractive index side and the high refractive index side with the refractive index of the light absorbing layer as the center are adjusted by a plurality of dielectric layers having different refractive indexes, so that a black tone with a tint can be achieved while reducing the number of layers. It is easy to obtain and easy to adjust to a deep color tone.

The refractive index of the low refractive index dielectric layer is preferably in the range of 1.55 or less.
When the refractive index of the low refractive index dielectric layer is 1.55 or less, it is easy to secure a difference in refractive index from the high refractive index dielectric layer, and it is easy to adjust to a lacquer-like black color with a sense of color and depth. .

The refractive index of the high refractive index dielectric layer is preferably in the range of 1.70 or more.
When the refractive index of the high refractive index dielectric layer is 1.70 or more, it is easy to secure a refractive index difference from the low refractive index dielectric layer, and it is easy to adjust to a lacquer-like black color with a sense of color and depth. .

The absolute value of the difference between the refractive index of the high refractive index dielectric layer and the refractive index of the low refractive index dielectric layer is preferably 0.3 or more.
When the absolute value of the difference between the refractive index of the high refractive index dielectric layer and the refractive index of the low refractive index dielectric layer is 0.3 or more, the gap between the low refractive index dielectric layer and the high refractive index dielectric layer is It is easy to secure the difference in refractive index and easily adjust to lacquer-like black with a sense of color and depth.

The reflectance Rs for S-polarized light preferably satisfies the following formula.
S-polarized light refers to polarized light in which electrolysis vibrates perpendicularly to the incident surface including incident light and reflected light, perpendicular to the surface of the dielectric layer of the laminated film.

  In the above formula, θ represents an incident angle of light incident in the stacking direction of the stacked film, satisfies 0 radian ≦ θ ≦ π / 3 radian (0 ° ≦ θ ≦ 60 °), Rs (θ) and f (Θ) is represented by the following formula.

In the above formula, θ represents an incident angle of light incident in the stacking direction of the stacked film, and satisfies 0 radian ≦ θ ≦ π / 3 radian.
λ is the wavelength of incident light, and its unit is nm. Λ ² represents the square of λ, λ ³ represents the third power of λ, and λ ⁴ represents the fourth power of λ.
A, B, C, D, and E are respectively A = 4.813 × 10 ⁻¹³ , B = −1.606 × 10 ⁻⁹ , C = 2.049 × 10 ⁻⁶ , and D = −1.212. × 10 ⁻³ , E = 1.847.

f (θ) is a factor indicating a deviation from an ideal reflection spectrum, and is a value obtained empirically as a value required for obtaining a black lacquered color tone. As is apparent from the above equation, f (θ) increases as the incident angle θ increases. That is, on the basis of the case where the incident angle θ is perpendicular to the surface of the dielectric film of the laminated body in the laminated film (that is, θ = 0 °), the reflectance is also vertical when the incident angle θ deviates from 0 °. This takes into consideration that the reflectance changes when the light is incident.
Therefore, P indicates the minimum value in the case where a deviation occurs in the range where the reflectance is allowed to be small in the range of the incident angle θ, and Q is a large value of the reflectance in the range of the incident angle θ. The maximum value when a deviation occurs in the allowable range on the side is shown. Therefore, the fact that the reflectance Rs for S-polarized light satisfies the range of P to Q means that a color tone similar to lacquer black is reproduced even when light is incident obliquely in the range of the incident angle θ. Is shown.

The optical adjustment layer may be an inorganic layer such as SiO ₂ , TiO ₂ , Al ₂ O ₃ , SiN, SiON, Ta ₂ O ₅ , ZrO ₂ , or MgF ₂ .
The optical adjustment layer can be suitably formed by a sputtering method.
Moreover, you may form by the apply | coating method using the adjustment liquid for application | coating containing resin suitable for adjusting a reflection spectrum. In this case, the optical adjustment layer is formed of a coating layer.

  The optical adjustment layer preferably has a micro-order or nano-order fine particle content of less than 30% by mass with respect to the solid content of the layer, and further does not contain the fine particles (zero mass%). It is more preferable. When the fine particles described above are contained, although depending on the size of the fine particles, the scattering effect is likely to occur, the gloss is likely to be impaired, and a high sense of depth may not be obtained.

The optical adjustment layer is preferably provided as a layer containing at least one compound selected from SiO ₂ , SiN, and Al ₂ O ₃ from the viewpoint of film flatness, water resistance, and scratch resistance.

The layer thickness of the low refractive index dielectric layer and the high refractive index dielectric layer is preferably 1 nm to 1 μm, and more preferably 3 nm to 0.5 μm. A layer thickness of 1 nm or more is advantageous in terms of improving the flatness of the film. If the layer thickness is 1 μm or less, it is easy to adjust interference (reflectance).
In addition, the thickness of the optical adjustment layer is preferably 0.05 μm to 2 μm from the viewpoint of achieving both adjustment of interference (reflectance) and scratch resistance.

-Base material-
The laminated structure of the present disclosure has a base material.
Examples of the base material include a resin material and an inorganic material.
The resin material and the inorganic material are preferably transparent materials. Here, “transparency” means that the transmittance of visible light having a wavelength of 400 nm to 700 nm is 80% or more. Therefore, a base material using a transparent resin material or an inorganic material refers to a base material having a visible light transmittance of 80% or more at a wavelength of 400 nm to 700 nm, and the visible light transmittance of the base material is 90% or more. It is preferable that

Examples of the resin material include acetyl cellulose resins such as triacetyl cellulose; polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate; polyethylene (PE), polymethylpentene, cycloolefin polymer, cycloolefin copolymer, and the like. Olefin resins; acrylic resins such as polymethyl methacrylate can be used.
Examples of the inorganic material include glass such as soda glass, potash glass, and lead glass; ceramics such as translucent piezoelectric ceramics (PLZT); quartz; fluorite;

  What is necessary is just to select the thickness of a base material suitably according to a use, 10 micrometers-5000 micrometers are preferable, 25 micrometers-250 micrometers are more preferable, 50 micrometers-200 micrometers are still more preferable.

  Also, the shape of the substrate is not particularly limited. For example, it is in the form of a roll, does not have enough flexibility to be wound into a roll, or has low flexibility but can be bent by applying a load. Either is acceptable.

  A single substrate may be used, or a plurality of substrates may be stacked and used as a multilayer structure. When it has a multilayer structure in which a plurality of base materials are stacked, a multilayer structure in which the same base materials are stacked may be used, or a multilayer structure in which different base materials are combined may be used.

The laminated structure of the present disclosure preferably has an aspect in which the surface roughness Ra on the side where the laminated film is disposed with respect to the base material is an arithmetic average value of 30 nm or less. The smooth surface with a surface roughness of 30 nm or less suppresses the reduction in glossiness due to the roughness of the surface, can maintain a more glossy luster, and thus has an excellent sense of depth. Become.
The surface roughness Ra is more preferably 15 nm or less. The surface roughness Ra is preferably as small as possible, but the lower limit may be, for example, 0.1 nm or more.

  The surface roughness Ra is a value measured in accordance with Japanese Industrial Standard (JIS) B0601 (2001). For example, surface information of a 5 μm square area is obtained using an atomic force microscope (manufactured by Brugger). It can be obtained from the measured value.

The laminated structure of the present disclosure includes an arithmetic average value of the interface roughness at the interface between the light absorption layer and the laminate, and an interface at the interface between the low refractive index dielectric layer and the high refractive index dielectric layer. An embodiment in which the arithmetic average value of roughness is 30 nm or less is preferable.
By having a smooth surface with an interface roughness of 30 nm or less, a reduction in glossiness due to the roughness of the interface can be suppressed, a more glossy gloss can be maintained, and as a result, a sense of depth is excellent. Become.
The interface roughness is more preferably 15 nm or less. The interface roughness is preferably as small as possible, but the lower limit may be, for example, 0.1 nm or more.

  The interface roughness is a value measured by cutting a section of the laminate by an ion beam etching method, observing the cut section with a transmission electron microscope (JEOL Ltd.), obtaining a photograph of the interface.

<Molded body>
The molded body of the present disclosure is obtained by molding the above-described laminated structure of the present disclosure in two dimensions or three dimensions. Since the molded body of the present disclosure is molded using the above-described laminated structure, it has a color (particularly bluish) and exhibits a lacquer-like black color with high blackness. Therefore, unlike a texture that is simply dark and glossy in black, for example, it has a bluish black tone, and the black tone is a reflected image that is sharp, but the reflectance is suppressed and the color has a sense of depth. appear. Therefore, a high-class feeling close to what is called a lacquered product is obtained.

The forming may be performed by any method as long as the laminated structure can be formed two-dimensionally or three-dimensionally, or may be formed using a mold.
Suitable examples of the molding method include thermoforming and vacuum forming.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

(Example 1)
-Fabrication of laminated structure-
Optical black ink GT-1000 (Canon Kasei Co., Ltd.) is applied onto a quartz (Qz) substrate cut to a size of 10 cm square, adjusted in concentration, and dried to absorb light with a dry thickness of 4 μm. A layer was formed. Thereafter, SiO ₂ layers and Al ₂ O ₃ layers are alternately laminated on the light absorption layer by reactive sputtering as shown in Table 1 below, and silicon oxide (SiO ₂ ) having a thickness shown in Table 1 below. An optical adjustment layer, which is a laminate in which two layers and _two aluminum oxide (Al ₂ O ₃ ) layers are laminated, was formed.
As described above, a black-colored laminated structure was produced.
In this example, the film thickness was simulated by using thin film calculation software Essential Macleod (Thin Film Center), and formed with the optimized film thickness shown in Table 1. The same applies to the other embodiments described below.

The refractive indexes of the SiO ₂ layer and the Al ₂ O ₃ layer are shown in Table 1 below. The refractive indexes of the SiO ₂ layer and the Al ₂ O ₃ layer are values at a wavelength of 550 nm measured by a spectroscopic ellipsometry method.
The average refractive index and average extinction coefficient of the light absorption layer are shown in Table 2 below. In addition, the average refractive index and average extinction coefficient of the light absorbing layer are measured by measuring the refractive index or extinction coefficient at 300 points every 1 nm in the wavelength range of 400 nm to 700 nm by the spectroscopic ellipsometry method, and averaging the measured values. And asked.
Note that the extinction coefficient of the and the SiO ₂ layer and _{the Al} 2 _{O 3} layer as measured in the same manner is less than 0.01, had none of the SiO ₂ layer and _{the Al} 2 _{O 3} layer has transparency.

-Measurement and evaluation-
The following measurement and evaluation were performed on the produced laminated structure. The results of measurement and evaluation are shown in Table 10 below and FIGS.

(1) Average reflectance a. Measurement:
Using the reflection spectral film thickness meter (Otsuka Electronics Co., Ltd.), the average reflectance R1 in the wavelength range of 400 nm to 500 nm, the wavelength range of 500 nm to 600 nm, with respect to the surface of the Al ₂ O ₃ layer of the produced laminated structure The average reflectance R2 and the average reflectance R3 in the wavelength region of 600 nm to 700 nm were measured. Each average reflectance was obtained by dividing the total reflectance measured every 1 nm within each wavelength range by the number of measurement points.
The average reflectances R1, R2 and R3 are the relational expressions of the formula a (R1>R2> R3), the formula b1, the formula b2 and the formula b3 (all in the range of 4.0% to 6.0%), respectively. The case where the relational expression was satisfied was evaluated as “G”, and the case where the above relational expression was not satisfied was evaluated as “NG”. Table 10 shows the results of measurement and evaluation.

B. Black tone:
The spectrum of the average reflectance measured above from 400 nm to 700 nm is shown in FIGS. The obtained spectrum was observed, and the spectral shape was determined and the black tone was evaluated according to the following evaluation criteria.
<Evaluation criteria for spectrum judgment>
A: It has almost the same shape as the reflection spectrum of black lacquer coating.
B: It has a shape different from the reflection spectrum of black lacquer coating.
<Black-tone evaluation criteria>
A: The reflectance in the wavelength region of 400 nm to 500 nm was higher than the reflectance in the wavelength region exceeding 500 nm, and it was a bluish black tone.
B: The reflectance in the wavelength region of 400 nm to 500 nm was about the same as or less than the reflectance in the wavelength region exceeding 500 nm, and the color was black with no bluish color added.
In addition, the case of “black with no blueness added” includes, for example, a case where there is no color, or a blackish color with greenishness or redness added.

C. Angle dependence:
Of the average reflectance measured above, the dependence of the average reflectance at wavelengths of 450 nm, 550 nm, and 650 nm on the incident angle of incident light was evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: The average reflectance satisfies P ≦ Rs (θ) ≦ Q at all wavelengths.
B: The average reflectance does not satisfy P ≦ Rs (θ) ≦ Q at any wavelength.

(2) Depth Sense The 30 layers of evaluators evaluated the depth sensation by the following method under a 1000 lux fluorescent lamp.
For the evaluator, the sample of Comparative Example 1 described later having the same size and the metal film are subjected to nickel (Ni) plating (Ebina Denka Kogyo Co., Ltd.), and the entire visible range of 400 nm to 700 nm as shown in FIG. The three types of Ni moth-eye structure film having a reflectance of 1% or less and the laminated structure produced in Example 1 were observed, and among the three types, it had a high-class feeling and high texture. Were selected and evaluated according to the following evaluation criteria.
<Evaluation criteria>
A: Among the three types, there are 15 or more evaluators who selected the laminated structure of Example 1.
B: Among the three types, there are less than 15 evaluators who selected the laminated structure of Example 1.

(3) Surface roughness and interface roughness The surface roughness Ra of the surface of the Al ₂ O ₃ layer (exposed surface of the optical adjustment layer 1) of the prepared laminated structure was measured using an atomic force microscope (manufactured by Brugger). It was determined by measuring the surface information of a 5 μm square area. Table 1 shows the results of the surface roughness.
In addition, the roughness of the interface between the light absorption layer using the black ink of the laminated structure and the SiO ₂ layer (optical adjustment layer 4) was observed with a transmission electron microscope (JEOL Ltd.). Photos were taken and measured. At this time, the cross section of the laminated structure was cut out by an ion beam etching method, and the cut cross section was performed. Table 1 shows the results of the interface roughness.

(Example 2)
In Example 1, except that the optical adjustment layer was changed as shown in Table 1 below, a black laminate structure was prepared and measured and evaluated in the same manner as in Example 1. The results of measurement and evaluation are shown in Table 10 below and FIGS. The SiN layer and the SiO ₂ layer were formed by sputtering.
The produced laminated structure has a layer structure of SiN layer / SiO ₂ layer / SiN layer / SiO ₂ layer / black ink layer / base material.

(Examples 3 to 5)
In Example 1, except that the optical adjustment layer was changed as shown in Table 3 below, a black tone laminate structure having an optical adjustment layer composed of 5 layers or 6 layers was produced in the same manner as in Example 1. In addition, measurement and evaluation were performed. The results of measurement and evaluation are shown in Table 10 below and FIGS. The surface roughness was measured on the exposed surface of the optical adjustment layer 2 in Examples 3 to 4, and on the exposed surface of the optical adjustment layer 1 in Example 5. The interface roughness was measured on the interface between the optical absorption layer 6 and the light absorption layer using black ink of the laminated structure.
The MgF ₂ layer was formed by electron beam evaporation, and the SiN layer, SiO ₂ layer, TiO ₂ layer, and Ta ₂ O ₅ layer were all formed by sputtering.
For example, in Example 3, the produced laminated structure has a layer structure of MgF ₂ layer / SiN layer / SiO ₂ layer / SiN layer / MgF ₂ layer / black ink layer / base material. Similarly, Examples 4 to 5 have a laminated structure.

(Comparative Example 1)
In Example 1, except that the optical adjustment layer was not formed on the light absorption layer (see Table 4), a black-toned laminated structure was produced in the same manner as in Example 1, and measurement and Evaluation was performed. The results of measurement and evaluation are shown in Table 10 below and FIGS.

(Comparative Examples 2-6)
In Example 1, it has the optical adjustment layer which consists of 4 layers or 5 layers like Example 1 except having changed the optical adjustment layer and the light absorption layer as shown in the following Table 4-Table 6, respectively. A black laminate structure was prepared and measured and evaluated. The results of measurement and evaluation are shown in Table 10 below and FIGS.
Here, the SiN layer, the chromium (Cr) layer, and the SiO ₂ layer, which are optical adjustment layers, were all formed by reactive sputtering.
Moreover, formation of the silver (Ag) layer and Cr layer which are light absorption layers was all performed by reactive sputtering.
In the simulation using the thin film calculation software Essential Macleod (Thin Film Center), the optical constants (average refractive index and average extinction coefficient) of Cr and Ag are as shown in Tables 7 to 8 below. , Handbook of Optical Constants of Solids data was used.

As the black resist, a titanium black resist (Color Mosaic, FUJIFILM Corporation) was used.
In addition, as an optical constant of a black resist, an average refractive index and an average extinction coefficient were measured by a spectroscopic ellipsometry method with respect to a coating film having a thickness of 200 nm formed by coating on a Si wafer. Was incorporated into the thin film calculation software Essential Macleod. The measured values of the average refractive index and the average extinction coefficient are shown in Table 9 below.

In Examples 1-2, as represented by the reflection spectrum shown in FIGS. 2-3, a spectrum shape similar to the reflection spectrum of black lacquer coating was obtained. The laminated structures of Examples 1 and 2 have a bluish black tone, unlike the texture that is simply dark and glossy in black, and the reflected image is sharp but has an antiglare effect. The reflectance was suppressed to the extent possible, and a color tone with a sense of depth was obtained. That is, it can be seen that by adjusting the film thickness, a lacquer-like black color having both a black tone with a color and a feeling of depth is realized.
4 to 6 show the reflectance when the incident angle of light is 0 °, 15 °, 30 °, 45 °, and 60 °. As shown in FIGS. 4 to 6, the reflectance Rs for S-polarized light satisfies the above-described P ≦ Rs ≦ Q and has a good color tone that does not depend on the incident angle of incident light. Therefore, even when the laminated structure is observed from an oblique direction, it appears as lacquer-like black, and a property similar to black lacquer is obtained.

  Further, in Examples 1 to 5, the black ink material used as the light absorption layer is the above-described formula c (N1> N2> N3> 1.55) and formula d (K1> K2> K3> 0.01). A black lacquer-like black with a bluish color was realized, and a good lacquer-like black with a sense of depth was obtained. That is, in the example satisfying the expressions c and d, it is considered that the color adjustment by the optical adjustment layer can be easily performed.

On the other hand, in the laminated structures of Comparative Examples 1 to 6, the average reflectance does not satisfy the formula a, the formula b1, the formula b2, and the formula b3. Therefore, as shown in FIG. 2 to FIG. 3, the reflection spectrum has a shape different from that of the black lacquered reflection spectrum, and a high sense of depth could not be obtained.
In particular, Comparative Examples 2, 3 and 6 have a layer structure in which a dielectric layer and a metal layer are laminated on a light absorption layer, and a low refractive index dielectric layer like the laminated structure of the present disclosure. And a layer structure in which high-refractive-index dielectric layers are alternately stacked. For this reason, none of the average reflectances satisfies the formula a, the formula b1, the formula b2, and the formula b3.
Further, the black resist used in Comparative Examples 2 and 4, the Ag layer used in Comparative Example 3, and the Cr layer used in Comparative Example 5 are represented by the above-described formula c (N1>N2>N3> 1.55) and The formula d (K1>K2>K3> 0.01) was not satisfied, and the black tone and the sense of depth were inferior to the examples.

  The laminated structure of the present disclosure can be suitably applied to materials, decorations, paints, and the like used for interior and exterior in a wide range of fields such as automobiles, electronic products, and building materials.

Claims (13)

A base material, and a laminated film disposed on the base material,
The laminated film is
A light absorption layer having an average extinction coefficient of 0.01 or more in the entire wavelength region of 400 nm to 700 nm;
And including two or more dielectric layers disposed adjacent to the light absorbing layer on the opposite side of the substrate as viewed from the light absorbing layer and having different refractive indexes, and between the two or more dielectric layers A low refractive index dielectric layer having a relatively low refractive index and a high refractive index dielectric layer having a relatively high refractive index between the two or more dielectric layers are stacked in contact with each other. An optical adjustment layer including a laminated body,
And having
A black-toned laminated structure that satisfies the following formula a and formulas b1, b2, and b3.
R1>R2> R3 Formula a
4.0% <R1 <6.0% Formula b1
4.0% <R2 <6.0% Formula b2
4.0% <R3 <6.0% Formula b3
R1 represents an average reflectance with respect to incident light parallel to the stacking direction of the laminate in the wavelength range of 400 nm to 500 nm, and R2 is incident parallel to the stacking direction of the stack in the wavelength range of 500 nm to 600 nm. The average reflectance with respect to light is represented, and R3 represents the average reflectance with respect to incident light parallel to the stacking direction of the stacked body in a wavelength range of 600 nm to 700 nm.   The refractive index of the low refractive index dielectric layer is lower than the refractive index of the light absorbing layer, and the refractive index of the high refractive index dielectric layer is higher than the refractive index of the light absorbing layer. Laminated structure.   The laminated structure according to claim 1 or 2, wherein a refractive index of the low refractive index dielectric layer is 1.55 or less.   The laminated structure according to any one of claims 1 to 3, wherein a refractive index of the high refractive index dielectric layer is 1.70 or more.   5. The absolute value of the difference between the refractive index of the high-refractive index dielectric layer and the refractive index of the low-refractive index dielectric layer is 0.3 or more. 6. Laminated structure. The laminated structure according to any one of claims 1 to 5, wherein the reflectance Rs for S-polarized light satisfies the following formula.

In the formula, θ represents an incident angle of light incident in the stacking direction of the laminated film, satisfies 0 radians ≦ θ ≦ π / 3 radians, and Rs (θ) and f (θ) are represented by the following formulas. .

In the formula, θ represents an incident angle of light incident in the stacking direction of the stacked film, and satisfies 0 radian ≦ θ ≦ π / 3 radian. λ is the wavelength of incident light, and its unit is nm. A, B, C, D, and E are respectively A = 4.813 × 10 ⁻¹³ , B = −1.606 × 10 ⁻⁹ , C = 2.049 × 10 ⁻⁶ , and D = −1.212. × 10 ⁻³ , E = 1.847. The laminated structure according to any one of claims 1 to 6, wherein the light absorption layer satisfies the following formula c and formula d.
N1>N2>N3> 1.55 formula c
K1>K2>K3> 0.01 Formula d
N1 represents an average refractive index in a wavelength range of 400 nm to 500 nm, N2 represents an average refractive index in a wavelength range of 500 nm to 600 nm, and N3 represents an average refractive index in a wavelength range of 600 nm to 700 nm. K1 represents an average extinction coefficient in a wavelength range of 400 nm to 500 nm, K2 represents an average extinction coefficient in a wavelength range of 500 nm to 600 nm, and K3 represents an average extinction coefficient in a wavelength range of 600 nm to 700 nm. .   The thickness of the said light absorption layer is 2 micrometers or more, The laminated structure of any one of Claims 1-7. The optical adjustment _layer, SiO _{2, SiN,} and the laminated structure according to any one of claims 1 to 8 comprising at least one compound selected from _Al 2 _{O 3.}   The laminate in the optical adjustment layer includes at least two layers of the low refractive index dielectric layer and at least two layers of the high refractive index dielectric layer, and the low refractive index dielectric layer and the high refractive index. The laminated structure according to any one of claims 1 to 9, which is a laminate of four or more layers in which dielectric layers are alternately laminated.   The laminated structure according to any one of claims 1 to 10, wherein an arithmetic average value of surface roughness Ra on a side where the laminated film is disposed with respect to the base material is 30 nm or less.   The arithmetic average value of the interface roughness at the interface between the light absorbing layer and the laminate, and the arithmetic average of the interface roughness at the interface between the low refractive index dielectric layer and the high refractive index dielectric layer of the multilayer film. The laminated structure according to any one of claims 1 to 11, which has a value of 30 nm or less.   The molded object formed by shape | molding the laminated structure of any one of Claims 1-12 in two dimensions or three dimensions.