JPWO2016175064A1 - Laminate - Google Patents

Abstract

It is a laminate having a surface layer on at least one side of the support substrate, and further has an optical thickness (layer thickness multiplied by the refractive index of the layer) on the absolute reflectance R1 on the surface layer side of the laminate and the surface layer. A laminate in which the absolute reflectance R2 when the layer L having a value of 72.5 nm is satisfied satisfies the following conditions. (A) −1.0% ≦ R1 (435.8) −R2 (435.8) ≦ 0.5% (B) −1.0% ≦ R1 (546.1) −R2 (546.1) ≦ 0.5% (C) −1.0% ≦ R1 (700.0) −R2 (700.0) ≦ 0.5% R1 (X): Absolute reflectance R1 at a wavelength Xnm on the surface layer side of the laminate . R2 (X): Absolute reflectance R2 at a wavelength Xnm when a layer L having an optical thickness (a value obtained by multiplying the layer thickness by the refractive index of the layer) of 72.5 nm is further provided on the surface layer. Provided is a laminate suitable for an antireflection member and a hard coat member, which has low reflectance, high transparency, and little contamination due to dirt such as fingerprints.

Description

  The present invention relates to a laminate, and more particularly to a laminate suitable for an antireflection member.

  In general, the antireflection member prevents a decrease in contrast and reflection of an image due to reflection of external light in an image display device such as a cathode ray tube display (CRT), a plasma display panel (PDP), or a liquid crystal display (LCD). Therefore, it is placed on the outermost surface of the display so as to reduce the reflectivity using the principle of optical interference. In recent years, electronic devices that are operated with fingers have been increasing recently. For example, in various displays such as smartphones / touch panels, keyboards, and remote controls for home appliances, a high-reflection antireflection member ( Anti-reflection film) is used. In addition, an antireflection member may be used on the surface of a case member called piano black, which is black and glossy for the purpose of enhancing the black color.

  Examples of the configuration of a general antireflection member include the following.

  Patent Document 1 discloses a high refractive index layer made of a material having a high refractive index and a low refractive index layer made of a material having a low refractive index as an optical article having an excellent antireflection effect and excellent friction resistance. An antireflection member having a laminated structure is disclosed.

  In Patent Document 2, as a structure for reducing the reflectance in a wider wavelength region and reducing the coloring in the visible light region, a film having a plurality of layers composed of a high refractive index layer and a low refractive index layer is provided. A multilayer laminated structure is described which is produced on the surface of a supporting substrate.

  In such an antireflection member, adhesion of fingerprint stains is a problem. Specifically, when a person's finger touches the surface of an object, the fingerprint adheres and loses cleanliness, that is, the fingerprint is recognized and gives an unpleasant impression that it looks dirty. It has become. In addition, the visibility is deteriorated, that is, the display image, the display signal, or the reflected image becomes unclear due to a difference in reflectance between the portion where the fingerprint is attached and the portion where the fingerprint is not attached. .

  As a technique for adhesion of fingerprint stains to the antireflection member, for example, the following techniques can be cited.

  Patent Document 3 discloses a resin composition for a low refractive index layer that utilizes the effect of reducing the amount of fingerprint adhesion due to the water and oil repellency of a fluorine-containing ultraviolet curable resin.

  Patent Document 4 discloses an anti-fingerprint coating product for the purpose of making fingerprints inconspicuous by using an oleophilic surface, a concavo-convex shape and low refractive index hollow silica.

  On the other hand, in Patent Document 5, as a technique focused on a laminated structure composed of layers having different refractive indexes for the purpose of suppressing visibility, a high refractive index layer, a low refractive index layer, and a transparent layer are formed on a substrate made of a transparent plastic film. It has a configuration in which conductive thin film layers are laminated in this order, the refractive index of the high refractive index layer is in the range of 1.70 to 2.50, the film thickness is in the range of 4 to 20 nm, and the refractive index of the low refractive index layer is 1. An electrode pattern visual recognition suppression film (index matching film) of a transparent electrode sheet using a transparent conductive laminated film characterized by having a thickness of .30 to 1.60 and a thickness of 20 to 50 nm is disclosed.

JP 2006-035624 A Japanese Patent Application Laid-Open No. 7-5542 JP 2014-142444 A JP 2011-068000 A JP 2010-015861 A

  The techniques described in Patent Documents 1 and 2 are techniques that provide an excellent antireflection effect by a laminated structure designed by adjusting the refractive index and thickness of the surface layer. When the present inventors examined this technique, it confirmed that the attached fingerprint was very conspicuous. This is due to the fact that the sebum constituting the fingerprint forms a new film on the surface of the laminate, resulting in a deviation in the original optical design. As a result, the “reflectance” and the “color of reflected light” change depending on the presence or absence of the fingerprint, so that the shape of the fingerprint and the portion wiped with the fingerprint are visually recognized as being discolored, and the problem cannot be solved. The techniques described in Patent Documents 1 and 2 are techniques specialized in reducing the reflectance of a member, but have not led to the idea that the optical characteristics change due to adhesion of dirt. On the other hand, by simply minimizing the reflectance before adhesion of dirt, the difference in reflectance from the fingerprint adhesion portion is increased, and on the contrary, fingerprints are more easily visible. Cannot achieve a sufficient reduction in fingerprint visibility.

  The technique described in Patent Document 3 is a technique for reducing the amount of fingerprint adhesion by providing an oil-repellent layer on the surface. When the present inventors examined this technique, it was possible to reduce the amount of sebum that adhered, but it was not possible to completely eliminate the adhesion. In addition, since the repelled sebum forms spherical droplets on the surface, it was confirmed that even a small amount of adhesion would be noticeable. In addition, sufficient transparency was not obtained with the resin composition for a low refractive index layer disclosed in Patent Document 1. In the technique described in Patent Document 3, there is no idea about the estimation of the amount of dirt adhering to the oil-repellent surface and the change in the optical design due to the presence of a sebum layer of several tens of nm. In the range, sufficient reduction in fingerprint visibility cannot be achieved.

  The technique described in Patent Document 4 is a technique aiming to make fingerprints inconspicuous by utilizing lipophilicity of the surface and imparting uneven shapes. When the present inventors examined this technique, it was confirmed that when the adhesion amount of the fingerprint is small, an excellent effect in reducing the visibility of the fingerprint is exhibited. However, this technique tends to increase the amount of sebum adhering to the surface because the surface becomes easy to become familiar with sebum. And it confirmed that an effect was not fully exhibited with respect to such a large amount of dirt. That is, it is unsuitable for applications such as a touch panel and a housing that are frequently touched by fingers. Similarly, in the technique described in Patent Document 4, there is no idea about the estimation of the amount of dirt adhering to the surface of the lipophilic surface and the change in the optical design due to the presence of a sebum layer of several tens of nanometers. In the estimated technical range, it is not possible to achieve a sufficient reduction in fingerprint visibility.

  On the other hand, the technique described in Patent Document 5 includes a refractive index adjusting layer that makes it difficult to visually recognize a metal electrode having a high refractive index when a metal electrode having a high refractive index is deposited by an optical design of a laminated structure. When the present inventors examined this refractive index adjustment layer, the reflectance in the visible light region is high and cannot be used as an antireflection member, and the reflectance of the fingerprint adhering portion is lowered, resulting in a difference in reflectance. It was confirmed. Since such a refractive index adjustment layer is designed on the assumption that it is located inside the element, it is not designed for contamination such as fingerprint adhesion, and it is difficult to achieve both antireflection properties. In the technique described in Patent Document 5, the purpose of suppressing the visibility of the electrode of the transparent conductive sheet having a high reflectivity is contradictory to the purpose of providing a laminate having a low reflectivity targeted by the present invention. The laminate of the present invention cannot be obtained by a simple combination.

  SUMMARY OF THE INVENTION In view of the above, the problem to be solved by the present invention is to provide a laminate that has low reflectance, high transparency, and fingerprints are hardly noticeable, that is, excellent in reducing fingerprint visibility. Specifically, it is an anti-reflective member that has low reflectance and high transparency, and fingerprints are not noticeable, or has low reflectance and high transparency, and fingerprints are not noticeable, and preferably has excellent scratch resistance. Another object of the present invention is to provide a laminate suitable as a hard coat member.

  In order to solve the above-mentioned problems, the present inventors first examined a member that is not an antireflection member and a mechanism of fingerprint visibility when a fingerprint adheres to the antireflection member as follows.

  When a fingerprint is attached to a member that is not an antireflection member, a thin film of sebum is formed on the surface, so that the optical design changes before and after the attachment. The components constituting the fingerprint are mainly oily liquid components mainly composed of fatty acids represented by oleic acid, water containing salt, and solids such as dust, dust and keratin. As a result of confirmation by the present inventors, these fingerprint components have a refractive index that is slightly lower than the refractive index of a member such as glass or acrylic resin, although there are some variations depending on the individual and the environment. . Even if fingerprints adhere to the surface of these members, they are relatively difficult to visually recognize as long as the amount is small. However, when the amount of fingerprints attached increases, the oil droplets and solid matter scatter light, so that the fingerprints are easily noticeable. In such a case, the surface of the member is wiped (wiped off) with a dry cloth or the like, so that the fingerprint is hardly visible.

  On the other hand, in the case of an antireflection member, the thickness of each layer having a different refractive index is designed to be about one-fourth of the wavelength of light. However, the optical design is abnormal, leading to discoloration (that is, a change in the color of the reflected light due to a change in the wavelength at which the reflectance becomes minimum) and a loss of the antireflection effect itself. Further, even if the refractive index of the member surface is brought close to the value of the sebum dirt attached, it is impossible to avoid a design shift due to a change in thickness.

  There are also problems with wiping. As a result of studies by the inventors, the actual condition of wiping with a dry cloth material is to spread the sebum adhering to the surface to form a uniform thin film, which can reduce the amount of sebum adhering to a certain amount or less. It is confirmed that it cannot be done.

  The present inventors incorporated these problems into the optical design by incorporating a dirt film formed on the surface of the member, and an optical design in which the optical characteristics in the visible light region are not easily changed regardless of the presence or absence of the dirt layer. It was solved by designing a laminated structure having

  That is, the present invention is as follows.

  (1) A laminated body having a surface layer on at least one surface of a supporting substrate, and further having an optical thickness on the surface layer side of the laminated body and an optical thickness (the refractive index of the layer in the layer thickness) The multilayer body is characterized in that the absolute reflectance R2 when the layer L having a value of 72.5 nm is provided satisfies the following condition.

(A) −0.5% ≦ R1 (435.8) −R2 (435.8) ≦ 1.0%
(B) −0.5% ≦ R1 (546.1) −R2 (546.1) ≦ 1.0%
(C) −0.5% ≦ R1 (700.0) −R2 (700.0) ≦ 1.0%
R1 (X): Absolute reflectance R1 at a wavelength Xnm on the surface layer side of the laminate
R2 (X): Absolute reflectance R2 at a wavelength Xnm when a layer L having an optical thickness (a value obtained by multiplying the layer thickness by the refractive index of the layer) of 72.5 nm is further provided on the surface layer
(2) The laminate according to (1), wherein the absolute reflectance R1 satisfies the following condition.

(D) 1.0% ≦ R1ave ≦ 3.0%
(E) −0.2% ≦ R1slope ≦ 0.2%
R1ave: average value of absolute reflectivity R1 at wavelengths from 380 nm to 780 nm R1slope: change amount of absolute reflectivity R1 per wavelength of 100 nm when the absolute reflectivity R1 is linearly approximated from wavelengths 380 nm to 780 nm (3) The surface layer is refracted Two or more layers having different rates, and the optical thickness of the first layer from the outermost surface of the surface layer (a value obtained by multiplying the layer thickness by the refractive index of the layer) is 40 nm or more and 100 nm or less. The laminate according to (1) or (2).

(4) The number of peaks exceeding the mean square roughness observed by an atomic force microscope (AFM) on the outermost surface of the surface layer is 500 or more and 1500 or less per 25 μm ² (1) To (3).

  (5) The surface layer includes two or more layers having different refractive indexes, and the second layer from the outermost surface of the surface layer includes inorganic particles that satisfy the following conditions (F) and (G). The laminate according to any one of (1) to (4), wherein

(F) Number average particle diameter of 5 nm to 80 nm (G) Inorganic particles linked and / or branched in a bead shape (6) The surface layer includes two or more layers having different refractive indexes, The laminated body according to any one of (1) to (5), wherein the refractive index of the second layer from the outermost surface is 1.45 to 1.55.

  (7) The laminate according to any one of (1) to (6), wherein the surface layer includes three or more layers having different refractive indexes.

  (8) A layer having an optical thickness (a value obtained by multiplying the thickness of the layer by the refractive index of the layer) from the outermost surface of the surface layer to the supporting base material side from the second layer is 2 μm or more and 5 μm or less ( The laminated body as described in 7).

  ADVANTAGE OF THE INVENTION According to this invention, the laminated body with low reflectance, high transparency, and the stain | pollution | contamination of a fingerprint cannot be conspicuous can be provided. The laminate of the present invention is suitable as an antireflection member or a hard coat member, and particularly suitable as an antireflection film or a hard coat film formed on a resin substrate. By using the laminate of the present invention, it is possible to provide an antireflection film having particularly low reflectivity, high transparency, inconspicuous fingerprint stains, and preferably excellent scratch resistance.

It is a cross-sectional schematic diagram showing the uniform state of the laminated body of this invention. It is a cross-sectional schematic diagram in case the laminated body of this invention contains another layer. It is a schematic diagram of a multilayer slide die coat. It is a schematic diagram of a multilayer slot die coat. It is a schematic diagram of a wet-on-wet coat.

  Hereinafter, embodiments of the present invention will be specifically described.

  The laminate of the present invention is a laminate having a surface layer on at least one surface of a support substrate, and further has an optical thickness (on the layer thickness) on the absolute reflectance R1 on the surface layer side of the laminate and the surface layer. The value obtained by multiplying the refractive index of the layer) The absolute reflectance R2 when the layer L of 72.5 nm is provided satisfies the following condition.

(A) −0.5% ≦ R1 (435.8) −R2 (435.8) ≦ 1.0%
(B) −0.5% ≦ R1 (546.1) −R2 (546.1) ≦ 1.0%
(C) −0.5% ≦ R1 (700.0) −R2 (700.0) ≦ 1.0%
R1 (X): Absolute reflectance R1 at a wavelength Xnm on the surface layer side of the laminate
R2 (X): Absolute reflectance R2 at a wavelength of Xnm when a layer L having an optical thickness (a value obtained by multiplying the layer thickness by the refractive index of the layer) of 72.5 nm is further provided on the surface layer.

  Hereinafter, “layer L having an optical thickness (a value obtained by multiplying the thickness of the layer by the refractive index of the layer) 72.5 nm” may be simply referred to as “layer L having an optical thickness of 72.5 nm”.

<Definition and optical properties, surface properties, mechanical properties of laminates>
First, the definition, optical thickness, and optical properties, surface properties, and mechanical properties of the laminate of the present invention will be described.

[Laminate, surface layer]
In the present invention, a laminate represents a series of members in which one or more layers are formed on the surface of at least one side of a support substrate. The surface layer represents one or more layers formed on the surface of the support base material. The support base material will be described later. Here, the layer in the present invention refers to the thickness direction (in the case of a planar shape) or the internal direction (in the case of a three-dimensional shape) from the surface of the laminate, and the thickness direction or the inside. A region having a finite thickness can be distinguished from a region adjacent to the direction by having a boundary surface in which the elemental composition, the shape of inclusions (particles, etc.), and physical properties are discontinuous. More specifically, cross-sectional observation of the laminate in the thickness direction from the surface with various composition / element analyzers (IR, XPS, XRF, EDAX, SIMS, etc.), electron microscope (transmission type, scanning type) or optical microscope Are distinguished by the discontinuous boundary surface.

[Optical thickness]
In the present invention, the “layer L having an optical thickness of 72.5 nm” is a layer having an optical design value corresponding to a stain film layer formed by adhesion of a fingerprint.

  The optical thickness in the present invention is generally synonymous with a physical quantity expressed as an optical distance or an optical path length, and is specifically defined as a value obtained by multiplying the layer thickness by the refractive index of the layer. In calculating the optical interference, when considering the phase difference of light, it is necessary to calculate an optical path that is longer for a material having a higher refractive index and shorter for a material having a lower refractive index. The thickness of the layer taking into account such a difference in refractive index is the optical thickness, and equal optical thickness means that the layers are optically equivalent.

  In the present invention, when the layer L is provided for the measurement of the absolute reflectance R2, it is possible to estimate the effect of the laminated body even if the optical thickness is not precisely 72.5 nm. Specifically, when the optical thickness of the layer L is higher than 72.5 nm, it corresponds to the fact that the dirt film formed on the surface is thicker, and it is estimated that the same effect as the present invention can be obtained. The On the other hand, when the optical thickness of the layer L is lower than 72.5 nm, the effect may be insufficient because it corresponds to a thinner dirt film formed on the surface.

  In the present invention, there are innumerable combinations of the refractive index of the layer and the thickness of the layer for obtaining the “layer L having an optical thickness of 72.5 nm” provided for the measurement of the absolute reflectance R2. A structure having a refractive index of 1.45 and a thickness of 50 nm is preferable from the viewpoint of easy layer formation. A specific method for producing and evaluating the layer L having an optical thickness of 72.5 nm will be described later.

[Absolute reflectance R1, R2]
In a laminate composed of a plurality of layers having different refractive indexes, the absolute reflectance is determined by two physical phenomena of “reflection at a layer interface” and “interference of reflected light at each layer interface”. With respect to reflection at the interface between two layers having a difference in refractive index, the reflectance can be estimated from the “refractive index of each layer” by a relational expression called “Fresnel equation”. On the other hand, interference between reflected lights can be estimated by a so-called “thin film interference” calculation model based on an optical path difference and a phase difference calculated from “thickness of each layer” and “refractive index”. That is, the thickness and refractive index of the laminate can be designed by optical simulation with respect to the target value of “absolute reflectance”.

  Specifically, the laminate of the present invention satisfies the following conditions.

(A) −0.5% ≦ R1 (435.8) −R2 (435.8) ≦ 1.0%
(B) −0.5% ≦ R1 (546.1) −R2 (546.1) ≦ 1.0%
(C) −0.5% ≦ R1 (700.0) −R2 (700.0) ≦ 1.0%
R1 (X): Absolute reflectance R1 at a wavelength Xnm on the surface layer side of the laminate
R2 (X): Absolute reflectance R2 at a wavelength of Xnm when a layer L having an optical thickness of 72.5 nm is further provided on the surface layer.

  Here, the absolute reflectance is a value indicating the ratio of the reflected light intensity to the incident light intensity, and is described as Rn or Rn (X) in the present invention. In addition, n is a natural number of 1 or 2, and when n = 1, the absolute reflectance on the surface layer side of the laminate is formed, and when n = 2, a layer having an optical thickness of 72.5 nm is further formed on the surface layer. The absolute reflectance when L is provided is represented. Rn (X) represents an absolute reflectance when light having a wavelength of X nm is incident. A specific method for measuring the absolute reflectance will be described later.

  The wavelengths of 435.8 nm, 546.1 nm, and 700.0 nm in (A) to (C) correspond to the wavelengths of the three primary colors defined in the RGB color system of the CIE standard color system. Therefore, the above (A) to (C) mean that the difference between R1 and R2 is a specific range in any reflected light of blue, green, and red.

  In any of the above (A) to (C), when R1-R2 is larger than 1.0%, the absolute reflectance after adhesion of the fingerprint at the wavelength decreases, so that the fingerprint smears. It may be darkly emphasized and easily visible. On the other hand, if it is smaller than -0.5%, the absolute reflectance after the fingerprint attachment increases, and the fingerprint stains are brightly emphasized and may be easily recognized. Note that the value of R1-R2 has a wide range of positive values because the absolute reflectance after fingerprint attachment is less noticeable even if the same absolute reflectance difference occurs.

[Average reflectance Rave]
In the laminate of the present invention, it is preferable that the average reflectance R1ave of R1 satisfies the following conditions.

(D) 1.0% ≦ R1ave ≦ 3.0%
R1ave: Average value of absolute reflectance R1 at wavelengths from 380 nm to 780 nm Here, the average reflectance is a value that means an average value of absolute reflectance R in the visible light region at wavelengths of 380 nm to 780 nm. In the present invention, Rave Describe. Further, when distinguishing from which layer the reflection is, a natural number n similar to the absolute reflectance described above is given. The average reflectance measurement and calculation method will be described later.

  In (D), when the average reflectance R1ave is larger than 3.0%, sufficient antireflection properties may not be obtained. On the other hand, when the average reflectance R1ave is less than 1.0%, there is no problem in the antireflection property itself, but the above-mentioned conditions (A) to (C) are satisfied in the refractive index range of a material that can actually exist. It may be difficult to obtain a satisfying configuration, and fingerprint smearing may be noticeable.

[Reflectance slope Rslope]
In the laminate of the present invention, it is preferable that the reflectance gradient R1 slope satisfies the following conditions.

(E) −0.2% ≦ R1slope ≦ 0.2%
R1 slope: A change amount of the absolute reflectance R1 per 100 nm wavelength when the absolute reflectance R1 is linearly approximated from a wavelength of 380 nm to 780 nm. Here, the reflectance inclination is the absolute reflectance R in the visible light region of the wavelength of 380 nm to 780 nm. It is a numerical value that means the rate of change, and corresponds to the value of the slope in linear approximation. In the present invention, the reflectance gradient is described as Rslope, and when distinguishing from which layer the reflection is made, a natural number n similar to the absolute reflectance described above is given. A method for calculating the reflectance gradient will be described later.

  When the reflectance slope is less than -0.2% or greater than 0.2%, the absolute reflectance is within the range of the condition at one or more wavelengths (A) to (C). May become difficult and fingerprint stains may be noticeable.

[Transparency of laminate]
In order for the laminate of the present invention to exhibit good properties, it is preferable that the transparency is high. If the transparency is low, for example, when used as an image display device, image quality may be degraded due to a decrease in image saturation. For evaluation of transparency, haze and total light transmittance can be used.

  Haze is an index of turbidity of a transparent material defined in JIS K 7136 (2000). The smaller the haze, the higher the transparency. On the other hand, the fact that the haze is large suggests that the surface of the laminate or the interface is rough and a shape that easily scatters light is formed.

  The haze of the laminate of the present invention is preferably 1.5% or less, more preferably 1.0% or less, and further preferably 0.5% or less. The smaller the haze value, the better in terms of transparency, but it is difficult to achieve 0%, and the practical lower limit in the laminate of the present invention is about 0.01%. On the other hand, if the haze is greater than 1.5%, the absolute reflectance value is apparently decreased, but the amount of scattered light is increased, so that the visibility of the image may be decreased.

  The total light transmittance is an index of light transmittance of a transparent material defined in JIS K 7361-1 (1997). The higher the light transmittance, the higher the transparency.

  The total light transmittance of the laminate of the present invention is preferably 88% or more, more preferably 91% or more, and further preferably 93% or more. Transparency improves as the value of total light transmittance increases, but the practical upper limit in the laminate of the present invention is about 96%. If the total light transmittance is less than 88%, the image may become dark.

[Surface characteristics of laminate]
It has been found that the laminate of the present invention preferably has a layer having fine irregularities on the surface, and in particular, there is a preferred range in the number of irregularities in a specific range per unit area. The reason for this is not clear, but it is estimated that by introducing a fine concavo-convex structure, the oil droplets made by the attached fingerprint components are made finer, and the attached fingerprints are less visible by reducing light scattering and absorption. doing. Specifically, the number of peaks exceeding the mean square roughness observed by an atomic force microscope (AFM) is preferably 500 or more and 1500 or less per 25 μm ² , and is 800 or more and 1200 or less. It is more preferable. Outside this range, the effect of reducing the size of the oil droplets constituting the fingerprint may be insufficient.

  Here, the mean square roughness is a square root of a value obtained by averaging the squares of deviations from the average line to the measurement curve, and is obtained from the roughness curve, and the peak is from the average line to the measurement curve. Means a distance exceeding the mean square roughness. In general, arithmetic mean roughness by AFM based on JIS R1683 (2007 edition) is used as an index of surface shape, but arithmetic mean roughness is a numerical value representing average depth information over the entire surface. It is impossible to evaluate the shape and number of local concavo-convex structures as the laminate of the present invention has.

[Mechanical properties of laminate]
Since the laminate of the present invention is a member arranged on the outermost surface, it is preferably HB or more, more preferably H or more, and more preferably 2H or more in surface hardness measurement by a pencil hardness test method described later. More preferably. When the pencil hardness is less than HB, defects such as dents are likely to occur on the surface, and as a result, the visibility of the image and the quality of the laminate may be reduced.

  In addition, since the laminate of the present invention is a member disposed on the outermost surface, it is preferably 3 or more, more preferably 4 or more, and 5 points in the scratch resistance test described later. More preferably. When the scratch resistance test is less than 3 points, scratches are likely to occur on the surface, and as a result, the visibility of the image and the quality of the laminate may be lowered.

  Then, the structure of each layer of the laminated body of this invention is demonstrated.

  FIG. 1 shows a preferred embodiment of the laminate of the present invention.

  As for the laminated body (1) of this aspect, the surface layer (3) is laminated | stacked on the one side of the support base material (2). The surface layer (3) includes three layers having different refractive indexes. As described later, there are preferable optical design ranges for the first layer (4) from the outermost surface to the second layer (5) from the outermost surface of the surface layer (3). Moreover, it has the layer (6) designed by the specific optical thickness mentioned later from the outermost surface of a surface layer (3) to the support base material side from the 2nd layer. Furthermore, the layer (7) which improves the adhesiveness of a surface layer and a support base material is contained in the side nearest to a support base material of a surface layer (3).

  Moreover, there is no upper limit in particular in the number of layers of the laminated body of this invention, and the aspect containing 1 or more additional layers (8) may be sufficient as FIG. 2 shows.

  In the laminate of the present invention, the surface layer preferably includes three or more layers having different refractive indexes. When the number of layers having different refractive indexes is two or less, it becomes difficult to satisfy the above-mentioned condition (E), and as a result, fingerprint smears may become conspicuous. The upper limit of the number of layers having different refractive indexes is not particularly limited, but is preferably 10 layers or less, more preferably 5 layers or less from the viewpoint of productivity and cost.

  In the laminate of the present invention, the optical thickness of the first layer from the outermost surface is preferably 40 nm or more and 100 nm or less, and more preferably 60 nm or more and 75 nm or less. This layer is a layer located on the outermost surface of the laminated body and contributes to the absolute reflectance value. If the optical thickness of the first layer from the outermost surface exceeds 100 nm, it is difficult to set R1ave in the above condition (D) to 1.0% or more, or to satisfy the condition (E). As a result, fingerprint smudges may become noticeable. On the other hand, when the optical thickness of the first layer from the outermost surface is less than 40 nm, R1ave in the above condition (D) may exceed 3.0%, resulting in sufficient antireflection properties. You may not get.

  In the laminate of the present invention, the refractive index of the second layer from the outermost surface of the surface layer is preferably 1.45 or more and 1.55 or less. Here, the refractive index is the rate at which the angle of the traveling direction changes at the interface when light travels from the air to a certain substance, and is measured by the method specified in JIS K 7142 (1996). Can do. The second layer from the outermost surface is a layer located between a buffer layer described later and the first layer from the outermost surface, and functions as an intermediate layer for adjusting the upper and lower layers. When the refractive index of the second layer from the outermost surface is less than 1.45, it is difficult to set R1ave in the above condition (D) to 1.0% or more, or to satisfy the condition (E). As a result, fingerprint smudges may become noticeable. On the other hand, if the refractive index of the second layer from the outermost surface exceeds 1.55, R1ave in the above condition (D) may be 3.0% or more, and as a result, sufficient antireflection properties are obtained. It may not be possible.

  The laminate of the present invention preferably has a layer having an optical thickness of 2 μm or more and 5 μm or less from the outermost surface of the surface layer to the support substrate side from the second layer. This layer can reduce the optical influence of the layer on the support substrate side, simplify the optical design, and at the same time give the coating film hardness, scratch resistance, etc., optical and mechanical buffering Acts as a layer. When the optical thickness of the buffer layer is less than 2 μm, the optical design may be easily shifted, and as a result, fingerprint stains may be noticeable. On the other hand, if the optical thickness of the buffer layer exceeds 5 μm, it may be difficult to match the optical design only with the design on the surface side, and as a result, sufficient antireflection properties may not be obtained. is there.

[Supporting substrate]
The laminate of the present invention has a support substrate.

  As the support substrate, any of an inorganic material such as glass and a plastic film can be used, but a plastic film is more preferable from the viewpoint of processability when forming the surface layer.

  Examples of plastic film materials include cellulose esters (eg, triacetyl cellulose, diacetyl cellulose, propionyl cellulose, butyryl cellulose, acetyl propionyl cellulose, nitrocellulose), polyamides, polycarbonates, polyesters (eg, polyethylene terephthalate, polyethylene naphthalate). , Poly-1,4-cyclohexanedimethylene terephthalate, polyethylene-1,2-diphenoxyethane-4,4′-dicarboxylate, polybutylene terephthalate), polystyrene (eg, syndiotactic polystyrene), polyolefin (eg, Polypropylene, polyethylene, polymethylpentene), polysulfone, polyethersulfone, polyarylate, polyetherimide, polymethyl Such methacrylate and polyether ketone contains. Of these, triacetyl cellulose, polycarbonate, polyethylene terephthalate and polyethylene naphthalate are preferred.

  The total light transmittance of the supporting base material is preferably 80 to 100%, and more preferably 86 to 100%. The total light transmittance is a ratio of light transmitted through a sample when irradiated with light, and can be measured according to JIS K 7361-1 (1997) as described above.

  The haze of the supporting base material is preferably 0.01 to 2.0%, more preferably 0.01 to 1.0%. As described above, haze is an index of turbidity of a transparent material specified in JIS K 7136 (2000). The smaller the haze, the higher the transparency.

  The support substrate preferably has a refractive index of 1.40 to 1.70. The refractive index can be measured by the method defined in JIS K 7142 (1996) as described above.

  The support substrate may contain an infrared absorber or an ultraviolet absorber. In the case of containing an infrared absorber or an ultraviolet absorber, the content is preferably 0.01 to 20% by mass, and 0.05 to 10% by mass, out of 100% by mass of all the components of the support substrate. More preferably.

The support substrate may contain particles of an inert inorganic compound as a slip agent. The _SiO 2 _Examples of the inert inorganic _{compound, TiO 2, BaSO 4, CaCO} 3, talc and kaolin.

  Various surface treatments can be applied to the surface of the support substrate. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Among these, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment, corona discharge treatment and ultraviolet treatment are more preferred.

  The support substrate may have layers (these are referred to as functional layers) such as an easy-adhesion layer, a hard coat layer, an antiblocking layer, an antistatic layer, an ultraviolet absorption layer, and an oligomer block layer. In the laminate of the present invention, when these functional layers have a clear interface and refractive index difference between the upper and lower layers, they may be layers derived from a supporting substrate in the production process. , Not as part of the support substrate, but as a layer of the surface layer.

<Method for producing laminate>
Then, the preferable method of manufacturing the laminated body of this invention is demonstrated.

  In the present invention, as a method for forming the surface layer, for example, vapor phase treatment such as vapor deposition, sputtering, CVD, liquid phase treatment such as coating, impregnation, plating, saponification, solid phase treatment such as transfer, bonding, And the method of forming on the surface of a support base material by the combination of these processes is mentioned. Among these, the vapor phase treatment by vapor deposition and the liquid phase treatment by coating are preferable, and more preferable among the liquid phase treatment by coating is a preferable coating composition described later on at least one surface of the supporting substrate. Is formed by applying, drying and curing sequentially or simultaneously.

  Here, “sequentially apply” or “sequential application” means that a surface layer is formed by applying-drying-curing one type of coating composition and then applying-drying-curing a different type of coating composition. Is intended to form. The size of the refractive index of the surface layer formed in “sequential application” can be controlled by appropriately selecting the type and number of coating compositions to be used. The surface layer formed by “sequential application” usually has a “multilayer structure” having a plurality of interfaces.

  Further, “simultaneously coating” or “simultaneous coating” is intended to dry and cure after coating two or more types of liquid films on a supporting substrate in the coating process. The surface layer formed in “simultaneous application” may form an “inclined structure” that does not have a clear interface, but it is optically equivalent to “multilayer structure” by designing the optical thickness to be equal. It is possible to produce a structure.

In the method for forming the surface layer of the laminate of the present invention, when the coating composition is sequentially applied, a dip coating method, a roller coating method, a wire bar coating method, a gravure coating method or a die coating method (US Pat. No. 2,681,294). The surface layer is preferably formed by applying to a support substrate or the like according to the specification No.). When two or more kinds of coating compositions are applied simultaneously, a multilayer slide die (9 ), And in the liquid film state before coating, the “multilayer slide die coat” in which the laminated liquid film is applied, and the multilayer slot die (10) as shown in FIG. “Multilayer slot die coat”, which is laminated at the same time, uses a plurality of single-layer slot dies (11) as shown in FIG. 5, forms one liquid film on the support substrate, and then laminates another layer in an undried state. It is preferable to form the surface layer by applying to a supporting base material by “wet-on-wet coating” (FIG. 5).

  Next, the liquid film applied on the support substrate or the like is dried. In order to completely remove the solvent from the obtained laminate, it is preferable that the liquid film is heated in the drying step.

  Examples of the drying method include heat transfer drying (adherence to a high-temperature object), convection heat transfer (hot air), radiant heat transfer (infrared ray), and others (microwave, induction heating). Among these, in the present invention, convection heat transfer or radiant heat transfer is preferable because it is necessary to make the drying speed uniform even in the width direction.

  Furthermore, you may perform the further hardening operation (hardening process) by irradiating a heat | fever or an active energy ray.

  In the curing step, when the coating composition A and the coating composition B described later are used and cured with heat, the temperature is preferably room temperature or higher and 200 ° C. or lower, and 80 ° C. or higher from the viewpoint of the activation energy of the curing reaction. 200 degrees C or less is more preferable.

  When curing with active energy rays, it is preferable to use electron beams (EB rays) and / or ultraviolet rays (UV rays) from the viewpoint of versatility.

  In the case of curing with ultraviolet rays, the outermost surface can prevent oxygen inhibition, so that the oxygen concentration is preferably as low as possible, and it is more preferable to cure in a nitrogen atmosphere (nitrogen purge). When the oxygen concentration is high, the hardening of the outermost surface is inhibited, and the surface hardening may be insufficient.

Examples of the type of ultraviolet lamp used when irradiating with ultraviolet rays include a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method. Case of UV cured using a high pressure mercury lamp is a discharge lamp type, illuminance of ultraviolet rays 100~3,000mW / cm ^2, preferably 200~2,000mW / cm ^2, more preferably 300~1,500mW / cm ² It is preferable to carry out ultraviolet irradiation under the following conditions. Also, integrated light quantity 100~3,000mJ / cm ² of ultraviolet rays, preferably 200~2,000mJ / cm ^2, more preferably it is preferred to perform ultraviolet irradiation in the conditions the 300~1,500mJ / cm ^2. Here, the illuminance of ultraviolet rays is the irradiation intensity received per unit area, and changes depending on the lamp output, the emission spectral efficiency, the diameter of the light emitting bulb, the design of the reflector, and the light source distance to the irradiated object. However, the illuminance of ultraviolet rays does not change depending on the conveyance speed. Further, the UV integrated light amount is irradiation energy received per unit area, and is the total amount of photons reaching the surface. The integrated light quantity is inversely proportional to the conveyance speed passing under the light source, and is proportional to the number of times of irradiation and the number of lamps.

<Ingredients in paint composition>
The coating composition preferably used in the method for producing the laminate of the present invention will be described.

  The surface layer of the laminate of the present invention comprises at least one paint comprising at least one of a crosslinkable material, a low refractive index material, a high refractive index material, an antifouling material, and a scratch resistant material and an organic solvent. It is preferably produced by a combination of coating compositions. These coating compositions may further contain additives such as surfactants, thickeners and leveling agents as necessary.

[Crosslinkable material]
Although it does not specifically limit as a crosslinkable material, From a viewpoint of manufacturability, it is preferable that it is a crosslinkable material which can be hardened | cured with a heat | fever and / or active energy ray. Only one type of crosslinkable material may be used, or two or more types may be mixed and used. Moreover, it is preferable to have a reactive part in a molecule | numerator from a viewpoint of hold | maintaining particle | grains in a film | membrane. Suitable examples of the reactive site were selected from the group consisting of alkoxysilyl group, silanol group, carboxyl group, hydroxyl group, epoxy group, vinyl group, allyl group, acryloyl group, methacryloyl group, acryloxy group, and methacryloxy group. Groups. It is particularly preferable to use polyfunctional (meth) acrylate as the crosslinkable material.

[Low refractive index material]
The first layer from the outermost surface of the surface layer of the present invention preferably contains a material having a lower refractive index than the other layers. Examples of the material having a lower refractive index include inorganic particles and resin materials.

As the inorganic particles, metal oxides, nitrides, borides, fluorides, carbonates, sulfates of metalloid elements or metal elements selected from Si, Na, K, Ca, Mg and Al are preferable, and silica particles (SiO ₂ ), alkali metal fluorides (NaF, KF, NaAlF ₆ etc.), and alkaline earth metal fluorides (CaF ₂ , MgF ₂ etc.) are more preferred, from the viewpoint of durability, refractive index, cost, etc. Silica particles are more preferred.

  When a fluororesin is used as the resin material, it is preferably a fluororesin having a low refractive index trifluoromethyl group, difluoromethyl group and ether bond as a main skeleton. In addition, it is preferable to use a fluororesin from the viewpoint of antifouling properties described later.

[High refractive index material]
The second layer from the outermost surface of the surface layer of the present invention preferably includes a material having a higher refractive index than the first layer from the outermost surface. Examples of materials having a high refractive index include inorganic particles used as the low refractive index material, inorganic particles having a refractive index higher than that of the resin material, and resin materials.

When inorganic particles are used as the high refractive index material, it is particularly preferable that the inorganic particles have a refractive index higher than that of the silica particles of the low refractive index material. As inorganic particles having such a high refractive index, inorganic compounds having a refractive index of 1.55 to 2.80 are preferably used. Specific examples of the inorganic compound include antimony oxide, antimony-containing zinc oxide, antimony-containing tin oxide (ATO), phosphorus-containing tin oxide (PTO), gallium-containing zinc oxide (GZO), and aluminum oxide (Al ₂ O ₃ ). , Zirconium oxide (ZrO ₂ ), and / or titanium oxide (TiO ₂ ). Of these, titanium oxide and zirconium oxide having a particularly high refractive index are preferred. Further, when a resin material is used as the high refractive material, it is preferable to use a compound having a high refractive index and a structure such as cycloolefin, carbonate, fluorene.

  The number average particle diameter of the inorganic particles is preferably 5 nm or more and 80 nm or less. When the number average particle diameter of the inorganic particles is smaller than 5 nm, the ability to form irregularities may be insufficient, and when the number average particle diameter is larger than 80 nm, the glossiness may be lowered.

  Further, the form of the inorganic particles is not particularly limited, but the inorganic particles have a long chain structure in which the inorganic particles are connected in a bead shape (a shape in which a plurality of particles are connected in a chain), or the connected inorganic particles are A branched or bent one is preferred. These are hereinafter referred to as beaded and / or branched inorganic particles.

  The bead-like and / or branched inorganic particles are those in which primary particles are bonded to each other by interposing a metal ion having a valence of 2 or more, and at least 3 or more, preferably 5 or more, Preferably 7 or more connected. The connection, branching and bending state of the bead-like and / or branched inorganic particles can be confirmed using a scanning electron microscope (SEM).

  In order to obtain a particularly preferable surface shape of the present invention, the surface modification necessary for stably dispersing the above-mentioned bead-like and / or branched inorganic particles in a good solvent of the binder raw material is made. Particularly preferred. For example, when an acrylic monomer or oligomer is used as a binder raw material, the surface modification requires an alkyl group, an alkenyl group, a vinyl group, a (meth) acryl group or the like having 1 to 5 carbon atoms on the surface. It is preferably introduced. Examples of commercially available products that satisfy this requirement include organosilica sol manufactured by Nissan Chemical Industries, Ltd. and MEK-ST-UP (MEK dispersion).

[Anti-fouling materials]
It is preferable to use an antifouling material for the first layer from the outermost surface of the laminate of the present invention because contamination due to dirt such as fingerprints can be further reduced. Antifouling materials include oil-repellent types typified by fluorine resins and lipophilic types typified by silicone resins. In the present invention, the thickness of the dirt layer formed on the laminate surface is reduced. It is preferable to use an oil-repellent antifouling material having the effect of

  More preferable antifouling materials include antifouling materials having a structure in which a fluorine segment and a silicone segment are copolymerized. Since the surface formed of such an antifouling material can be easily made into a thin film by wiping off the attached fingerprint while maintaining the oil repellency of the fluorine material, the effect of the present invention is very easily obtained. Examples of commercially available antifouling materials having such a structure include a fluorine-based interfacial modifier from DIC Corporation, a trade name “Megafac” series, and the like.

[Scratch resistant material]
The layer having an optical thickness of 2 μm or more and 5 μm or less that the laminate of the present invention has on the support base side from the second layer from the outermost surface is preferably a layer containing a scratch-resistant material. Accordingly, the layer can have hardness and scratch resistance. The scratch-resistant material for forming such a layer is not particularly limited, and a commercially available hard coat material or a material having scratch repair properties can be suitably used.

  Examples of commercially available hard coat materials include “Taisei Fine Chemical Co., Ltd. (Organic-Inorganic Hybrid Coat Material“ STR-SiA ”)”, “Toa Gosei Co., Ltd. (trade name“ Photo-curing SQ Series ”), “Toyo Ink Co., Ltd .; (trade name“ Rioduras ”(registered trademark))” and the like can be used, and these materials can be preferably used.

  In addition, examples of commercially available scratch-repairing materials include “China Paint Co., Ltd. (trade name“ Folceed ”series”) and “Aika Industry Co., Ltd. (trade name“ Aika Aitoron ”series)”. Can be mentioned.

[Organic solvent]
The organic solvent is not particularly limited, but a solvent having a boiling point of 200 ° C. or less at normal pressure is preferable from the viewpoint of the smoothness of the surface layer during coating and drying. Specific examples include water, alcohols, ketones, ethers, esters, hydrocarbons, amides, fluorines and the like. These organic solvents can be used alone or in combination of two or more.

<Use of laminate>
Hereinafter, preferred applications of the laminate of the present invention will be described.

[Antireflection member]
The laminate of the present invention can be suitably used for an antireflection member. The antireflection member refers to a member in which a surface layer having an antireflection function is formed on at least one surface of various supporting base materials. When the base material is a plastic film, it is generally called an antireflection film. The antireflection member using the laminate of the present invention may be further provided with an easy-adhesion layer, a moisture-proof layer, an antistatic layer, a shield layer, an undercoat layer, a protective layer, and the like. The shield layer is provided to shield electromagnetic waves and infrared rays.

[Hard coat member]
The laminate of the present invention can be suitably used for a hard coat member. When the support substrate constituting the hard coat member is a plastic film, it is generally called a hard coat film. When the laminate of the present invention is used as a hard coat member, R1ave in the condition (D) for the average reflectance may be 3.0% or more, and if it is 6.0% or less, the hard coat member It can be used as When R1ave exceeds 6.0%, it is difficult to adopt a configuration that satisfies the conditions (A) to (C), and the attached fingerprint stains may become conspicuous.

  Next, although this invention is demonstrated based on an Example, this invention is not necessarily limited to these.

<Preparation of coating composition>
Hereinafter, the coating composition used for forming the first layer from the outermost surface of the surface layer is the coating composition A, and the coating composition used for forming the second layer is the coating composition. The coating compositions corresponding to the object B and the third and fourth layers are also referred to as coating compositions C and D, respectively.

[Coating composition A1]
The following materials were mixed to obtain a coating composition A1.
Non-particle type low refractive index coating agent X-12-2510A (Shin-Etsu Silicone Co., Ltd .: solid content 3% by mass)
97 parts by mass fluorinated additive RS-75 (DIC Corporation: solid content 40% by mass) 0.23 parts by mass isopropyl alcohol 2.77 parts by mass Photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.09 parts by mass [Coating composition A2]
The following materials were mixed to obtain a coating composition A2.
Particle-containing low refractive index coating agent X-12-2530N (Shin-Etsu Silicone Co., Ltd .: solid content 4% by mass)
72.75 parts by mass Fluorine-based additive RS-75 (DIC Corporation: solid content 40% by mass) 0.23 parts by mass Isopropyl alcohol 27.03 parts by mass [Coating composition A3]
The following materials were mixed to obtain a coating composition A3.
Non-particle type low refractive index coating agent X-12-2510A (Shin-Etsu Silicone Co., Ltd .: solid content 3% by mass)
100 parts by mass photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.09 parts by mass [Coating composition A4]
The following materials were mixed to obtain a coating composition A4.
Non-particle type low refractive index coating agent X-12-2510A (Shin-Etsu Silicone Co., Ltd .: solid content 3% by mass)
97 parts by mass Silicone-containing fluorine-based additive RS-56 (DIC Corporation: solid content 40% by mass)
0.23 parts by mass Isopropyl alcohol 2.77 parts by mass Photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.09 parts by mass [Coating composition A5]
The following materials were mixed to obtain a coating composition A5.
Non-particle type low refractive index coating agent X-12-2510A (Shin-Etsu Silicone Co., Ltd .: solid content 3% by mass)
97 parts by mass Silicone-containing acrylate EBECRYL 1360 (Daicel Ornex Co., Ltd .: solid content 100% by mass) 0.09 parts by mass isopropyl alcohol 2.91 parts by mass Photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.09 parts by mass [Coating composition A6]
The following materials were mixed to obtain a coating composition A6.
Particle-containing low refractive index coating agent X-12-2530N (Shin-Etsu Silicone Co., Ltd .: solid content 4% by mass)
72.75 parts by mass Silicone-containing fluorine-based additive RS-56 (DIC Corporation: solid content 40% by mass)
0.23 parts by mass Isopropyl alcohol 27.03 parts by mass

[Coating composition A7]
The following materials were mixed to obtain a coating composition A7.
Non-particle type low refractive index coating agent X-12-2510A (Shin-Etsu Silicone Co., Ltd .: solid content 3% by mass)
30.0 parts by mass binder raw material KAYARAD DPHA (Nippon Kayaku Co., Ltd .: solid content 100% by mass)
2.01 parts by mass fluorine-based additive RS-75 (DIC Corporation: solid content 40% by mass) 0.23 parts by mass isopropyl alcohol 67.77 parts by mass photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.09 parts by mass [Coating composition A8]
The following materials were mixed to obtain a coating composition A8.
Binder raw material KAYARAD DPHA (Nippon Kayaku Co., Ltd .: solid content 100% by mass)
5.82 parts by mass Fluorine-based additive RS-75 (DIC Corporation: solid content 40% by mass) 0.45 parts by mass ethyl acetate 93.73 parts by mass Photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.18 parts by mass [Coating composition A9]
The following materials were mixed to obtain a coating composition A9.
Hard coat coating material Z-877 (Aika Industry Co., Ltd .: solid content 40% by mass)
72.75 parts by mass Fluorine-based additive RS-75 (DIC Corporation: solid content 40% by mass) 2.25 parts by mass ethyl acetate 25.0 parts by mass [Coating composition B1]
The following materials were mixed to obtain a coating composition B1.
Binder raw material KAYARAD DPHA (Nippon Kayaku Co., Ltd .: solid content 100% by mass)
6.0 parts by mass ethyl acetate 94.0 parts by mass photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.18 parts by mass [Coating composition B2]
The following materials were mixed to obtain a coating composition B2.
Binder raw material KAYARAD PET-30 (Nippon Kayaku Co., Ltd .: solid content 100% by mass)
6.0 parts by mass ethyl acetate 94.0 parts by mass photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.18 parts by mass [Coating composition B3]
The following materials were mixed to obtain a coating composition B3.
High refractive index coating agent EA-HR034 (Osaka Gas Chemical Co., Ltd .: solid content 100% by mass)
3.6 parts by mass binder raw material KAYARAD DPHA (Nippon Kayaku Co., Ltd .: solid content 100% by mass)
2.4 parts by mass of ethyl acetate 94.0 parts by mass of photoinitiator Irgacure 184 (BASF Corporation: solid content of 100% by mass)
0.18 parts by mass [Coating composition B4]
The following materials were mixed to obtain a coating composition B4.
High refractive index coating agent 550C-22 (China Paint Co., Ltd .: solid content 30% by mass)
20.0 parts by mass Methyl isobutyl ketone 80.0 parts by mass [Coating composition B5]
The following materials were mixed to obtain a coating composition B5.
Non-particle type low refractive index coating agent X-12-2510A (Shin-Etsu Silicone Co., Ltd .: solid content 3% by mass)
80 parts by mass binder raw material KAYARAD PET-30 (Nippon Kayaku Co., Ltd .: solid content 100% by mass)
0.6 parts by mass Isopropyl alcohol 19.4 parts by mass Photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.09 parts by mass [Coating composition B6]
The following materials were mixed to obtain a coating composition B6.
Binder raw material KAYARAD DPHA (Nippon Kayaku Co., Ltd .: solid content 100% by mass)
4.2 Part by mass beaded organosilica sol MEK-ST-UP (Nissan Chemical Industries, Ltd .: solid content 20% by mass)
9.0 parts by mass Methyl isobutyl ketone 86.6 parts by mass Photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.18 parts by mass [Coating composition B7]
The following materials were mixed to obtain a coating composition B7.
Binder raw material KAYARAD DPHA (Nippon Kayaku Co., Ltd .: solid content 100% by mass)
4.2 parts by mass of organosilica sol MEK-ST (Nissan Chemical Industries, Ltd .: solid content of 30% by mass)
6.0 parts by mass Methyl isobutyl ketone 89.6 parts by mass Photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.18 parts by mass [Coating composition B8]
The following materials were mixed to obtain a coating composition B8.
Binder raw material KAYARAD DPHA (Nippon Kayaku Co., Ltd .: solid content 100% by mass)
5.6 parts by mass organosilica sol MEK-ST-ZL (Nissan Chemical Industries, Ltd .: solid content 30% by mass)
1.4 parts by mass Methyl isobutyl ketone 92.8 parts by mass Photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.18 parts by mass [Coating composition B9]
The following materials were mixed to obtain a coating composition B9.
Binder raw material KAYARAD DPHA (Nippon Kayaku Co., Ltd .: solid content 100% by mass)
3.6 parts by mass beaded organosilica sol MEK-ST-UP (Nissan Chemical Industries, Ltd .: solid content 20% by mass)
12.0 parts by mass Methyl isobutyl ketone 84.2 parts by mass Photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.18 parts by mass [Coating composition B10]
The following materials were mixed to obtain a coating composition B10.
Binder raw material KAYARAD DPHA (Nippon Kayaku Co., Ltd .: solid content 100% by mass)
2.4 parts by mass of beaded organosilica sol MEK-ST-UP (Nissan Chemical Industries, Ltd .: solid content 20% by mass)
18.0 parts by mass Methyl isobutyl ketone 79.4 parts by mass Photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.18 parts by mass [Coating composition B11]
The following materials were mixed to obtain a coating composition B11.
Binder raw material KAYARAD DPHA (Nippon Kayaku Co., Ltd .: solid content 100% by mass)
3.0 parts by mass beaded organosilica sol MEK-ST-UP (Nissan Chemical Industries, Ltd .: solid content 20% by mass)
15.0 parts by mass Methyl isobutyl ketone 81.8 parts by mass Photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.18 parts by mass [Coating composition C1]
The following materials were mixed to obtain a coating composition C1.
Hard coat coating material Z-877 (Aika Industry Co., Ltd .: solid content 40% by mass)
75.0 parts by mass Ethyl acetate 25.0 parts by mass [Coating composition C2]
The following materials were used as the coating composition C2.
Wound repairing coating material Z-913-3 (Aika Industry Co., Ltd .: solid content 40% by mass)
100.0 parts by mass [Coating composition C3]
The following materials were mixed to obtain a coating composition C3.
Hard coat coating material Z-878 (Aika Industry Co., Ltd .: solid content 40% by mass)
75.0 parts by mass Ethyl acetate 25.0 parts by mass [Coating composition C4]
The following materials were mixed to obtain a coating composition C4.
High refractive index coating agent EA-HR034 (Osaka Gas Chemical Co., Ltd .: solid content 100% by mass)
5.4 parts by mass binder raw material KAYARAD DPHA (Nippon Kayaku Co., Ltd .: solid content 100% by mass)
0.6 parts by mass Photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.18 parts by mass of ethyl acetate 94.0 parts by mass [Coating composition C5]
The following materials were mixed to obtain a coating composition C5.
Hard coat coating material Z-729-37 (Aika Industry Co., Ltd .: solid content 50 mass%)
80.0 parts by mass Methyl isobutyl ketone 20.0 parts by mass [Coating composition D1]
The following materials were mixed to obtain a coating composition D1.
Hard coat coating material Z-877 (Aika Industry Co., Ltd .: solid content 40% by mass)
75.0 parts by mass Ethyl acetate 25.0 parts by mass [Number average particle diameter (primary particles)]
Observation and measurement were performed with a scanning electron microscope (SEM). The observation sample was prepared by diluting the coating composition in a dispersion medium (isopropyl alcohol) to a solid content concentration of 0.5% by mass, dispersing with ultrasonic waves, and dropping and drying on a conductive tape. The number average particle diameter is observed at a magnification such that the number of aggregates of primary particles per field of view is 10 or more and 50 or less, and the diameter of the circumscribed circle of the primary particles is obtained from the obtained image. Based on the number-based arithmetic average length described in JIS Z8819-2 (2001 edition), the number average particle size was determined from the value measured for 100 primary particles by increasing the number of observations as the equivalent particle size.

<Method for creating laminate>
Hereinafter, a method for producing a laminate will be described. “Lumirror” (registered trademark) U48 (manufactured by Toray Industries, Inc.) coated with an easy-adhesion paint on a PET resin film and “Lumirror” (registered trademark) without an easy-adhesion paint applied as a support substrate T60 (made by Toray Industries, Inc.) was used. Table 1 shows the composition of each laminate and the combination of the supporting substrate and the coating composition used. Under the conditions and compositions described in Table 1, laminates of examples and comparative examples were prepared. That is, after applying the coating composition described above on the supporting substrate while adjusting the coating amount so as to have the thickness shown in Table 1 with a slot die coater, the first stage drying shown below is performed, Two stages of drying were performed.
First stage Hot air temperature 50 ℃
Hot air wind speed 1.5m / s
Wind direction Parallel to the coating surface Drying time 0.5 minutes Second stage Hot air temperature 100 ° C
Hot air wind speed 5m / s
Wind direction Vertical to coating surface Drying time 1 minute Note that the wind speed of the hot air is a value converted from the measured dynamic pressure of the blowing part to the wind speed.

About each coating composition except the coating compositions A2 and A9 which do not require UV curing after drying, an illuminance of 600 W / cm ² using a 160 W / cm ² high-pressure mercury lamp lamp (manufactured by Eye Graphics Co., Ltd.). The film was cured by irradiation with ultraviolet light having an integrated light amount of 800 mJ / cm ² under an oxygen concentration of 0.1% by volume.

<Formation of layer L>
The laminate produced by the above-mentioned method is cut out to 5 × 10 cm, the following coating composition L is applied to the surface layer side with a bar coater, and then cured by the same drying / curing method as the production method of the laminate. A resin layer L having a refractive index of 1.45 and a thickness of 50 nm was prepared.

[Coating composition L]
The following materials were mixed to obtain a coating composition L.
Binder raw material HPA (Osaka Organic Chemical Industry: solid content 100% by mass) 2.0 parts by mass ethyl acetate 98.0 parts by mass Photoinitiator Irgacure 184 (BASF Corporation: solid content 100% by mass)
0.06 parts by mass.

<Evaluation of laminate>
The performance evaluation shown next was implemented about the produced laminated body, and the obtained result was described in Table 2 to Table 4. Unless otherwise specified, the measurement was performed three times by changing the location of one sample in each example and comparative example, and the average value was used.

[Measurement of absolute reflectance]
The absolute reflectance was evaluated using a spectrophotometer UV-3100 manufactured by Shimadzu Corporation. Measurement is performed in the direction in which light is incident from the surface layer side of the laminate or the layer L side formed on the laminate by the above-described method, and black vinyl is applied on the non-measurement surface to prevent back reflection. The tape was stuck with a rubber roller. Next, for absolute reflectances of 435.8 nm, 546.1 nm, and 700.0 nm, 1.0 points before and after the wavelength to be measured are designated at a total of 11 points every 0.2 nm, and the absolute reflectance for each wavelength is measured, and the average value thereof Are Rn (438.5), Rn (546.1), and Rn (700.0), respectively, where n is a natural number, and when n = 1, the absolute reflectance on the surface layer side of the laminate is n = 2 represents the absolute reflectance when the layer L prepared by the above-described method is provided). On the other hand, for the absolute reflectance used for calculation of the average reflectance and the reflectance gradient described later, the wavelength range from 380 nm to 780 nm was measured at intervals of 0.5 nm.

[Calculation of average reflectance and slope of reflectance]
For the absolute reflectance data in the wavelength range of 380 nm to 780 nm and the measurement interval of 0.5 nm measured by the above method, the average value was calculated, and this was used as the average reflectance Rave.

  On the other hand, with respect to the reflectance slope, the absolute reflectance data at each wavelength described above is taken into Microsoft Excel 2010, a linear approximation formula is calculated by the least square method, and the amount of change in absolute reflectance around 100 nm is calculated based on the slope. The reflectance gradient Rslope was calculated.

[Layer thickness of surface layer]
By observing the cross section using a transmission electron microscope (TEM), the cross-sectional shape and layer thickness of the 1st layer and 2nd layer on a support base material were measured. The thickness of each layer was measured according to the following method. The thickness of each layer was read by software (image processing software ImageJ / Developer: National Institutes of Health (NIH)) from an image obtained by photographing an ultrathin section of a cross section of the surface layer with a TEM at a magnification of 200,000 times. . The average value obtained by measuring the layer thickness of 30 points in total was taken as the film thickness.

[Refractive index of surface layer]
The number of surface layers of the laminate and the thickness of each layer were measured using the transmission electron microscope (TEM) described above. Based on these information, the refractive index of each layer is the absolute reflection in the range of 300-800 nm with respect to the surface layer of the laminate by a reflection spectral film thickness meter (trade name [FE-3000] manufactured by Otsuka Electronics). The refractive index at 550 nm is obtained according to the method described in [Film thickness measuring device general catalog P6 (nonlinear least squares method)] manufactured by Otsuka Electronics Co., Ltd. using the software [FE-Analysis] attached to the device. It was.

The optical constants (C ₁ , C ₂ , C ₃ ) are calculated by the least square method (curve fitting method) using Cauchy's dispersion formula (Formula 1) as an approximate expression of the wavelength dispersion of the refractive index, and the refractive index at 550 nm is calculated. It was measured.

[Measurement of root mean square roughness and number of peaks]
After cutting the laminate at an arbitrary place, using an atomic force microscope (AFM) (Digital Instruments, NanoScope IIIa ver. 5.31R1), observation mode = DFM mode, scanner = FS-20A, cantilever = Surface morphology was observed with DF-3, observation field of view = 5 × 5 μm ² , resolution of 1024 × 512 pixels, and an observation image was obtained. Next, in order to set 100% of the mean square roughness as a peak threshold, analysis was performed by setting “Peak Thrsh (% rms)” to 100%, and the number of peaks was obtained.

[transparency]
The transparency of the laminate was determined by measuring the total light transmittance and haze. The measurement of total light transmittance and haze is based on JIS K7136 (2000) and JIS K7361-1 (1997), using the Nippon Denshoku Industries Co., Ltd. haze meter, and the opposite side to the support base material of a laminated body sample. The measurement was carried out by placing it on the apparatus so as to transmit light from the (surface layer side). In addition, it measured in three different places of the same sample, and employ | adopted the average value.

[Surface hardness measurement by pencil hardness test method]
After leaving the laminated film at a temperature of 20 ° C. for 12 hours, the surface hardness of the surface layer was measured in accordance with scratch hardness (pencil method) described in JIS K 5600-5-4 (1999) in the same environment.

[Abrasion resistance]
It addressed the steel wool to be 200 g / cm ² load on the surface layer side of the laminate (# 0000) vertically, the length of 1cm describes the approximate number of scratches are visible upon 10 reciprocates classification below 3 or more points were accepted.
5 points: 0 4 points: 1 or more, less than 5
3 points: 5 or more, less than 10
2 points: 10 or more and less than 20
1 point: 20 or more.

[Fingerprint resistance (low fingerprint visibility)]
For low fingerprint visibility, place the laminate on the black paper with the surface layer side up, rub your finger (index finger) and thumb 3 times to press the fingerprint, and slowly put your finger (index finger) on the surface layer surface. The visibility of the attached fingerprint was evaluated according to the following evaluation criteria, and 5 or more points were accepted.
10 points: The fingerprint is not visually recognized or the difference from the non-attached part is not recognized. 7 points: The fingerprint is hardly visible or not recognized as the fingerprint. 5 points: The fingerprint is slightly visible, but hardly noticed. Points: Fingerprints are visually recognized. 1 point: Fingerprints are clearly visually recognized and very worrisome. The above evaluation was performed on 10 subjects, and the average value was obtained. The numbers after the decimal point were rounded off.

[Fingerprint resistance (low visibility after wiping off fingerprints)]
After attaching the fingerprint by the above-mentioned method, next, wipe using a cellulose long fiber nonwoven fabric gauze ("Hize" gauze NT-4 manufactured by Kawamoto Sangyo Co., Ltd.) having a folded dimension of 12.5 × 12.5 cm. went. The low visibility after fingerprint wiping evaluated the visibility after wiping by this wiping method according to the following evaluation criteria, and gave 5 or more points as pass.
10 points: almost unrecognizable when wiped 3 times 7 points: almost unrecognizable after 3 times of wipe 5 points: Dirt remains after wiping 3 or 4 times, but almost visible when wiped 5 times 3 points: When wiping 10 times, it becomes almost unnoticeable 1 point: Even after wiping 10 times or more, the above-mentioned evaluation remains on 10 subjects, and the average value was obtained. The numbers after the decimal point were rounded off.

[Fingerprint resistance (low fingerprint visibility under forced conditions)]
Fingerprint low visibility under forced conditions is placed on black paper with the surface of the laminate facing up, rubbing the finger (forefinger) pressing the fingerprint and the thumb three times, and then placing the finger on the surface of the surface layer. The index of the fingerprint attached when the (index finger) was pushed slowly and the length of 2 cm was reciprocated 10 times was evaluated according to the following evaluation criteria, and 5 or more points were accepted.
10 points: The fingerprint is not visually recognized or the difference from the non-attached part is not recognized. 7 points: The fingerprint is hardly visible or not recognized as the fingerprint. 5 points: The fingerprint is slightly visible, but hardly noticed. Points: Fingerprints are visually recognized. 1 point: Fingerprints are clearly visually recognized and very worrisome. The above evaluation was performed on 10 subjects, and the average value was obtained. The numbers after the decimal point were rounded off.

  The laminate of the present invention includes, for example, a plastic optical component, a touch panel, a film type liquid crystal element, a plastic container; a protective coating material for preventing contamination of floor materials, wall materials, artificial marble and the like as building interior materials; film type liquid crystal It can be used for an antireflection film such as an element, a touch panel, and a plastic optical component. Specifically, LCD screens for smartphones, TVs, car navigation systems, personal computers, signal indicators for guidance, warning, and evacuation guidance, glasses, sunglasses, telescopes, camera lenses, and transparent covers for watch dials Can be suitably used.

DESCRIPTION OF SYMBOLS 1 Laminated body 2 Support base material 3 Surface layer 4 From the outermost surface of a surface layer to the 1st layer 5 From the outermost surface of a surface layer to the 2nd layer 6 From the outermost surface of a surface layer to the 2nd layer Layer 7 having optical thickness of 2 μm or more and 5 μm or less on the supporting substrate side Layer 8 for improving adhesion between surface layer and supporting substrate 8 Additional layer 9 Multilayer slide die 10 Multilayer slot die 11 Single layer slot die

Claims (8)

It is a laminate having a surface layer on at least one side of the support substrate, and further has an optical thickness (layer thickness multiplied by the refractive index of the layer) on the absolute reflectance R1 on the surface layer side of the laminate and the surface layer. A laminate in which the absolute reflectance R2 when the layer L having a value of 72.5 nm is satisfied satisfies the following conditions.
(A) −0.5% ≦ R1 (435.8) −R2 (435.8) ≦ 1.0%
(B) −0.5% ≦ R1 (546.1) −R2 (546.1) ≦ 1.0%
(C) −0.5% ≦ R1 (700.0) −R2 (700.0) ≦ 1.0%
R1 (X): Absolute reflectance R1 at a wavelength Xnm on the surface layer side of the laminate
R2 (X): Absolute reflectance R2 at a wavelength Xnm when a layer L having an optical thickness (a value obtained by multiplying the layer thickness by the refractive index of the layer) of 72.5 nm is further provided on the surface layer The laminate according to claim 1, wherein the absolute reflectance R1 satisfies the following condition.
(D) 1.0% ≦ R1ave ≦ 3.0%
(E) −0.2% ≦ R1slope ≦ 0.2%
R1ave: average value of absolute reflectance R1 from 380 nm to 780 nm R1 slope: change amount of absolute reflectance R1 per wavelength of 100 nm when absolute reflectance R1 is linearly approximated from 380 nm to 780 nm   The surface layer includes two or more layers having different refractive indexes, and the optical thickness of the first layer from the outermost surface of the surface layer (a value obtained by multiplying the layer thickness by the refractive index of the layer) is 40 nm or more. The laminated body of Claim 1 or 2 which is 100 nm or less. The number of peaks exceeding the root mean square roughness observed by an atomic force microscope (AFM) on the outermost surface of the surface layer is 500 or more and 1500 or less per 25 μm ^2. Laminated body. The surface layer includes two or more layers having different refractive indexes, and the second layer from the outermost surface of the surface layer includes inorganic particles that satisfy the following conditions (F) and (G). To 4. The laminate according to any one of 4 to 4.
(F) Number average particle diameter of 5 nm to 80 nm (G) Inorganic particles linked and / or branched in a bead shape   The surface layer includes two or more layers having different refractive indexes, and the refractive index of the second layer from the outermost surface of the surface layer is 1.45 or more and 1.55 or less. The laminated body in any one.   The laminate according to any one of claims 1 to 6, wherein the surface layer includes three or more layers having different refractive indexes. The optical thickness (a value obtained by multiplying the thickness of the layer by the refractive index of the layer) from the outermost surface of the surface layer to the support base material side from the second layer is a layer having a thickness of 2 μm or more and 5 μm or less. The laminated body of description.