WO2016098658A1 - Layered body - Google Patents

Abstract

Provided is a layered body in which flexibility and high surface hardness are both obtained at the same time. A layered body in which a surface layer is layered on a supporting substrate, the layered body characterized in that a maximum value at which the elastic modulus of the surface layer is higher than the elastic modulus of the supporting substrate and a minimum value at which the elastic modulus of the surface layer is lower than the elastic modulus of the supporting substrate are present in the elastic modulus distribution in the thickness direction of the surface layer, and the elastic modulus on the interface side of the surface layer with the supporting substrate and the elastic modulus of the outermost surface side of the surface layer are both higher than the elastic modulus of the supporting substrate.

Description

Laminated body

The present invention relates to a laminate having both high surface hardness and flexibility.

Conventionally, a plastic film provided with a surface layer made of a synthetic resin or the like has been used for the purpose of protecting the surface of optical materials such as color filters and flat panel displays (for preventing scratches and imparting antifouling properties). These surface layers are required to have scratch resistance as an important characteristic from the viewpoint of surface protection. Therefore, in general, a coating composition containing various prepolymers and oligomers such as organosilanes and polyfunctional acrylics described in Non-Patent Document 1 is coated, dried, heated, or cured by UV or UV curing. "Density material" is used to provide scratch resistance. Further, scratch resistance is imparted by using a so-called “hard coat material” in which the surface hardness of the coating film is increased using an “organic-inorganic hybrid material” combined with various surface-modified fillers.

On the other hand, in recent years, taking advantage of the light and flexible characteristics of plastic films, not only the display surface of PCs and smartphones, but also the “curved surface protection” of the housing surface and the so-called “flexible device” The use for the housing which is rich in property is progressing. In such applications, in addition to the “surface hardness” such as the scratch resistance and dent durability of the surface layer, it is possible to achieve both “flexibility”, that is, cracking and peeling hardly occur even during bending. It is requested.

In the hard coat material, as a laminate focusing on the compatibility between scratch resistance and flexibility, Patent Document 1 and Patent Document 2 indicate that “adhesion between hard coat / base material, film bending crack, curl and the like are practically acceptable. A “hard coat film that can fall within the range and has a pencil hardness value of 4H or higher” is disclosed. Specifically, “a cured resin coating layer formed by providing a cured resin layer containing inorganic or organic internal crosslinked ultrafine particles, and further providing a clear cured resin thin film not containing inorganic or organic internal crosslinked ultrafine particles. , And "a cured resin coating layer consisting of a two-layer structure in which a cured resin coating layer comprising a blend of a radical polymerization resin and a cationic polymerization resin and a cured resin coating layer comprising only a radical polymerization resin are formed in this order" Has been.

On the other hand, Patent Document 3 discloses “a hard coat film that improves surface hardness and prevents damage to the hard coat film due to stress concentration, and is hard to be damaged”. Specifically, “the hard coat layer is formed in two or more layers, and the elastic modulus σm of the hard coat layer formed closest to the transparent substrate is higher than the elastic modulus σs of the hard coat layer of the surface layer. Has been proposed.

Patent Document 4 discloses “a laminate with a hard coat layer that can be easily produced, has excellent film adhesion, and has high film strength and scratch resistance”. Specifically, “a structure in which two layers having different inorganic particle concentrations are alternately stacked, a layer group having a high inorganic particle concentration is an A layer unit, and a layer group having a low inorganic particle concentration is a B layer unit. A layered product with a hard coat layer in which the sum ΣAh of the dry film thickness of the A layer unit and the sum ΣBh of the dry film thickness of the B layer unit satisfy the relationship ΣAh ≧ ΣBh ”is proposed ing.

Japanese Patent Laid-Open No. 2000-052472 JP 2000-071392 A JP 2000-214791 A International Publication No. 2009/130975 Pamphlet

However, since the plastic film using the “hard coat material” for the surface layer has a very high surface hardness, that is, an elastic modulus, a large amount of stress is generated due to slight deformation at the time of bending, and cracks are easily generated. . On the other hand, the configurations of Patent Document 1 and Patent Document 2 suppress “curling” due to shrinkage of the hard coat layer. The configuration of Patent Document 1, that is, “a hard coat film obtained by laminating a coat layer having an elastic modulus in the range of 1.0 GPa to 6.0 GPa on a coat layer having an elastic modulus in the range of 0.5 GPa to 4.5 GPa”. And the configuration of Patent Document 2, that is, “a hard coat formed by laminating a coat layer having an elastic modulus in the range of 2.0 GPa to 4.5 GPa on a coat layer having an elastic modulus in the range of 1.5 GPa to 4.5 GPa. As a result of an investigation by the present inventors on “film”, sufficient “flexibility” has not been obtained.

On the other hand, the configuration proposed in Patent Document 3 is “the elastic modulus σm of the hard coat layer formed closest to the base material is higher than the elastic modulus σs of the hard coat layer of the surface layer”. However, when the present inventors confirmed these configurations, it was found that a higher elastic modulus of the outermost layer is advantageous for the surface hardness.

Further, the configuration of Patent Document 4, that is, “a group of inorganic particles having a high inorganic particle concentration of 30.0% by volume to 70.0% by volume and an inorganic particle concentration of 0% by volume to 40.0% by volume In the following “hard coat layer in which layer groups with low inorganic particle concentration are alternately laminated”, although the surface hardness is improved, the resin material is selected from highly crosslinkable actinic ray curable resin, so it can be used in the first place. The design is not flexible.

Therefore, an object of the present invention is to provide a laminate having both high surface hardness and sufficient flexibility to withstand use on a curved surface.

In order to solve the above-mentioned problems, the present inventors have intensively studied and as a result, completed the following invention. That is, the present invention is as follows.
(1) A laminate in which a surface layer is laminated on a supporting base material, and in the elastic modulus distribution in the thickness direction of the surface layer, a maximum value and an elastic modulus are higher than the elastic modulus of the supporting base material. There is a minimum value lower than the elastic modulus of the supporting substrate, and both the elastic modulus on the interface side with the supporting substrate in the surface layer and the elastic modulus on the outermost surface side are both higher than the elastic modulus of the supporting substrate. A featured laminate.
(2) The laminate according to (1), wherein the maximum elastic modulus in the elastic modulus distribution in the thickness direction of the surface layer is 100 to 10,000 times the minimum elastic modulus.
(3) The laminate according to (1) or (2), wherein the minimum elastic modulus in the elastic modulus distribution in the thickness direction of the surface layer is 0.1 GPa or less.
(4) In the elastic modulus distribution in the thickness direction of the surface layer, there are alternately a maximum value where the elastic modulus is higher than the elastic modulus of the supporting base material and a minimum value where the elastic modulus is lower than the elastic modulus of the supporting base material, The laminated body according to any one of (1) to (3), wherein the thickness and the elastic modulus calculated from the elastic modulus distribution satisfy the following relationship:
10 ≦ (Tb [nm] / Ta [nm]) × (Ea [MPa]) / Eb [MPa]) ≦ 1,000 (Formula 1)
Ta [nm]: Average thickness of the portion where the elastic modulus is higher than the elastic modulus of the supporting substrate Tb [nm]: Average thickness of the portion where the elastic modulus is lower than the elastic modulus of the supporting substrate Ea [MPa] : Average value of maximum elastic modulus Eb [MPa]: Average value of minimum elastic modulus (5) The surface layer includes inorganic particles having anisotropic shapes satisfying the following: (1) to (4) The laminated body in any one of.
1.2 ≦ Rl / Rs ≦ 20,000 (Formula 2)
1 nm ≦ Rs ≦ 100 nm (Formula 3)
Rl [nm]: Long diameter of the inorganic particles Rs [nm]: Short diameter of the inorganic particles (6) Presence of the inorganic particles having the anisotropic shape in the thickness direction in a cross section perpendicular to the support substrate of the surface layer The laminated body according to any one of (1) to (5), wherein the frequency F satisfies the following condition.
Fa <Fb (Formula 4)
Fa: Presence frequency of a portion where the elastic modulus is higher than the elastic modulus of the supporting base material Fb: Presence frequency of a portion where the elastic modulus is lower than the elastic modulus of the supporting base material

According to the present invention, a laminate having both high surface hardness and flexibility can be provided. The laminate of the present invention has excellent surface hardness compared to a homogeneous resin layer of equivalent thickness, and at the same time, it suppresses the occurrence of curling due to stress concentration, cracking during peeling and peeling of the coating film. it can.

It is a conceptual diagram of the cross-sectional schematic diagram of the laminated body of this invention, and the elastic modulus distribution of the thickness direction in a cross section. It is a conceptual diagram of the elastic modulus distribution in the thickness direction, the maximum elastic modulus, and the minimum elastic modulus. It is a conceptual diagram of the elastic modulus distribution in the thickness direction, the maximum elastic modulus, the minimum elastic modulus, and the average value thereof. It is a conceptual diagram of the part whose elastic modulus distribution and elastic modulus of a thickness direction are higher than the elastic modulus of a support base material, and a part whose elastic modulus is lower than the elastic modulus of a support base material. It is an example (multilayer slide die coat) of the manufacturing method which forms a surface layer. It is an example (multilayer slot die coat) of the manufacturing method which forms a surface layer. It is an example of a manufacturing method (wet-on-wet coat) for forming a surface layer.

In achieving the above-mentioned problem, the technical difficulty lies in both the hardness, that is, the high elastic modulus and the flexibility, that is, the low elastic modulus. In any of the inventions of Patent Documents 1 to 4, the balance between hardness and flexibility is adjusted by the elastic modulus of the material, the resin type, or the amount of particles. However, these methods cannot achieve the above-mentioned problems. The cause is that the elastic modulus of the material used for imparting flexibility is too high.

Therefore, the present inventors first examined in detail the “occurrence of scratches by the pencil hardness test” in terms of hardness. As a result, it was confirmed that the forms of scratches generated in the pencil hardness test were classified into the following three types. That is, (1) scratches caused by the outermost surface of the film, (2) scratches caused by the interface in which the elastic modulus changes discontinuously in the film, and (3) scratches caused by the supporting substrate. That is, (1) is a scratch caused by insufficient hardness of the surface layer, (2) is a scratch caused by an interlayer such as interface peeling, and (3) is a dent caused by bending of the substrate. From this, the properties required for the surface layer to suppress the occurrence of scratches by the pencil hardness test are (I) the outermost surface layer has a high elastic modulus, and (II) the surface layer and the supporting substrate There is no stress strain at the interface of (III), and (III) the stress propagating to the substrate is reduced.

And when the present inventors conducted an examination based on the above design guidelines, a surface layer that satisfies the conditions described later is a material whose elastic modulus is lower than the elastic modulus of the supporting base material while maintaining the surface hardness. It was found that it can be incorporated. That is, the present inventors have a surface layer that has excellent surface hardness as described above, and suppresses the occurrence of curling due to stress concentration, cracks during bending, and peeling of the coating film as the surface layer of the laminate. The laminated body which has is found. This will be described below with reference to the drawings.

First, the laminate of the present invention is a laminate 3 in which a surface layer 2 is laminated on one surface of a support base 1 as shown in FIG. The surface layer 2 has a nonuniform elastic modulus distribution in the thickness direction. The elastic modulus of the surface layer may be a laminate in which a plurality of layers having different elastic moduli are laminated as long as the conditions described later are satisfied, and the elastic modulus is different in the thickness direction within the same layer. Such a layer may be used.

Further, the “elastic modulus of the cross section of the laminate” in the present invention is measured by an atomic force microscope. Elastic modulus measurement with an atomic force microscope is a compression test with a probe of a very small portion, and measures the degree of deformation due to pressing force. Therefore, using a cantilever with a known spring constant, the elastic modulus in the cross section at each position in the thickness direction of the surface layer is measured. Specifically, the laminate is cut, and the elastic modulus in the cross section at each position in the thickness direction of the surface layer is measured with an atomic force microscope. Details will be described in the Examples section, but the cantilever obtained by using the atomic force microscope shown below, contacting the tip of the cantilever tip to the cross section of the surface layer, and measuring the force curve with a pressing force of 55 nN Can be measured. At this time, the spatial resolution in the thickness direction depends on the scanning range of the atomic force microscope and the number of scanning lines, but under realistic measurement conditions, the lower limit is approximately 50 nm. Details and a measuring method will be described later.

Atomic force microscope: MFP-3DSA-J manufactured by Asylum Technology
Cantilever: A cantilever “R150-NCL-10 made by NANOSENSORS (material Si, spring constant 48 N / m, radius of curvature of the tip 150 nm).
Hereinafter, the preferable form of the elasticity modulus of a surface layer is demonstrated.

[The elastic modulus of the supporting substrate and the elastic modulus of the surface layer]
First, as shown in FIG. 2, in the “elastic modulus distribution in the thickness direction of the surface layer” plotted with the thickness of the surface layer on the horizontal axis and the elastic modulus of the cross section measured by the above method on the vertical axis, It is preferable that a portion having a higher elastic modulus and a portion having a lower elastic modulus than the elastic modulus 9 of the material cross section exist. When there is no portion having a high elastic modulus as described above, the surface layer has insufficient elastic modulus, so that sufficient hardness may not be obtained. On the other hand, when there is no portion having a low elastic modulus, there is a case where flexibility, in particular, suppression of cracking against bending becomes insufficient, and the problem cannot be achieved. The “elastic modulus distribution in the thickness direction of the surface layer” is expressed as a continuous curve in FIG. 2, but is actually a set of data points measured at intervals of 100 nm. The change in elastic modulus at intervals less than 100 nm has little effect on the hardness or flexibility of the laminate, so the effect of elastic modulus change that is not detected under the above measurement conditions is practically ignored. can do. The details of the method of measuring the “elastic modulus distribution in the thickness direction of the surface layer” will be described later.

[Elastic modulus of outermost surface and elastic modulus of interface with supporting substrate]
In the present invention, it is preferable that both the elastic modulus on the outermost surface side and the elastic modulus on the interface side are higher than the elastic modulus of the supporting substrate. Here, the “outermost surface” refers to the outermost surface of the surface layer. The “interface” refers to the interface between the surface layer and the supporting substrate (that is, the boundary line between the surface layer and the supporting substrate). When the elastic modulus on the outermost surface side is lower than the elastic modulus of the supporting base material, even if there is a portion with a higher elastic modulus inside, it may be easily damaged. Further, when the elastic modulus on the interface side is lower than the elastic modulus of the supporting base material, scratches caused by the supporting base material may easily occur. In particular, the elastic modulus on the outermost surface side is preferably the highest in the surface layer. Here, the “elastic modulus on the outermost surface side” is the elastic modulus of the outermost surface in the surface layer. However, in measuring the modulus of elasticity in the cross section, the modulus of elasticity on line 4 in FIG. 1 located on the true outermost surface is not an accurate value of the surface layer. Is the “elastic modulus on the outermost surface side”. The “elastic modulus on the interface side” refers to the elastic modulus at the interface between the surface layer and the support substrate. However, in the measurement of the elastic modulus in the cross section, the elastic modulus on the line 6 in FIG. 1 located at the true interface does not become an accurate value of the interface, so in reality, the boundary line 6 between the surface layer and the supporting substrate The measured value 7 on the 100 nm surface layer side is defined as “interface side elastic modulus”.

[Maximum modulus and minimum modulus]
On the other hand, in the elastic modulus distribution in the thickness direction of the surface layer (FIG. 2), the “maximum elastic modulus 14” that is the maximum elastic modulus in the surface layer and the “minimum elastic modulus 15” that is the minimum elastic modulus in the surface layer. There is a favorable relationship between “ Specifically, the maximum elastic modulus is preferably 100 times or more and 10,000 times or less than the minimum elastic modulus. When the relationship between the maximum elastic modulus and the minimum elastic modulus is not within the above-mentioned range, specifically, when it is smaller than 100 times, either physical property of hardness or flexibility is insufficient, and it becomes difficult to achieve both. There is a case. On the other hand, when it exceeds 10,000 times, a sudden change in elastic modulus tends to cause distortion in the surface layer, which may lead to a decrease in pencil hardness and peeling of the film.

Furthermore, there is a preferable numerical range for the minimum elastic modulus 15. Specifically, it is preferably 0.1 GPa or less, more preferably 0.05 GPa or less, and particularly preferably 0.01 GPa or less. When the minimum elastic modulus is higher than 0.1 GPa, the aforementioned flexibility is likely to be insufficient, and cracks and curls are likely to occur.

Here, the “maximum elastic modulus” refers to the maximum value of the elastic modulus in the elastic modulus distribution in the thickness direction of the surface layer measured by the method described later. The “minimum elastic modulus” refers to the minimum value of the elastic modulus in the elastic modulus distribution in the thickness direction of the surface layer measured by the method described later.

[Relationship between maximum and minimum elastic modulus and thickness]
Further, there is a preferable relationship between the elastic modulus and the thickness as a structure that makes it difficult to generate deformation strain due to stress in the surface layer. Specifically, in the elastic modulus distribution in the thickness direction of the surface layer, as shown in FIG. 3, the maximum value (maximum elastic modulus 16) and the elastic modulus are higher than the elastic modulus 9 of the supporting substrate. It is preferable that a minimum value (minimum elastic modulus 18) lower than the elastic modulus 9 of the material exists. Moreover, in the elastic modulus distribution in the thickness direction of the surface layer, it is preferable that both the elastic modulus on the interface side of the surface layer with the supporting substrate and the elastic modulus on the outermost surface side are higher than the elastic modulus of the supporting substrate. Furthermore, in the elastic modulus distribution in the thickness direction of the surface layer, as shown in FIG. 4, a maximum value (maximum elastic modulus 16) in which the elastic modulus is higher than the elastic modulus 9 of the supporting substrate, and the elastic modulus is the supporting substrate. The minimum value (minimum elastic modulus 18) lower than the elastic modulus 9 is “alternately” and the average value of the thickness 20 of the portion where the elastic modulus is higher than the elastic modulus 9 of the supporting base material and the elastic modulus is supported. It is more preferable that the average value of the thickness 21 of the portion lower than the elastic modulus 9 of the base material satisfies the following relational expression.
10 ≦ (Tb [nm] / Ta [nm]) × (Ea [MPa]) / Eb [MPa]) ≦ 1,000
Here, Ta [nm] is the average value of the thickness of the portion where the elastic modulus is higher than the elastic modulus of the supporting substrate, and Tb [nm] is the average value of the thickness of the portion where the elastic modulus is lower than the elastic modulus of the supporting substrate. Ea [MPa] is the average value 17 of the maximum elastic modulus, and Eb [MPa] is the average value 19 of the minimum elastic modulus.

Here, the maximum value (maximum elastic modulus 16) in which the elastic modulus is higher than the elastic modulus of the supporting base material means that the elastic modulus is higher than the elastic modulus of the supporting base material and, as shown in FIG. When the relationship between the thickness and the elastic modulus is graphed, it means a maximum value (a value at which the slope becomes zero). Moreover, the minimum value (minimum elastic modulus 18) in which the elastic modulus is lower than the elastic modulus of the supporting base material is that the elastic modulus is lower than the elastic modulus of the supporting base material and, as shown in FIG. When the relationship with the elastic modulus is graphed, it means a minimum value (a value at which the slope becomes zero).

Further, in the elastic modulus distribution in the thickness direction of the surface layer, there are alternately a maximum value whose elastic modulus is higher than that of the supporting substrate and a minimum value whose elastic modulus is lower than that of the supporting substrate. Satisfying the following requirements (1) to (4) when the elastic modulus distribution in the thickness direction of the surface layer is measured by the method described in the example section.
(1) There are at least two local maximums and local minimums.
(2) There is no minimum value that is an elastic modulus higher than the elastic modulus of the supporting substrate.
(3) There is no maximum value that is an elastic modulus lower than the elastic modulus of the supporting substrate.
(4) When the maximum value and the minimum value are arranged in order in the thickness direction, there is a permutation in which (i) maximum value-minimum value-maximum value-minimum value or (ii) minimum value-maximum value-minimum value-maximum value There is at least one.

Furthermore, “the average value of the thickness of the portion where the elastic modulus is higher than the elastic modulus of the supporting base material” is the average of the thickness of each portion where the elastic modulus existing in the surface layer is higher than the elastic modulus of the supporting base material. Value. Furthermore, “the average value of the thickness of the portion where the elastic modulus is lower than the elastic modulus of the supporting substrate” means the average thickness of each portion where the elastic modulus existing in the surface layer is lower than the elastic modulus of the supporting substrate. Value.

Moreover, the average value of the maximum elastic modulus is the average value of the maximum values having an elastic modulus higher than the elastic modulus of the supporting substrate existing in the surface layer, and the average value of the minimum elastic modulus is the value in the surface layer. The structure of the surface layer that realizes the above-mentioned elastic modulus, which is the average value of the minimum values having an elastic modulus lower than the elastic modulus of the existing supporting substrate, is a layer having a high elastic modulus, that is, a hard layer and an elastic modulus. A low layer, that is, a “multi-layer structure” in which soft layers are alternately stacked, or an integral layer without a clear interface, but having a distribution in elastic modulus due to bias of constituent components such as particles and resins For example, “inclined structure”. Details of the structure of the surface layer and the manufacturing method thereof will be described later in the section of [Manufacturing Method of Laminate].

The above-mentioned relational expression is a parameter representing the “flexibility” of the laminate defined based on the ratio between the elastic modulus and thickness of the components constituting the surface layer. The increase in this parameter means that Tb, that is, “the thickness of the portion where the elastic modulus is lower than the elastic modulus of the supporting substrate” is relatively large, or that Eb, that is, “minimum elastic modulus” is relatively small. All correspond to the softening of the laminate. Conversely, a decrease in this parameter corresponds to an increase in the hardness of the laminate.

Specifically, when the above relational expression is smaller than 10, the flexibility of the entire surface layer is likely to be insufficient, and cracks and curls are likely to occur. On the other hand, if it is larger than 1,000, the hardness of the entire surface layer tends to be insufficient, and peeling at the interface and a decrease in pencil hardness may be caused.

When the above relational expression is decomposed into a component A having a high elastic modulus and a component B having a low elastic modulus, it is decomposed into “Ea / Ta” and “Eb / Tb”, that is, “(elastic modulus) / (film thickness)”. Can do. On the other hand, when considering the resultant force acting on the spring, the “spring length” is a value that is inversely proportional to the “spring constant”, and generally the value of the spring constant decreases as the length increases. Here, when considering indentation in the thickness direction, the “coating thickness” is a value corresponding to the “spring length”, and the thicker the thickness, the lower the spring constant needs to be estimated. Therefore, the above-mentioned relational expression can be considered as a preferable numerical range of “spring constant corrected by coating film thickness”.
Hereinafter, embodiments of the present invention will be described in detail.

[Laminated body and surface layer]
The “surface layer” in the present invention refers to a layer formed on a support substrate, and a combination of all the series of layers including the surface layer and the support substrate is referred to as a “laminate”. That is, when only one layer is formed on the support base material, the one layer becomes a “surface layer”. For example, when two or more layers are formed on a supporting base material, all the two or more layers excluding the supporting base material are referred to as one “surface layer”.

Here, the “layer” refers to a portion having a finite thickness that can be distinguished from the surface side of the laminate in the thickness direction by having a boundary surface and a portion adjacent to the thickness direction. More specifically, when the cross section of the said laminated body is cross-sectional-observed with an electron microscope (a transmission type, a scanning type) or an optical microscope, it points out what is distinguished by the presence or absence of a discontinuous interface. The laminate of the present invention may be in a planar state or a three-dimensional shape after being molded as long as it has a surface layer exhibiting the above-mentioned physical properties. The thickness of the entire surface layer is not particularly limited, but is preferably 1 μm or more and 50 μm or less, and more preferably 3 μm or more and 20 μm or less.

In addition to the scratch resistance, particularly the repeated scratch resistance and moldability, the laminate is a subject of the present invention, as well as antifouling properties, antireflection properties, antistatic properties, antifouling properties, electrical conductivity, heat ray reflectivity, You may have a layer which has other functions, such as near-infrared absorptivity, electromagnetic wave shielding, and easy adhesion, and these functions may be provided to the said surface layer.

[Supporting substrate]
The material constituting the support substrate used in the laminate of the present invention may be either a thermoplastic resin or a thermosetting resin, may be a homo resin, may be a copolymer or a blend of two or more types. Good. More preferably, the resin constituting the support substrate is preferably a thermoplastic resin from the viewpoint of moldability.

Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polystyrene and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyester resins, polycarbonate resins and polyarylate resins. Fluorine resins such as polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluoroethylene resin, tetrafluoroethylene-6-fluoropropylene copolymer, vinylidene fluoride resin, acrylic Resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, polylactic acid resins, and the like can be used. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. The thermoplastic resin is more preferably a polyester resin, a polycarbonate resin, or a methacrylic resin from the viewpoint of strength, heat resistance, and transparency, and a polyester resin is particularly preferable.

The polyester resin in the present invention is a general term for polymers having an ester bond as a main bond chain, and is obtained by polycondensation of an acid component and its ester with a diol component. Specific examples include polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, and the like. These may be copolymerized with other dicarboxylic acids and their esters or diol components as acid components or diol components. Among these, polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferable in terms of transparency, dimensional stability, heat resistance and the like.

In addition, for the support substrate, various additives such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducers, thermal stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, A dopant for adjusting the refractive index may be added. The support substrate may be either a single layer configuration or a laminated configuration.

The surface of the support substrate can be subjected to various surface treatments before forming the surface layer. 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 and ultraviolet treatment are more preferred.

In addition to the surface layer of the present invention, a functional layer such as an easy-adhesion layer, an antistatic layer, an undercoat layer, and an ultraviolet absorption layer can be provided in advance on the surface of the support substrate. It is preferable to provide a layer.

In addition, the elasticity modulus of the support base material in this invention means the elasticity modulus of the support base material measured by the method mentioned later. Here, even if it is a support base material which does not have elastic modulus distribution, even if it is a support base material which has elastic modulus distribution in the thickness direction, the elastic modulus measured by the method mentioned later is called elastic modulus of a support base material.

[Coating composition]
The laminate of the present invention forms a surface layer having a structure capable of achieving the above-mentioned physical properties by applying, drying and curing a coating composition on a supporting substrate using a laminate production method described later. can do. Here, the “coating composition” is a liquid composed of a solvent and a solute, and is a material that can be applied to the above-mentioned supporting substrate and volatilized, removed, and cured in a drying process to form a surface layer. Point to. Here, the “type” of the coating composition refers to liquids that are different in part even in the type of solute constituting the coating composition. This solute is a resin or a material that can form them in the coating process (hereinafter referred to as a precursor), particles, and polymerization initiators, curing agents, catalysts, leveling agents, ultraviolet absorbers, antioxidants, etc. Consists of various additives.

The surface layer of the present invention comprises a coating composition A capable of forming the aforementioned “part having a higher elastic modulus than the elastic modulus of the cross section of the supporting substrate” and a coating composition capable of forming a “part having a lower elastic modulus”. It is preferable to form by using at least two types of coating compositions of B and sequentially or simultaneously coating on a supporting substrate.

[Coating composition A]
As the coating composition A, a hard coat coating material that forms a coating layer having a high elastic modulus can be suitably used. The elastic modulus of the coating layer single layer film preferably has an elastic modulus of 6 GPa to 200 GPa. As specific components, it is preferable to have a highly crosslinkable binder component containing many reactive sites and a particle component for imparting elastic modulus. As a coating material capable of forming a hard coat layer having a particularly high elastic modulus, it is preferable to use a composite coating material of an organic material and an inorganic material called an organic-inorganic hybrid coating material. Examples of organic-inorganic hybrid coating materials include “Taisei Fine Chemical Co., Ltd .; (organic-inorganic hybrid coating material“ STR-SiA ”)” and “Toagosei Co., Ltd .; (trade name“ photo-curing type SQ series ”)” And “Toyo Ink Co., Ltd .; (trade name“ Rioduras ”(registered trademark))” and the like, and these materials can be preferably used. A typical form of the organic-inorganic hybrid coating material preferably includes a highly crosslinkable binder composed of inorganic particles having a high elastic modulus and an organic compound. Preferred particle components and binder components will be described later.

[Coating composition B]
As the coating composition B, a resin coating material rich in flexibility and moldability can be suitably used. The elastic modulus of the coating layer single film preferably has an elastic modulus of 1 MPa to 100 MPa. Specifically, those commercially available as scratch-repairing coating materials, moldable HC (Hard Coating) coating materials, or adhesives can be suitably used. Part of it may contain a particulate material.

Examples of scratch-repairable coating materials and moldable HC coating materials are “China Paint Co., Ltd. (trade name“ Forseed ”series”) and “Aika Industry Co., Ltd. (trade name“ Aika Itron ”series)”. Etc. Examples of pressure-sensitive adhesives include acrylic adhesives such as “Toagosei Co., Ltd .;“ Aron Tuck ”series”, “Soken Chemicals Co., Ltd .;“ SK Dyne ”(registered trademark) series”, and silicone adhesives as “ Adhesives of “Toray Dow Corning Co., Ltd.” and “Shin-Etsu Silicone Co., Ltd.” can be mentioned. A preferable paint component will be described later.

[Particulate material, particle component]
The surface layer of the laminate of the present invention preferably contains a particle component. In particular, the coating composition A suitable for forming the surface layer of the present invention preferably contains particles. Here, the particles may be either inorganic particles or organic particles, but inorganic particles are preferred from the viewpoint of durability.

The number of types of inorganic particles is preferably 1 or more and 20 or less. The number of types of inorganic particles is more preferably 1 or more and 10 or less, and particularly preferably 1 or more and 4 or less. Here, “inorganic particles” include those subjected to surface treatment. This surface treatment means introducing a compound onto the particle surface by chemical bonds (including covalent bonds, hydrogen bonds, ionic bonds, van der Waals bonds, hydrophobic bonds, etc.) and adsorption (including physical adsorption and chemical adsorption). Point to.

Here, the kind of inorganic particles is determined by the kind of elements constituting the inorganic particles, and when some surface treatment is performed, the kind is determined by the kind of elements constituting the particles before the surface treatment. For example, since titanium oxide (TiO ₂ ) and nitrogen-doped titanium oxide (TiO _2−x N _x ) in which part of oxygen of titanium oxide is substituted with nitrogen as an anion, the elements constituting the inorganic particles are different, Different types of inorganic particles. Further, if particles (ZnO) consisting only of the same element, for example, Zn and O, even if there are a plurality of particles having different number average particle diameters, and the composition ratio of Zn and O is different, These are the same type of particles. Even if there are a plurality of Zn particles having different oxidation numbers, as long as the elements constituting the particles are the same (in this example, all elements other than Zn are the same), these are the same kind of particles. .

In addition, the particles contained in the coating composition suitable for forming the surface layer of the present invention change its surface state by heat, ionizing radiation or the like in a process such as coating, drying, curing or vapor deposition. And is included in the surface layer. Here, the particles present in the coating composition used in the present invention are “particulate material”, and the coating composition is present in the surface layer formed by a process such as coating, drying, curing or vapor deposition. The particles are called “particle components”.

The inorganic particles are not particularly limited, but are preferably metal or metalloid oxides, nitrides, borides, chlorides, carbonates, sulfates, composite oxides containing two metals, metalloids, Different elements may be introduced between the lattices, lattice points may be replaced with different elements, or lattice defects may be introduced.

The inorganic particles are oxide particles in which at least one metal or semimetal selected from the group consisting of Si, Al, Ca, Zn, Ga, Mg, Zr, Ti, In, Sb, Sn, Ba, and Ce is oxidized. More preferably.

Specifically, silica (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), indium oxide (In ₂ O ₃ ), tin oxide It is at least one metal oxide or semimetal oxide selected from the group consisting of (SnO ₂ ), antimony oxide (Sb ₂ O ₃ ), and indium tin oxide (In ₂ O ₃ ). Particularly preferred is silica (SiO ₂ ).

As the particle component of the coating composition for forming the surface layer of the present invention, it is particularly preferable that the surface modification necessary for stably dispersing silica in a good solvent as a binder raw material is made. For example, when acrylic monomers and oligomers are used as the raw material for the binder, the surface modification requires an alkyl group, alkenyl group, vinyl group, (meth) acryl group or the like having a carbon number of 1 to 5 as a minimum. It is preferable that it is introduced on the surface.

Here, the number average particle diameter of the inorganic particles means the number-based arithmetic average length diameter described in JIS Z8819-2 (2001). In both the particle component and the particle material, the primary particles are observed using a scanning electron microscope (SEM), a transmission electron microscope, etc., and the diameter of the circumscribed circle of each primary particle is defined as the particle diameter. Refers to the calculated value. In the case of a laminate, the number average particle diameter can be determined by observing the surface or cross section. In the case of a coating composition, the coating composition diluted with a solvent is dropped and dried. Thus, it is possible to prepare and observe a sample.

[Inorganic particles with anisotropic shape]
Further, the surface layer of the laminate of the present invention particularly preferably contains inorganic particles having an anisotropic shape. The coating composition suitable for forming the surface layer of the present invention preferably contains inorganic particles having an anisotropic shape, and particularly preferably contains inorganic particles having an anisotropic shape in the coating composition B. Here, the inorganic particles having an anisotropic shape mean that the shape is not a spherical shape but a biased particle. Specifically, needle-like, plate-like or spherical particles are bound in a chain. It means beaded particles. When the inorganic particles contained in the surface layer have the anisotropic shape as described above, the hardness of the surface layer can be imparted while maintaining the flexibility of the entire laminate. The cause of the compatibility between flexibility and hardness is not clear, but by adding inorganic particles having an anisotropic shape, only the stress in the shear direction may increase while the stress in the indentation direction is maintained. It has been confirmed that it is possible to suppress the breakage of the laminated film due to shear.

Favorable shapes exist for the inorganic particles having the anisotropic shape. Specifically, Rl / Rs, which is the ratio of the long diameter Rl to the short diameter Rs of the inorganic particles, is preferably 1.2 or more and 20,000 or less, and more preferably 1.5 or more and 10,000 or less. More preferred. When Rl / Rs is smaller than 1.2, the difference between the indentation stress and the shear stress described above becomes difficult to occur, and the flexibility of the surface layer may be lowered. On the other hand, even if Rl / Rs is high, the performance of the laminate is not deteriorated immediately, but if Rl / Rs exceeds 20,000, thixotropy occurs in the coating material, and uniform coating is performed. May be difficult.

On the other hand, the short diameter Rs is preferably 1 nm or more and 100 nm or less, and particularly preferably 3 nm or more and 50 nm or less. When Rs is less than 1 nm, the volume ratio of the inorganic particles in the laminate becomes small, and a sufficient hardness improvement effect may not be obtained. On the other hand, when Rs exceeds 100 nm, the contribution to the aforementioned indentation stress is increased, and the flexibility of the surface layer may be reduced. A method for measuring the long diameter Rl and the short diameter Rs will be described later.

Further, the difference between the indentation stress and the shear stress described above is particularly noticeable when the binder component described later is a flexible binder. Therefore, the inorganic particles having the anisotropic shape have a modulus of elasticity of the laminate. It is particularly preferable that a large amount exists in a portion lower than the elastic modulus of the material. Specifically, the presence frequency of inorganic particles having an anisotropic shape, which will be described later, satisfies (Equation 4), that is, the elasticity of the laminate is higher than the portion where the modulus of elasticity of the laminate is higher than the modulus of elasticity of the support substrate. It is preferable that the modulus is large in a portion lower than the elastic modulus of the supporting substrate. When the existence frequency of the inorganic particles having an anisotropic shape at a portion where the elastic modulus of the laminated body is higher than the elastic modulus of the supporting base material is large, the effect of suppressing breakage due to shearing of the laminated film is sufficiently obtained. Since it becomes impossible or the flexibility of a coating film falls, it may become difficult to make flexibility and hardness of a laminated body compatible.

Inorganic particles having an anisotropic shape are oxidized with at least one metal or metalloid selected from the group consisting of Si, Al, Ca, Zn, Ga, Mg, Zr, Ti, In, Sb, Sn, Ba and Ce. More preferably, it is an oxide particle.

Specifically, silica (SiO ₂ ), aluminum oxide (Al ₂ O ₃ ), zinc oxide (ZnO), zirconium oxide (ZrO ₂ ), titanium oxide (TiO ₂ ), indium oxide (In ₂ O ₃ ), tin oxide It is at least one metal oxide or semimetal oxide selected from the group consisting of (SnO ₂ ), antimony oxide (Sb ₂ O ₃ ), and indium tin oxide (In ₂ O ₃ ). Particularly preferred is aluminum oxide (Al ₂ O ₃ ) or aluminum oxide hydrate (AlOOH) serving as a precursor thereof.

[Binder material, binder component]
The coating composition suitable for forming the surface layer of the present invention preferably contains a binder raw material. Here, the binder refers to a compound having a reactive site or a higher order compound formed by the reaction. Here, the binder present in the coating composition used in the present invention is “binder material”, and the binder present in the surface layer formed by coating, drying, curing treatment, vapor deposition or the like of the coating composition. Is called “binder component”. The reactive site refers to a site that reacts with other components by external energy such as heat or light. Among such reactive sites, preferred are silanol groups in which alkoxysilyl groups and alkoxysilyl groups are hydrolyzed from the viewpoint of reactivity, carboxyl groups, hydroxyl groups, epoxy groups, vinyl groups, allyl groups, acryloyl groups, And a methacryloyl group. The coating composition A suitable for forming the surface layer of the present invention preferably contains a “highly crosslinkable binder” described later, and the coating composition B preferably contains at least a “flexible binder” described later. May be contained simultaneously.

[Highly crosslinkable binder]
The highly crosslinkable binder can be suitably used mainly as a binder component of the coating composition A, and may be contained in the coating composition B from the viewpoint of improving adhesion and film forming property. A material having 2 or more and 20 or less reactive sites in one molecule is preferable. Either a thermosetting resin or an ultraviolet curable resin may be used, and two or more kinds of blends may be used.

Thermosetting resins suitable for highly crosslinkable binders are composed of a hydroxyl group-containing resin and a polyisocyanate compound. Examples of hydroxyl group-containing resins include acrylic polyols, polyether polyols, polyester polyols, polyolefin polyols, polycarbonate polyols, and urethane polyols. These may be one kind or a blend of two or more kinds. The hydroxyl value of the hydroxyl group-containing resin is preferably in the range of 1 to 200 mgKOH / g from the viewpoints of durability, hydrolysis resistance, and adhesion when formed into a coating film. When the hydroxyl value is less than 1, curing of the coating film hardly proceeds, and durability and strength may decrease. On the other hand, when the hydroxyl group is greater than 200, the curing shrinkage is too large, and the adhesion may be lowered.

The acrylic polyol containing a hydroxyl group in the present invention is obtained, for example, by polymerizing an acrylic ester or a methacrylic ester as a component. Such an acrylic resin can be easily prepared, for example, by copolymerizing a methacrylic acid ester as a component and a carboxylic acid group-containing monomer such as (meth) acrylic acid, itaconic acid, and maleic anhydride as necessary. Can be manufactured. Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and tert-butyl. (Meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, methylhexyl (meth) acrylate, cyclododecyl (meth) acrylate, isobornyl (meth) acrylate Etc. Examples of such an acrylic polyol containing a hydroxyl group include DIC Corporation (trade name “Acridic” (registered trademark) series, etc.), Taisei Fine Chemical Co., Ltd. (trade name “Acrit” (registered trademark) series, etc. ), Nippon Shokubai Co., Ltd .; (trade name “Akreset” (registered trademark) series, etc.), Mitsui Chemicals Co., Ltd. (trade name “Takelac” (registered trademark) UA series), etc. Can be used.

Examples of the polyester polyol containing a hydroxyl group in the present invention include aliphatic glycols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, decanediol, and cyclohexanedimethanol, and succinic acid and adipine. Aliphatic polyester polyol reacted as an essential raw material component with an aliphatic dibasic acid such as acid, sebacic acid, fumaric acid, suberic acid, azelaic acid, 1,10-decamethylenedicarboxylic acid, cyclohexanedicarboxylic acid, or ethylene glycol Aromatic polymers obtained by reacting aliphatic glycols such as propylene glycol and butanediol with aromatic dibasic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid as essential raw material components Ester polyols.

Examples of such polyester polyols containing hydroxyl groups include DIC Corporation (trade name “Polylite” (registered trademark) series, etc.), Kuraray Co., Ltd. (trade name “Kuraray polyol” (registered trademark) series, etc.), Takeda. Yakuhin Kogyo Co., Ltd. (trade name “Takelac” (registered trademark) U series) can be mentioned, and these products can be used.

Examples of the polyolefin-based polyol containing a hydroxyl group in the present invention include polymers and copolymers of diolefins having 4 to 12 carbon atoms such as butadiene and isoprene, diolefins having 4 to 12 carbon atoms, and 2 to 22 carbon atoms. Among the α-olefin copolymers, the compound contains a hydroxyl group. The method for containing a hydroxyl group is not particularly limited, and for example, there is a method of reacting a diene monomer with hydrogen peroxide. Furthermore, you may make saturated aliphatic by hydrogenating the remaining double bond. Examples of such polyolefin-based polyols containing hydroxyl groups include Nippon Soda Co., Ltd. (trade name “NISSO-PB” (registered trademark) G series, etc.), Idemitsu Kosan Co., Ltd .; (trade name “Poly bd” (registered trademark). ) Series, “Epaul” (registered trademark) series, etc.), and these products can be used.

As the polycarbonate polyol containing a hydroxyl group in the present invention, for example, a polycarbonate polyol obtained using only dialkyl carbonate and 1,6-hexanediol can be used. Polycarbonate polyol obtained by copolymerizing 1,6-hexanediol and 1,4-butanediol, 1,5-pentanediol, or 1,4-cyclohexanedimethanol as a diol in terms of lower crystallinity Is preferably used.

As the polycarbonate polyol containing such a hydroxyl group, Asahi Kasei Chemicals Co., Ltd., which is a copolymerized polycarbonate polyol; (trade names “T5650J”, “T5652”, “T4671”, “T4672”, etc.), Ube Industries, Ltd .; Trade names such as “ETERNACLL” (registered trademark) UM series), and these products can be used.

The urethane polyol containing a hydroxyl group in the present invention is, for example, a reaction between a polyisocyanate compound and a compound containing at least two hydroxyl groups in one molecule at a ratio such that the hydroxyl group is excessive with respect to the isocyanate group. Obtained. Examples of the polyisocyanate compound used in this case include hexamethylene diisocyanate, toluene diisocyanate, m-xylene diisocyanate, and isophorone diisocyanate. Examples of the compound containing at least two hydroxyl groups in one molecule include polyhydric alcohols, polyester diol, polyethylene glycol, polypropylene glycol, and polycarbonate diol.

The polyisocyanate compound used for the thermosetting resin in the present invention refers to a resin containing an isocyanate group, a monomer or an oligomer containing an isocyanate group. Examples of the compound containing an isocyanate group include methylene bis-4-cyclohexyl isocyanate, trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, and tolylene diisocyanate. Examples include isocyanurate bodies, isocyanurate bodies of hexamethylene diisocyanate, (poly) isocyanates such as a burette body of hexamethylene isocyanate, and block bodies of the above isocyanates. Polyisocyanate compounds used in such thermosetting resins include Mitsui Chemicals, Inc. (trade name “Takenate” (registered trademark) series, etc.), Nippon Polyurethane Industry Co., Ltd .; (trade name “Coronate” (registered trademark). Asahi Kasei Chemicals Corporation; (trade name “Duranate” (registered trademark) series, etc.), DIC Corporation (trade name “Burnock” (registered trademark) series, etc.).

On the other hand, as a suitable ultraviolet curable resin in the highly crosslinkable binder, polyfunctional acrylate monomer, oligomer, alkoxysilane, alkoxysilane hydrolyzate, alkoxysilane oligomer, urethane acrylate oligomer, etc. are preferable, and polyfunctional acrylate monomer, oligomer, urethane. An acrylate oligomer is more preferable.

Examples of the polyfunctional acrylate monomer include polyfunctional acrylates having two or more (meth) acryloyloxy groups in one molecule and modified polymers thereof. Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol triacrylate hexanemethylene diisocyanate urethane polymer, and the like can be used. These monomers can be used alone or in combination of two or more.

Commercially available polyfunctional acrylic compositions include Mitsubishi Rayon Co., Ltd. (trade name “Diabeam” (registered trademark) series, etc.), Nippon Synthetic Chemical Industry Co., Ltd. (trade name “SHIKOH” (registered trademark)). ) Series), Nagase Sangyo Co., Ltd .; (trade name “Denacol” (registered trademark) series, etc.), Shin-Nakamura Chemical Co., Ltd. (trade name “NK ester” series, etc.), DIC Corporation; "(Registered trademark) etc.), Toagosei Co., Ltd .; (" Aronix "(registered trademark) series etc.), NOF Corporation; (" Blemmer "(registered trademark) series etc.), Nippon Kayaku Co., Ltd .; Name “KAYARAD” (registered trademark) series, etc.), Kyoeisha Chemical Co., Ltd. (trade name “light ester” series, etc.) , It is possible to use these products.

[Flexible binder]
The flexible binder can be suitably used mainly as a binder component of the coating composition B. A material having 4 or less reactive sites in one molecule is preferable, and the active reactive sites may be deactivated like an acrylic polymer. Preferred materials for the flexible binder are exemplified below.

Preferred forms of the coating composition B include “a coating composition for forming a scratch-repairing resin layer”, “a moldable HC coating material” having a breaking elongation of about 5 to 50%, and “an adhesive”.

The coating composition for forming the scratch-repairable resin layer includes: (1) a segment containing at least one selected from the group consisting of a polycaprolactone segment, a polycarbonate segment and a polyalkylene glycol segment in the solute; It is particularly preferable to include a resin or precursor containing a segment. Each of these segments can be confirmed by TOF-SIMS, FT-IR, or the like.

On the other hand, as a pressure-sensitive adhesive, “rubber-based pressure-sensitive adhesive” using the most general rubber and tackifier, “acryl-based pressure-sensitive adhesive” that can give various functions with an acrylic polymer copolymer, excellent temperature characteristics, Although it has chemical resistance, any of the high-cost “silicone-based pressure-sensitive adhesive” can be suitably used. However, from the viewpoint of compatibility with the high elastic modulus layer and cost, “acrylic pressure-sensitive adhesive” It is particularly preferable to use

[solvent]
The coating composition A and the coating composition B preferably contain a solvent. The number of solvent types is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and still more preferably 1 or more and 6 or less. Here, the “solvent” refers to a substance that is liquid at room temperature and normal pressure, and can be removed from the coating film by evaporating almost the whole amount in the drying step after coating.

Here, the type of solvent is determined by the molecular structure constituting the solvent. That is, the same elemental composition and the same type and number of functional groups have different bond relationships (structural isomers), which are not structural isomers, but what conformations are in three-dimensional space Those that do not overlap exactly even if they are removed (stereoisomers) are treated as different types of solvents. For example, 2-propanol and n-propanol are handled as different solvents.

[Other additives]
The coating composition A and the coating composition B preferably contain a polymerization initiator, a curing agent, and a catalyst. A polymerization initiator and a catalyst are used to accelerate the curing of the surface layer. As the polymerization initiator, those capable of initiating or accelerating polymerization, condensation or crosslinking reaction by anion, cation, radical polymerization reaction or the like of components contained in the coating composition are preferable.

Various polymerization initiators, curing agents and catalysts can be used. In addition, the polymerization initiator, the curing agent, and the catalyst may be used alone, or a plurality of polymerization initiators, curing agents, and catalysts may be used simultaneously. Furthermore, you may use together an acidic catalyst, a thermal-polymerization initiator, and a photoinitiator. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid and the like. Examples of the thermal polymerization initiator include peroxides and azo compounds. Examples of the photopolymerization initiator include alkylphenone compounds, sulfur-containing compounds, acylphosphine oxide compounds, amine compounds, and the like.

As the photopolymerization initiator, an alkylphenone compound is preferable from the viewpoint of curability. Specific examples of the alkylphenone compounds include 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl)- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-phenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- 1- (4-phenyl) -1-butane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butane, 1-cyclohexyl-phenylketone, 2-methyl-1-phenylpropane-1-one , 1- [4- (2-Ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, bis (2-phenyl-2-oxoacetic acid) oxybisethylene, and materials thereof And the like having a high molecular weight.

The progress of the polymerization reaction by the thermal polymerization initiator or photopolymerization initiator can be controlled by the amount of heat or the amount of light applied, and when the surface layer is formed by sequential coating, the progress of the polymerization is incomplete. By applying the next layer, a mixed layer having intermediate physical properties can be formed without forming a clear interface.

In addition, a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, etc. may be added to the coating composition A and the coating composition B used for forming the surface layer as long as the effects of the present invention are not impaired. . Thereby, the surface layer can contain a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, and the like. Examples of the leveling agent include acrylic copolymers, silicone-based and fluorine-based leveling agents. Specific examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, oxalic acid anilide-based, triazine-based and hindered amine-based ultraviolet absorbers. Examples of the antistatic agent include metal salts such as lithium salt, sodium salt, potassium salt, rubidium salt, cesium salt, magnesium salt and calcium salt.

[Manufacturing method of laminate]
The production method of the laminate of the present invention uses a production method in which at least the coating composition A and the coating composition B are formed by applying, drying, and curing sequentially or simultaneously on the supporting substrate. More preferred.

Here, “sequentially apply” or “sequentially apply” means that after coating-drying-curing one type of coating composition, the surface layer is then formed by coating-drying-curing a different type of coating composition. Intended to form. The surface layer formed in “sequential coating” can be selected by appropriately selecting the type and number of coating compositions to be used. You can control the size. The surface layer formed by “sequential application” usually has a “multilayer structure” having a plurality of interfaces, but by appropriately selecting the type, composition, drying conditions, and curing conditions of the coating composition, It is also possible to control the separation and diffusion of the material species to form a pseudo gradient structure. With the layer structure as described above, the elastic modulus distribution in the surface layer can be changed stepwise or continuously.

Another manufacturing method is a method in which two or more kinds of coating compositions are formed by simultaneously applying, drying and curing on a supporting substrate. There are no particular restrictions as long as the number of types of coating compositions is two or more. Here, “simultaneous application” or “simultaneous application” is intended to dry and cure after applying two or more types of liquid films on a supporting substrate in the application step. The surface layer formed in “simultaneous application” forms an “inclined structure” having no clear interface.

In this production method, the coating method is 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) when the aforementioned coating composition is sequentially applied. It is preferable to form a surface layer by applying it to a supporting base material, etc. In addition, when simultaneously applying two or more kinds of coating compositions as described above, after laminating liquid films in order before application “Multilayer Slide Die Coat” to be applied (FIG. 5), “Multilayer Slot Die Coat” to be laminated on the substrate simultaneously with application (FIG. 6), and a single layer of liquid film formed on the support substrate, then undried Any of “wet-on-wet coat” (FIG. 7) or the like in which another layer is laminated.

Next, the liquid film applied on the support substrate or the like is dried. In addition to completely removing the solvent from the resulting laminate, it is preferable that the drying process involves heating the liquid film.

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

Furthermore, a further curing operation (curing step) by irradiating heat or energy rays may be performed. In the curing step, when the coating composition A and the coating composition B are used and cured by heat, the temperature is preferably from room temperature to 200 ° C., and from the viewpoint of the activation energy of the curing reaction, 80 ° C. or more and 200 ° C. The following is more preferable, and in order to form the mixed layer having the above-described intermediate physical properties, it is more preferable that the temperature is 80 ° C. or higher and 100 ° C. or lower.

Further, when curing with active energy rays, electron beams (EB rays) and / or ultraviolet rays (UV rays) are preferable 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. On the other hand, in the layer forming the inside of the surface layer, it is preferable because the next coating layer easily penetrates by promoting oxygen inhibition, and the mixed layer having the above-mentioned intermediate physical properties is easily formed. .

Examples of the ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method. When UV curing is performed using a high-pressure mercury lamp that is a discharge lamp method, the illuminance of UV is 100 to 3,000 mW / cm ² , preferably 200 to 2,000 mW / cm ² , more preferably 300 to 1,500 mW / cm ^2. It is preferable to perform ultraviolet irradiation under the following conditions, and the cumulative amount of ultraviolet light is 100 to 3,000 mJ / cm ² , preferably 200 to 2,000 mJ / cm ² , more preferably 300 to 1,500 mJ / cm ^2. It is preferable to perform ultraviolet irradiation under conditions. 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 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 irradiation speed passing under the light source, and is proportional to the number of irradiations and the number of lamps.

[Application example]
The laminate of the present invention can be widely used for a member having a curved surface in order to achieve both excellent surface hardness and flexibility, for example, an electrical appliance, an automobile interior member, and a building member.

Examples include plastic products such as glasses / sunglasses, cosmetic boxes, food containers, smartphone housings, touch panels, keyboards, home appliances such as remote controls for TVs and air conditioners, buildings, dashboards, car navigation systems, touch panels, and rooms. It can be suitably used for vehicle interior parts such as mirrors, and the surfaces of various printed materials.

Next, the present invention will be described based on examples, but the present invention is not necessarily limited thereto.

<Preparation of coating composition A>
[Coating composition A1]
The following materials were mixed and diluted with ethyl acetate to obtain a coating composition A1.
・ Organic-inorganic hybrid HC coating material 80.0 parts by mass (“Aika Aitoron” Z-729-18 Aika Industry Co., Ltd.)
-Ethyl acetate 20.0 mass parts.

[Coating composition A2]
Dipentaerythritol hexaacrylate 18.8 parts by mass Particle additive C1 (silica particle dispersion) 44.4 parts by mass (“MEK-AC-2140Z” Nissan Chemical Industries, Ltd.)
-Ethyl acetate 35.6 mass parts-Photoradical polymerization initiator 1.2 mass parts ("Irgacure" (trademark) 184 BASF Japan Ltd.).

[Coating composition A3]
-Dipentaerythritol hexaacrylate 38.8 mass parts-Ethyl acetate 60.0 mass parts-Photoradical polymerization initiator 1.2 mass parts ("IRGACURE" (trademark) 184 BASF Japan Ltd.).

[Coating composition A4]
・ 36.8 parts by mass of dipentaerythritol hexaacrylate (“Aika Itron” Z-729-18 Aika Industry Co., Ltd.)
-Particle additive C3 2.0 mass parts-Ethyl acetate 60.0 mass parts-Photoradical polymerization initiator 1.2 mass parts ("IRGACURE" (trademark) 184 BASF Japan Ltd.).

<Preparation of coating composition B>
<Synthesis of urethane acrylate>
[Toluene acrylate 1 in toluene solution]
50 parts by mass of toluene, isocyanurate-modified type of hexamethylene diisocyanate (Takenate D-170N, manufactured by Mitsui Chemicals), 76 parts by mass of polycaprolactone-modified hydroxyethyl acrylate (Placcel FA5, manufactured by Daicel Chemical Industries, Ltd.), dibutyltin 0.02 part by mass of laurate and 0.02 part by mass of hydroquinone monomethyl ether were mixed and held at 70 ° C. for 5 hours. Thereafter, 79 parts by mass of toluene was added to obtain a toluene solution of urethane acrylate 1 having a solid content concentration of 50% by mass.

[Toluene solution of urethane acrylate 2]
Isocyanurate-modified hexamethylene diisocyanate (Takenate D-170N, Mitsui Chemicals, Inc., isocyanate group content: 20.9% by mass), 50 parts by mass of polyethylene glycol monoacrylate (Blenmer AE-150, manufactured by NOF Corporation) Value: 264 (mg KOH / g)) 53 parts by weight, dibutyltin laurate 0.02 part by weight and hydroquinone monomethyl ether 0.02 part by weight were charged, and the reaction was carried out while maintaining at 70 ° C. for 5 hours. After the completion, 102 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK) was added to the reaction solution to obtain a toluene solution of urethane acrylate 2 having a solid content concentration of 50% by mass.

[Coating composition B1]
The following materials were mixed and diluted with ethyl acetate to obtain a coating composition B1.
-Solid content concentration of urethane acrylate 1-4.9 parts by mass of toluene solution-Solid content concentration of urethane acrylate 2-4.9 parts by mass of toluene solution-90.05 parts by mass of ethyl acetate-Photoradical polymerization Initiator 0.15 parts by mass (“Irgacure” (registered trademark) 184 BASF Japan Ltd.).

[Coating composition B2]
The following materials were mixed and diluted with ethyl acetate to obtain a coating composition B2.
・ Self-healing paint 7.1 parts by mass (“Folceed” NO.521C China Paint Co., Ltd.)
-92.86 mass parts of ethyl acetate.

[Coating composition B3]
The following materials were mixed and diluted with ethyl acetate to obtain a coating composition B3.
・ Acrylic adhesive 16.7 parts by mass (“SK Dyne” 1439U Soken Chemical Co., Ltd.)
-Ethyl acetate 83.26 mass parts-Curing agent 0.08 mass part (Curing agent E-50C Soken Chemical Co., Ltd.).

[Coating composition B4]
-Solid content concentration of urethane acrylate 1-toluene solution 4.85 parts by mass-Solid content concentration of urethane acrylate 2-50% by weight-toluene solution 4.85 parts by mass-Particle additive C2 0.1 part by mass-Acetic acid 90.05 parts by mass of ethyl and 0.15 parts by mass of radical photopolymerization initiator (“Irgacure” (registered trademark) 184 BASF Japan Ltd.).

[Coating composition B5]
-Solid content concentration of urethane acrylate 1-toluene solution 4.85 parts by mass-Solid content concentration of urethane acrylate 2-50% by weight-toluene solution 4.85 parts by mass-Particle additive C3 0.1 part by mass-Acetic acid 90.05 parts by mass of ethyl and 0.15 parts by mass of radical photopolymerization initiator (“Irgacure” (registered trademark) 184 BASF Japan Ltd.).

[Coating composition B6]
-Solid content concentration of urethane acrylate 1-toluene solution 4.85 parts by mass-Solid content concentration of urethane acrylate 2-50% by weight-toluene solution 4.85 parts by mass-Particle additive C4 0.1 part by mass-Acetic acid 90.05 parts by mass of ethyl and 0.15 parts by mass of radical photopolymerization initiator (“Irgacure” (registered trademark) 184 BASF Japan Ltd.).

[Coating composition B7]
-Solid content concentration of urethane acrylate 1-toluene solution 4.85 parts-Solid content concentration of urethane acrylate 2-50% by weight-toluene solution 4.85 parts-Particle additive C5 0.1 part-acetic acid 90.05 parts by mass of ethyl and 0.15 parts by mass of radical photopolymerization initiator (“Irgacure” (registered trademark) 184 BASF Japan Ltd.).

[Coating composition B8]
-Solid content concentration of urethane acrylate 1-4.85 parts by mass of toluene solution-Solid content concentration of urethane acrylate 2-4.85 parts by mass of toluene solution-0.1 part by mass of particle additive C6-Acetic acid 90.05 parts by mass of ethyl and 0.15 parts by mass of radical photopolymerization initiator (“Irgacure” (registered trademark) 184 BASF Japan Ltd.).

[Coating composition B9]
-Solid content concentration of urethane acrylate 1-4.85 parts by mass of toluene solution-Solid content concentration of urethane acrylate 2-4.85 parts by mass of toluene solution-0.1 part by mass of particle additive C7-Acetic acid 90.05 parts by mass of ethyl and 0.15 parts by mass of radical photopolymerization initiator (“Irgacure” (registered trademark) 184 BASF Japan Ltd.).

[Coating composition B10]
-Solid content concentration of urethane acrylate 1-toluene solution 4.85 parts by mass-Solid content concentration of urethane acrylate 2-50% by weight-toluene solution 4.85 parts by mass-Particle additive C8 0.1 part by mass-Acetic acid 90.05 parts by mass of ethyl and 0.15 parts by mass of radical photopolymerization initiator (“Irgacure” (registered trademark) 184 BASF Japan Ltd.).

<Particle additive C>
The following particle dispersions were used as the particle additive C, respectively. Details of the shape of each particle component are shown in Table 1.
Particle additive C1: Silica particle dispersion (“MEK-AC-2140Z” Nissan Chemical Industries, Ltd.)
Particle additive C2: Boehmite dispersion (columnar boehmite sol, manufactured by Kawaken Fine Chemical Co., Ltd.)
Particle additive C3: Boehmite dispersion (columnar boehmite sol, manufactured by Kawaken Fine Chemical Co., Ltd.)
Particle additive C4: layered silicate (“Lucentite SPN” Corp Chemical) 1 wt% IPA dispersion particle additive C5: chained silica particle dispersion (“MEK-ST-UP” Nissan Chemical Industries, Ltd.)
Particle additive C6: Boehmite dispersion (Fibrous boehmite sol Kawaken Fine Chemical Co., Ltd.)
Particle additive C7: Silica particle dispersion (“MEK-ST-L” Nissan Chemical Industries, Ltd.)
Particle additive C8: Silica particle dispersion (“MEK-ST-2040” Nissan Chemical Industries, Ltd.)
<Method for producing laminate>
As a supporting substrate, “Lumirror” (registered trademark) U48 (manufactured by Toray Industries, Inc.) having a thickness of 50 μm in which an easy-adhesive paint is applied on a PET resin film was used. Coating compositions A and B are applied onto the supporting substrate using a wire bar, and the coating is adjusted so that the thickness of the surface layer after drying becomes the specified film thickness, and then the drying process and curing are performed under the following conditions: The process was performed. A surface layer was formed on the support substrate by sequentially repeating these series of coating, drying, and curing.

Table 1 shows the method for preparing the laminate, the coating composition to be used, and the theoretical film thickness of each layer corresponding to each of the examples and comparative examples.
"Drying process of UV curing 1"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coating surface side: 5 m / sec, anti-coating surface side: 5 m / sec Wind direction: coating surface side: parallel to substrate surface, anti-coating surface side: vertical residence time to substrate surface: 2 Minutes "UV curing 1 curing process"
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: 200 ppm or less.
"Drying process of UV curing 2"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coating surface side: 5 m / sec, anti-coating surface side: 5 m / sec Wind direction: coating surface side: parallel to substrate surface, anti-coating surface side: vertical residence time to substrate surface: 2 Minute "UV curing 2 curing process"
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: Atmospheric atmosphere.
"Drying / curing process of thermosetting 1"
Air temperature and humidity: Temperature: 80 ° C
Wind speed: coating surface side: 5 m / sec, anti-coating surface side: 5 m / sec Wind direction: coating surface side: parallel to substrate surface, anti-coating surface side: vertical residence time to substrate surface: 2 Laminates of Examples 1 to 19 and Comparative Examples 1 to 6 were prepared by a method of minutes or more.

<Evaluation of laminate>
The produced laminate was subjected to the following performance evaluation, and the results obtained are shown in Tables 2 to 4. Unless otherwise specified, in each of the examples and comparative examples, the measurement was performed three times at different locations for each sample, and the average value was used.

[Measurement of elastic modulus by atomic force microscope]
The laminates of Examples 1 to 19 and Comparative Examples 1 to 6 were embedded and cured with an electron microscope epoxy resin (Quetol 812 manufactured by Nissin EM Co., Ltd.), and then a cross section was cut out by a freezing microtome method. And fixed to a dedicated sample fixing base. Using an AFM “MFP-3DSA-J” manufactured by Asylum Technology and a cantilever “R150-NCL-10 (material Si, spring constant 48 N / m, radius of curvature of the tip 150 nm) manufactured by NANOSENSORS” A force curve (cantilever moving speed 2 μm / s, maximum indentation load 2 μN) was measured on the cross section in the Contact mode.

From the Force-Ind curve obtained from the force curve, the elastic modulus distribution in the thickness direction was obtained by performing analysis based on the Hertz theory attached to the software “IgorPro 6.22A MFP3D101010 + 1313” attached to the AFM apparatus. Tip Geometry = Sphere, Radius = 150 nm, Select = Fused Silica, νTip = 0.17, Etip = 74.9 GPa, νSample = 0.33, Force tab Low = 10%, Force tab High = 90% Calculated.

[Measurement of elastic modulus distribution in cross-sectional thickness direction]
The surface image was measured in the tapping mode and the resolution of 512 × 512 pixels for the cross section of the laminate prepared by the above method. Subsequently, the magnification was adjusted from the obtained surface image so that the thickness of the surface layer was within the viewing angle. At this time, the interface between the surface layer and the supporting substrate is observed as a bright line or dark line due to a mismatch in elastic modulus at the boundary between the surface layer and the supporting substrate, and the center of this bright line or dark line is a measurement standard in the thickness direction of the surface layer. A line. Similarly, for the outermost surface, the center of the bright line or dark line generated by the mismatch in elastic modulus between the surface layer and the embedding resin was used as a measurement reference line in the thickness direction of the surface layer. In the following measurement, the term “distance from the outermost surface” refers to the distance from the center of the bright line or dark line on the outermost surface, and the term “distance to the outermost surface” refers to the distance from the outermost surface. The distance to the center of the bright line or dark line. Similarly, the term “distance from the interface between the surface layer and the supporting substrate” refers to the distance from the center of the bright line or dark line at the above-mentioned interface, and the term “distance to the interface between the surface layer and the supporting substrate”. The distance to the center of the bright line or dark line at the aforementioned interface.

The distance between the aforementioned surface layer-supporting substrate interface and the outermost surface was defined as the total thickness of the surface layer. Next, a data group on a straight line running through the surface layer was selected from lattice point-like measurement points with a resolution of 512 × 512. Further, the distance in the thickness direction from the interface between the surface layer and the supporting substrate at each data point is calculated from the angle formed by the straight line perpendicular to the surface layer to which the above data group belongs and the normal line of the laminate. The elastic modulus distribution in the thickness direction was obtained by measuring the elastic modulus by the above-described method so as to be approximately 100 nm. At this time, the point in the thickness direction from the interface between the surface layer and the supporting substrate is less than 100 nm (reference numeral 10 in FIG. 1) and the distance from the outermost surface is less than 100 nm (reference numeral 11 in FIG. 1). Since it is easily affected by the interface and surface, it was excluded from the measurement. When the measurement is performed by the above method, the lower limit of the distance between the measurement points that can be set practically is determined from the thickness of the surface layer and the resolution. Specifically, it is about 1/500 of the thickness of the surface layer. For example, if the thickness of the surface layer is 50 μm, the spatial resolution is about 100 nm. Although it is possible to further increase the resolution in setting the apparatus, the above-mentioned value of about 100 nm is a practically measurable value from the curvature of the cantilever, the number of measurement points, and the like.

Next, as the elastic modulus on the outermost surface side and the interface side, there is no elasticity in the surface layer because it exists at a position 100 nm inside from the outermost surface (reference numeral 5 in FIG. 1) and at a position 100 nm inside from the interface (reference numeral 7 in FIG. 1). It selected for work and made the average value of the measurement result in each 5 places the elastic modulus of the outermost surface side and the interface side.

[Measurement of elastic modulus of supporting substrate]
Similarly, the elastic modulus of the cross section was measured for the supporting substrate. Regarding the measurement position, in the supporting substrate, from the point of the distance of 100 nm from the interface between the supporting substrate and the surface layer to the supporting substrate side (for example, reference numeral 8 in FIG. 1), the thickness direction of the supporting substrate (the surface layer exists) The elastic modulus was measured at intervals of 100 nm in the direction opposite to the direction in which it was performed. Measure from the interface between the support substrate and the surface layer to a distance corresponding to the same thickness as the surface layer (for example, if the thickness of the surface layer is 3 μm, 3 μm from the interface between the support substrate and the surface layer) The elastic modulus is measured at intervals of 100 nm up to the distance), and the average value is taken as the elastic modulus of the supporting substrate.

[Calculation of parameters from elastic modulus distribution in the thickness direction]
Based on the parameters in the thickness direction obtained by the method described above, the maximum elastic modulus, the minimum elastic modulus, the average value (Ta) of the thickness where the elastic modulus is higher than the elastic modulus of the supporting substrate, and the elastic modulus is the supporting substrate. The average value of the thickness (Tb), the average value of the maximum elastic modulus (Ea), and the average value of the minimum elastic modulus (Eb) of the portion lower than the elastic modulus of each were calculated by the following methods.

First, among the obtained elastic moduli, among the measurement points where the measurement position in the thickness direction belongs to the surface layer, the maximum elastic modulus is the maximum elastic modulus, and the minimum elastic modulus is the minimum elastic modulus. Next, the points where the elastic modulus becomes maximum are extracted from the measurement points belonging to the surface layer, and further all of the values larger than the elastic modulus of the supporting base material are extracted from these maximum values, and Ea is obtained as an average value thereof. Obtained. Eb was also calculated in the same manner except that a minimum value was extracted instead of the maximum value and a value smaller than the elastic modulus of the support base was used.

Next, from the elastic modulus distribution in the thickness direction and the elastic modulus of the supporting substrate, a portion where the elastic modulus is higher than the elastic modulus of the supporting substrate and a portion where the elastic modulus is lower than the elastic modulus of the supporting substrate were calculated. The concept is shown in FIG. 3, specifically, the coordinates of the intersection of the “elastic modulus of the supporting substrate” and the “elastic modulus distribution in the thickness direction” were calculated by the following method. As described above, since the “elastic modulus distribution in the thickness direction” is a set of discrete data points at intervals of 100 nm, “one elastic modulus is lower than the elastic modulus of the supporting substrate and the other elastic modulus is supported. Two adjacent points satisfying the condition “higher than the elastic modulus of the base material” are extracted, and the coordinates of the intersection of the straight line connecting the two points satisfying the condition and the straight line indicating the elastic modulus of the supporting base material (hereinafter, the coordinates of the intersection point) Calculated). Then, the distance in the thickness direction between the intersections is calculated from the calculated coordinates of each intersection, and “the thickness of the portion where the elastic modulus is higher than the elastic modulus of the supporting substrate” and “the elastic modulus is higher than the elastic modulus of the supporting substrate. “Low thickness”. Note that the thickness on the interface side with the support substrate is the distance from the surface layer-support substrate interface (reference numeral 13 in FIG. 4) to the coordinate of the shortest intersection (reference numeral 22 in FIG. 4). The thickness of the portion higher than the elastic modulus of the supporting substrate ”. Further, the thickness on the outermost surface side is the distance from the outermost surface (reference numeral 12 in FIG. 4) to the shortest intersection (reference numeral 23 in FIG. 4) of “the portion where the elastic modulus is higher than the elastic modulus of the supporting substrate. "Thickness". Furthermore, the elastic modulus is the elasticity of the supporting substrate by averaging the thickness of the portion where the calculated elastic modulus is lower than the elastic modulus of the supporting substrate and the thickness of the portion where the elastic modulus is lower than the elastic modulus of the supporting substrate. The average value (Ta) of the thickness of the portion higher than the modulus and the average value (Tb) of the thickness of the portion where the elastic modulus is lower than the elastic modulus of the supporting substrate were calculated.

[Shape measurement of inorganic particles having anisotropic shape]
The shape of the inorganic particles contained in the cross section of the surface layer was measured by observing the cross section using a transmission electron microscope (TEM). The shape of the inorganic particles was measured according to the following method. First, an ultrathin section of the cross section of the laminate was taken with a TEM at a magnification of 200,000 times. Subsequently, the image is converted to gray scale using the image processing software EasyAccess Ver 6.7.1.23, and the white balance is adjusted so that the brightest and darkest parts are within the 8-bit tone curve, and the boundaries of the inorganic particles are clear. The contrast was adjusted so that it could be distinguished. Then, using the software (image processing software ImageJ / Developer: National Institutes of Health (NIH)), the pixels are binarized at the boundary described above, and individual inorganic particles are analyzed by the Analyze Particles (particle analysis) function. The area of the corresponding area was extracted, and the area of the corresponding area was approximated to an ellipse by Fit Ellipse, and the value of Major was determined as the long diameter, and the value of Minor was determined as the short diameter. The above analysis was performed on a total of 50 individual inorganic particles, and the maximum value of the long diameter was the long diameter Rl and the minimum value of the short diameter was the short diameter Rs.

[Measurement of existence frequency of inorganic particles with anisotropic shape]
Subsequently, the presence frequency of the inorganic particles was calculated from the cross-sectional observation of the same transmission electron microscope (TEM). First, an ultrathin section of the cross section of the laminate was taken with a TEM at a magnification of 50,000 times. Next, the image was converted to a gray scale by image processing software EasyAccess Ver6.7.23, and the white balance was adjusted so that the brightest part and the darkest part were within an 8-bit tone curve. Further, the contrast was adjusted so that the boundaries of the inorganic particles could be clearly identified, and rotation / trimming was performed so that the interface between the surface layer and the supporting substrate (reference numeral 13 in FIG. 4) was horizontal. Next, the “thickness of the portion where the elastic modulus is higher than the elastic modulus of the supporting substrate” and the “elastic modulus is the supporting base” obtained by the method described in the section “Calculation of parameters from elastic modulus distribution in the thickness direction” described above. The image was subdivided into strips in a direction parallel to the interface along the value of “thickness of the portion lower than the elastic modulus of the material”. Next, using the software (image processing software ImageJ / Developer: National Institutes of Health (NIH)), the pixels are binarized on the boundary described above, and each inorganic particle is analyzed by the Analyze Particles (particle analysis) function. The area formed by the particles was extracted, and the area of the corresponding area was calculated therefrom. Similarly, the area formed by the cut strip-shaped image was calculated, and the area ratio of the inorganic particles in the strip was calculated as the presence frequency of the inorganic particles. Of the existence frequencies calculated as described above, the average value of the values obtained from the strip formed by the “thickness of the portion where the elastic modulus is higher than the elastic modulus of the supporting base material” is the elastic modulus from the elastic modulus of the supporting base material. The average value of the values obtained from the strip formed by the “thickness of the portion where the elastic modulus is lower than the elastic modulus of the supporting substrate” is the portion where the elastic modulus is lower than the elastic modulus of the supporting substrate. The existence frequency Fb was determined.

[Surface hardness measurement by pencil hardness test method for surface layer]
The prepared laminate is allowed to stand under normal conditions (24 ° C., relative humidity 65%) for 12 hours, and then in accordance with the scratch hardness (pencil method) described in JIS K 5600-5-4 (1999) in the same environment. The surface hardness of the layer was measured.

[Scratch resistance of surface layer]
The prepared laminate is allowed to stand under normal conditions (24 ° C., relative humidity 65%) for 12 hours, and then steel wool (# 0000) having a load of 1,000 g / cm ² is perpendicular to the surface having the surface layer. The approximate number of scratches visually observed when the length of 5 cm was reciprocated 10 times was described, and the following classification was performed.
5 points: 0 4 points: 1 or more Less than 5 3 points: 5 or more Less than 10 2 points: 10 or more Less than 20 1 point: 20 or more.

[Flexibility of laminate]
The prepared laminate is allowed to stand under normal conditions (24 ° C., relative humidity 65%) for 12 hours, and then is bent in the same environment as described in JIS K 5600-5-1 (1999) (cylindrical mandrel method) Evaluation was performed according to type 1 of The mandrels having diameters of 2, 3, 4, and 5 mm were used, and classification was performed as follows according to the minimum diameter at which cracks and coating film peeling were not observed by visual judgment. The same evaluation was carried out under the condition that the surface having the surface layer was folded (mountain fold) and the condition that the surface having the surface layer was folded (valley fold).
5 points: 2 mmφ crack, no peeling 4 points: 2 mmφ crack, peeling 3 mmφ crack, no peeling 3 points: 3 mmφ crack, peeling 4 mmφ crack, no peeling 2 points: 4 mmφ crack, peeling 5 mmφ crack, no peeling 1 point: 5 mmφ Cracking and peeling.

[Curlability of laminate]
The prepared laminate was allowed to stand under normal conditions (24 ° C., relative humidity 65%) for 12 hours, then cut into a 10 cm square shape and left on a horizontal plane. Next, the distance between the four corner points of the laminate and the horizontal plane was measured, and classified into five levels based on the average of the numerical values.
5 points: less than 1 mm 4 points: 1 mm or more, less than 10 mm 3 points: 10 mm or more, less than 20 mm 2 points: 20 mm or more 1 point: cylindrical and cannot be measured.

[Adhesion of surface layer]
The prepared laminate was allowed to stand under normal conditions (24 ° C., relative humidity 65%) for 12 hours, and then 100 pieces of 1 mm ² crosscuts were placed on the surface having the surface layer, and “Cello tape” (registered) manufactured by Nichiban Co., Ltd. (Trademark) is affixed on it, reciprocated three times with a load of 19.6 N using a rubber roller, pressed, peeled off in the direction of 90 degrees, and evaluated in five stages based on the number of remaining conductive layers (5:96) To 100, 4:81 to 95, 3:71 to 80, 2:61 to 70, 1: 0 to 60).

The laminate according to the present invention can also be used for imparting similar functions to the surfaces of plastic molded products, home appliances, buildings, vehicle interiors, and various printed materials.

DESCRIPTION OF SYMBOLS 1 Support base material 2 Surface layer 3 Laminate 4 Outer surface 5 of surface layer Measurement point 6 of elastic modulus of the outermost surface side Interface 7 of surface layer and support base material Measurement point 8 of elastic modulus of interface side Elasticity of support base material Rate measurement start point 9 Elastic modulus of supporting substrate 10 Region 11 where measurement is not performed due to influence of supporting substrate 12 Region where measurement is not performed due to influence of surface 12 Position of outermost surface of surface layer 13 Surface layer-supporting substrate interface Position 14 Maximum elastic modulus 15 Minimum elastic modulus 16 Maximum elastic modulus 17 Average value of maximum elastic modulus 18 Minimum elastic modulus 19 Average value of minimum elastic modulus 20 The elastic modulus distribution in the thickness direction and the elastic modulus are larger than the elastic modulus of the supporting substrate. Thickness 21 of the high portion The elastic modulus distribution in the thickness direction and the thickness 22 of the portion where the elastic modulus is lower than the elastic modulus of the supporting base material Among the points where the elastic modulus of the supporting base material and the surface layer are equal, the surface layer and the supporting base Point 23 closest to the interface of the material The elastic modulus of the supporting substrate and the surface layer are equal. Among consisting point, the closest point 24 multilayer slide die 25 multilayer slot die 26 monolayers slot die on the outermost surface

Claims (6)

1. A laminate in which a surface layer is laminated on a supporting substrate, and in the elastic modulus distribution in the thickness direction of the surface layer, the maximum value and the elastic modulus are higher than the elastic modulus of the supporting substrate. There is a minimum value lower than the elastic modulus of the surface layer, and both the elastic modulus on the interface side with the supporting substrate and the elastic modulus on the outermost surface side in the surface layer are both higher than the elastic modulus of the supporting substrate. Laminated body.
2. 2. The laminate according to claim 1, wherein the maximum elastic modulus in the elastic modulus distribution in the thickness direction of the surface layer is 100 to 10,000 times the minimum elastic modulus.
3. The laminate according to claim 1 or 2, wherein the minimum elastic modulus in the elastic modulus distribution in the thickness direction of the surface layer is 0.1 GPa or less.
4. In the elastic modulus distribution in the thickness direction of the surface layer, a maximum value whose elastic modulus is higher than the elastic modulus of the supporting substrate and a minimum value whose elastic modulus is lower than the elastic modulus of the supporting substrate are alternately present, and the elastic modulus distribution 4. The laminate according to claim 1, wherein a thickness and an elastic modulus calculated from the above satisfy the following relationship.
   10 ≦ (Tb [nm] / Ta [nm]) × (Ea [MPa]) / Eb [MPa]) ≦ 1,000 (Formula 1)
   Ta [nm]: Average thickness of the portion where the elastic modulus is higher than the elastic modulus of the supporting substrate Tb [nm]: Average thickness of the portion where the elastic modulus is lower than the elastic modulus of the supporting substrate Ea [MPa] : Average value of maximum elastic modulus Eb [MPa]: Average value of minimum elastic modulus
5. The laminate according to any one of claims 1 to 4, wherein the surface layer includes inorganic particles having an anisotropic shape satisfying the following.
   1.2 ≦ Rl / Rs ≦ 20,000 (Formula 2)
   1 nm ≦ Rs ≦ 100 nm (Formula 3)
   Rl [nm]: Long diameter of the inorganic particle Rs [nm]: Short diameter of the inorganic particle
6. 6. The existence frequency F in the thickness direction of the inorganic particles having the anisotropic shape in a cross section perpendicular to the supporting base material of the surface layer satisfies the following condition. Laminated body.
   Fa <Fb (Formula 4)
   Fa: Presence frequency of a portion where the elastic modulus is higher than the elastic modulus of the supporting base material Fb: Presence frequency of a portion where the elastic modulus is lower than the elastic modulus of the supporting base material

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