KR102540277B1 - Layered body - Google Patents

Abstract

A laminate having both high surface hardness and flexibility is provided. It is a laminate in which a surface layer is laminated on a support substrate, and in the distribution of the elastic modulus in the thickness direction of the surface layer, there is a maximum value having a higher modulus of elasticity than the modulus of elasticity of the supporting substrate and a minimum value having a lower modulus of elasticity than the modulus of elasticity of the supporting substrate, and in the surface layer A layered product characterized in that both the modulus of elasticity at the interface side with the supporting substrate and the modulus of elasticity at the outermost surface side are higher than the modulus of elasticity of the supporting substrate.

Description

Laminate {LAYERED BODY}

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

BACKGROUND ART Conventionally, a plastic film provided with a surface layer made of synthetic resin or the like is used for the purpose of protecting the surface of an optical material such as a color filter or a flat panel display (preventing scratches or imparting antifouling properties, etc.). In these surface layers, scratch resistance is required as an important characteristic from the viewpoint of surface protection. Therefore, in general, a coating composition containing various prepolymers, oligomers, etc., such as organosilane-based or polyfunctional acrylic-based materials described in Non-Patent Document 1, is applied, dried, heat-cured, or UV-cured as a "high cross-linking density material". ” is used to impart scratch resistance. In addition, scratch resistance is imparted by using a so-called "hard coating material" in which the surface hardness of the coating film is increased by using an "organic-inorganic hybrid material" or the like in which various surface-modifying fillers are combined.

On the other hand, in recent years, taking advantage of the light and flexible characteristics of plastic films, not only display surfaces such as personal computers and smartphones, but also "protection of curved surfaces" such as housing surfaces, and flexible devices rich in flexibility such as so-called "flexible devices" The use of housing is in progress. In such applications, in addition to "surface hardness" such as scratch resistance and damage durability of the surface layer, it is required to achieve both resistance to cracking and peeling even during bending, that is, "flexibility".

In the hard coating material, as a laminate focusing on both scratch resistance and flexibility, in Patent Document 1 and Patent Document 2, "Adhesion between hard coating / substrate, film bending cracks, curl, etc. can be accommodated within a practical allowable range, , Hard coating film having a pencil hardness value of 4H or more” is disclosed. Specifically, "a cured resin film layer formed by providing a cured resin layer containing inorganic or organic internally crosslinked ultrafine particles, and then further providing a thin film of clear cured resin containing no inorganic or organic internally crosslinked ultrafine particles" A "cured resin coating layer comprising a two-layer structure in which a cured resin coating layer containing a blend of a radical polymerization type resin and a cation polymerization type resin and a cured resin coating layer containing only a radical polymerization type resin are formed in this order" has been proposed. .

On the other hand, Patent Literature 3 discloses "a hard coat film that improves surface hardness, prevents damage to the hard coat film due to stress concentration, and is less prone to scratches." Specifically, "a hard coat film characterized in that 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 surface hard coat layer" is proposed. .

Further, Patent Literature 4 discloses "a laminate with a hard coat layer that can be produced easily, has excellent film adhesion, and has high film strength and excellent abrasion resistance." Specifically, "a structure in which two layers having different concentrations of inorganic particles are alternately laminated, and when the layer group with the high inorganic particle concentration is the A-layer unit and the layer group with the low inorganic particle concentration is the B-layer unit, the corresponding A laminate with a hard coat layer characterized in that the sum of dry film thicknesses of A-layer units ΣAh and the sum of dry film thicknesses of corresponding B-layer units ΣBh satisfy the relationship ΣAh ≥ ΣBh” has been proposed.

Japanese Unexamined Patent Publication No. 2000-052472 Japanese Unexamined Patent Publication No. 2000-071392 Japanese Unexamined Patent Publication No. 2000-214791 International Publication No. 2009/130975 pamphlet

Plastic Hard Coating Application Technology Published by CMC, Co., Ltd. 2004

However, since the surface hardness, that is, the elastic modulus, of the plastic film using the above-mentioned "hard coating material" for the above-mentioned surface layer is extremely high, a slight deformation during bending generates large stress and easily cracks. On the other hand, the structure of Patent Document 1 and Patent Document 2 is to suppress "occurrence of curl" due to shrinkage of the hard coat layer. The configuration of Patent Document 1, that is, “a hard coating film formed by laminating a coating layer having an elastic modulus in the range of 0.5 GPa to 4.5 GPa on a coating layer having an elastic modulus in the range of 1.0 GPa to 6.0 GPa” and the configuration of Patent Document 2, that is, “elastic modulus” When the present inventors investigated a hard coating film formed by laminating a coating layer having an elastic modulus in the range of 2.0 GPa to 4.5 GPa on a coating layer in the range of 1.5 GPa to 4.5 GPa, sufficient "flexibility" could not be obtained.

On the other hand, the configuration proposed in Patent Literature 3 is that "the elastic modulus σm of the hard coat layer formed closest to the substrate is higher than the elastic modulus σs of the surface hard coat layer". However, when the present inventors confirmed these structures, it was found that, conversely, a higher elastic modulus of the outermost layer is advantageous for surface hardness.

Further, the structure of Patent Document 4, that is, "a layer group having a high inorganic particle concentration of 30.0 vol% or more and 70.0 vol% or less of an inorganic particle concentration, and a layer having a low inorganic particle concentration of 0 vol% or more and 40.0 vol% or less of an inorganic particle concentration" In the hard coat layer in which groups are laminated alternately," an improvement in surface hardness is seen, but since the resin material is selected from highly crosslinkable actinic light curing resins, it is not designed to obtain flexibility in the first place.

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

In order to solve the above problems, the present inventors have completed the following inventions as a result of repeated research. That is, this invention is as follows.

(1) A laminate in which a surface layer is laminated on a support substrate, and in the distribution of the elastic modulus in the thickness direction of the surface layer, there is a maximum value having a higher modulus of elasticity than the modulus of elasticity of the supporting substrate and a minimum value having a lower modulus of elasticity than the modulus of elasticity of the supporting substrate, A layered product characterized in that both the modulus of elasticity at the interface side with the supporting substrate in the surface layer and the modulus of elasticity at the outermost surface side are higher than the modulus of elasticity of the supporting substrate.

(2) The laminate according to (1), characterized in that the maximum elastic modulus in the elastic modulus distribution in the thickness direction of the surface layer is 100 times or more and 10,000 times or less the minimum elastic modulus.

(3) The laminate according to (1) or (2), wherein the surface layer has a minimum modulus of elasticity of 0.1 GPa or less in the distribution of elastic modulus in the thickness direction.

(4) In the elastic modulus distribution in the thickness direction of the surface layer, a maximum value having an elastic modulus higher than the elastic modulus of the supporting base material and a local minimum value having a lower elastic modulus than the elastic modulus of the supporting base material alternately exist, and the thickness and elastic modulus calculated from the elastic modulus distribution are as follows The laminate according to any one of (1) to (3), which satisfies the relationship of

10≤(Tb[nm]/Ta[nm])×(Ea[MPa])/Eb[MPa])≤1,000... (Equation 1)

Ta [nm]: average value of the thickness of the part where the modulus of elasticity is higher than the modulus of elasticity of the supporting substrate

Tb [nm]: average value of the thickness of the part where the modulus of elasticity is lower than the modulus of elasticity 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 (1) to (4), wherein the surface layer contains inorganic particles having an anisotropic shape that satisfies the following.

1.2≤Rl/Rs≤20,000... (Equation 2)

1nm≤Rs≤100nm... (Equation 3)

Rl [nm]: major diameter of inorganic particles

Rs [nm]: short diameter of inorganic particles

(6) Any one of (1) to (5), characterized in that the frequency of existence F in the thickness direction of the inorganic particles having an anisotropic shape in a cross section perpendicular to the supporting substrate of the surface layer satisfies the following conditions: The laminate according to one claim.

Fa<Fb... (Equation 4)

Fa: Existence frequency of a part where the modulus of elasticity is higher than the modulus of elasticity of the supporting substrate

Fb: Existence frequency of a part where the modulus of elasticity is lower than the modulus of elasticity of the supporting base material

ADVANTAGE OF THE INVENTION According to this invention, the laminated body which made high surface hardness and flexibility compatible can be provided. The layered product of the present invention has excellent surface hardness compared to a resin layer having an equal thickness and is uniform, and at the same time, generation of curl due to stress concentration, cracking during bending, and peeling of the coating film can be suppressed.

1 is a schematic cross-sectional diagram of a laminate of the present invention and a conceptual diagram of elastic modulus distribution in the thickness direction in a cross-section.
2 is a conceptual diagram of the distribution of the modulus of elasticity in the thickness direction, the maximum modulus of elasticity, and the minimum modulus of elasticity.
3 is a conceptual diagram of the distribution of elastic modulus in the thickness direction, the maximum modulus of elasticity, the minimum modulus of elasticity, and their average values.
Fig. 4 is a conceptual diagram of a portion having a distribution of elastic modulus in the thickness direction and a portion having an elastic modulus higher than the elastic modulus of the supporting substrate, and a portion having the elastic modulus lower than the elastic modulus of the supporting substrate.
5 is an example of a manufacturing method for forming a surface layer (multilayer slide die coating).
6 is an example of a manufacturing method for forming a surface layer (multilayer slot die coating).
7 is an example of a manufacturing method for forming a surface layer (wet-on-wet coating).

In achieving the above object, its technical difficulty lies in coexistence of hardness, ie, high elastic modulus, and flexibility, ie, low elastic modulus. Although the inventions of Patent Literatures 1 to 4 all adjust the hardness and flexibility balance according to the elastic modulus, resin type, or particle amount of the material, these methods cannot achieve the above-mentioned problems. The reason for this is that the modulus of elasticity of the material used for imparting flexibility is too high.

Therefore, the inventors of the present invention first studied in detail "occurrence of scratches by the pencil hardness test" in terms of hardness. As a result, it was confirmed that the form of scratches generated in the pencil hardness test was classified into the following three categories. That is, they are (1) flaws resulting from the outermost surface of the film, (2) flaws resulting from the interface where the modulus of elasticity discontinuously changes within the film, and (3) flaws resulting from the supporting base material. That is, (1) is a scratch caused by insufficient hardness of the surface layer, (2) is a scratch caused between layers such as peeling at the interface, and (3) is a dent caused by bending of the base material. 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 of the surface layer has a high elastic modulus, (II) there is no stress strain in the surface layer and at the interface with the supporting substrate, , (III) three points of reducing the stress propagating to the base material.

Then, when the present inventors conducted an examination based on the above design guideline, it was found that a material having an elastic modulus lower than the elastic modulus of the supporting base material can be inserted into the surface layer that satisfies the conditions described below while maintaining the hardness of the surface. . That is, the present inventors have found a laminate having a surface layer as a surface layer of a laminate, which has excellent surface hardness as described above and at the same time suppresses curling due to stress concentration, cracking during bending, or peeling of a coating film. It demonstrates using drawing below.

First, the laminate of the present invention is a laminate 3 in which a surface layer 2 is laminated on one side of a supporting substrate 1 as shown in FIG. 1 . And, the surface layer 2 has a non-uniform elastic modulus distribution in its thickness direction. In addition, the elastic modulus of the surface layer may be a laminate in which a plurality of layers having different elastic moduli are stacked, as long as the conditions described later are satisfied, or a layer in which the elastic modulus is different in the thickness direction within the same layer.

In addition, the "elastic modulus of the cross section of a laminate" in the present invention is measured by an atomic force microscope. The elastic modulus measurement by an atomic force microscope is a compression test using a probe of a very small part, and the degree of deformation due to the compression force is measured. Therefore, the elastic modulus in the cross section of each position in the thickness direction of the surface layer is measured using a cantilever having a known spring constant. Specifically, the laminate is cut, and the modulus of elasticity in the cross section at each position in the thickness direction of the surface layer is measured with an atomic force microscope. Details are described in the section of Examples. Using an atomic force microscope shown below, the probe at the tip of the cantilever is brought into contact with the end face of the surface layer, and the force curve is measured with a pressing force of 55 nN. The resulting cantilever deflection amount is measured. can Further, at this time, the spatial resolution in the thickness direction depends on the scan range and the number of scan lines of the atomic force microscope, but the lower limit is about 50 nm under realistic measurement conditions. Details and measurement methods will be described later.

Atomic Force Microscope: MFP-3DSA-J manufactured by Asylum Technologies

Cantilever: NANOSENSORS cantilever "R150-NCL-10 (material Si, spring constant 48 N/m, tip curvature radius 150 nm).

Hereinafter, a preferable aspect of the modulus of elasticity of the surface layer will be described.

[Elastic modulus of support substrate and elastic modulus of surface layer]

First, in the "elastic modulus distribution in the thickness direction of the surface layer" in which the thickness of the surface layer as shown in FIG. 2 is plotted on the horizontal axis and the elastic modulus of the cross section measured by the above method is plotted on the vertical axis, "Comparison with elastic modulus 9 of the cross section of the supporting substrate Therefore, it is preferable that a portion having a high elastic modulus and a portion having a low elastic modulus exist.” In the case where the above-mentioned portion does not have a high elastic modulus, sufficient hardness may not be obtained because the elastic modulus of the surface layer is insufficient. Conversely, in the case of not having the portion having a low elastic modulus described above, flexibility, in particular, suppression of cracks against bending becomes insufficient, and the subject may not be achieved. In addition, "the distribution of elastic modulus in the thickness direction of the surface layer" is expressed as a continuous curve in Fig. 2, but in reality it is a set of data points measured at intervals of 100 nm. Regarding minute changes in elastic modulus at intervals of less than 100 nm, since they have little effect on the hardness or flexibility of the laminate, the influence of changes in elastic modulus that are not detected under the above measurement conditions can be practically ignored. In addition, the detail of the measuring method of "the elastic modulus distribution of the thickness direction of a surface layer" is mentioned later.

[The modulus of elasticity on the outermost surface side and the modulus of elasticity on the interface side with the supporting substrate]

In the present invention, it is preferable that both the elastic modulus of the outermost surface side and the elastic modulus of 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. In addition, the "interface" refers to the interface between the surface layer and the supporting substrate (ie, the boundary line between the surface layer and the supporting substrate). When the modulus of elasticity of the outermost surface side is lower than the modulus of elasticity of the supporting base material, even if there is a part having a higher elastic modulus inside, it may be easily damaged. In addition, when the modulus of elasticity of the interface side is lower than the modulus of elasticity of the supporting substrate, scratches caused by the supporting substrate may be easily generated. In particular, the elastic modulus of the outermost surface side is preferably the highest among the surface layers. Here, the "elastic modulus of the outermost surface side" is the elastic modulus of the outermost surface in the surface layer. However, in the measurement of the modulus of elasticity in the cross section, since the modulus of elasticity on the 4 lines in Fig. 1 located at the top surface is not an accurate value of the surface layer, in reality the value of the measurement point 5 100 nm inside from the top surface Let it be "elastic modulus of the outermost surface side." In addition, the "elastic modulus at the interface side" refers to the elastic modulus at the interface between the surface layer and the supporting substrate. However, in the measurement of the modulus of elasticity in the cross section, the modulus of elasticity on the line 6 in Fig. 1 located at the positive interface is not an accurate value of the interface, so in reality it is 100 nm from the boundary line 6 between the surface layer and the supporting substrate on the surface layer side Let the measured value (7) of "the elastic modulus on the interface side".

[Maximum modulus and minimum modulus of elasticity]

On the other hand, in the elastic modulus distribution in the thickness direction of the surface layer (FIG. 2), there is a gap between the "maximum modulus of elasticity (14)", which is the maximum value of the modulus of elasticity in the surface layer, and the "minimum modulus of elasticity (15)", which is the minimum value of the modulus of elasticity in the surface layer. A desirable relationship exists. Specifically, it is preferable that the maximum modulus of elasticity is 100 times or more and 10,000 times or less of 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 hardness or flexibility may be insufficient, and compatibility of the two may be difficult. On the other hand, when the ratio exceeds 10,000 times, distortion tends to occur in the surface layer due to a rapid change in elastic modulus, resulting in a decrease in pencil hardness and peeling of the film in some cases.

Additionally, there is a preferred numerical range for the minimum modulus of elasticity (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 modulus of elasticity is higher than 0.1 GPa, the aforementioned flexibility tends to be insufficient, and cracks and curls tend to occur in some cases.

Here, "maximum elastic modulus" means 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. In addition, "minimum elastic modulus" means the minimum value of the elastic modulus in the elastic modulus distribution of the thickness direction of the surface layer measured by the method mentioned later.

[Relationship between maximum elastic modulus and minimum elastic modulus and thickness]

Further in the surface layer, as a structure that makes it difficult to generate deformation distortion with respect to stress, a favorable relationship exists between the modulus of elasticity and the thickness. Specifically, in the distribution of elastic modulus in the thickness direction of the surface layer, as shown in FIG. It is desirable that there exists a local minimum value (minimum elastic modulus 18) lower than . Further, in the distribution of elastic modulus in the thickness direction of the surface layer, it is preferable that both the modulus of elasticity at the interface side with the supporting substrate in the surface layer and the modulus of elasticity at the outermost surface side are higher than the modulus of elasticity of the supporting substrate. Furthermore, in the distribution of elastic modulus in the thickness direction of the surface layer, as shown in FIG. The average value of the thickness 20 of the part where local minimum values (minimum elastic modulus 18) lower than that exist "alternatively" and the elastic modulus is higher than the elastic modulus 9 of the supporting base material, and the elastic modulus is higher than the elastic modulus 9 of the supporting base material It is more preferable that the average value of the thickness 21 of the lower portion satisfies the following relational expression.

10≤(Tb[nm]/Ta[nm])×(Ea[MPa])/Eb[MPa])≤1,000

Here, Ta [nm] is the average thickness value of the portion where the elastic modulus is higher than the elastic modulus of the supporting substrate, Tb [nm] is the average thickness value of the portion where the elastic modulus is lower than the elastic modulus of the supporting substrate, and Ea [MPa] is the average value of the maximum elastic modulus (17 ), and Eb [MPa] is the average value of the minimum elastic modulus (19).

Here, the maximum value (maximum modulus of elasticity 16) in which the modulus of elasticity is higher than the modulus of elasticity of the supporting base material means that the modulus of elasticity is higher than the modulus of elasticity of the supporting base material, and as shown in FIG. 3, the relationship between the thickness of the surface layer and the modulus of elasticity is graphed. In this case, it refers to the maximum value (the value at which the slope becomes zero). In addition, the minimum value (minimum modulus of elasticity 18) in which the modulus of elasticity is lower than the modulus of elasticity of the supporting base material is a case where the modulus of elasticity is lower than the modulus of elasticity of the supporting base material, and the relationship between the thickness of the surface layer and the modulus of elasticity is graphed as shown in FIG. , the local minimum (the value at which the slope is zero).

Further, in the distribution of the elastic modulus in the thickness direction of the surface layer, a maximum value having a higher modulus of elasticity than the modulus of elasticity of the supporting base material and a minimum value having a lower modulus of elasticity than the modulus of elasticity of the supporting base material alternately exist. When the elastic modulus distribution is measured, it means that all of the following requirements (1) to (4) are satisfied.

(1) There are at least two local maxima and two local minima.

(2) There is no local minimum value that is a higher modulus of elasticity than the modulus of elasticity of the supporting substrate.

(3) There is no maximum value that is an elastic modulus lower than the elastic modulus of the supporting base material.

(4) When the maxima and minima are arranged in order in the thickness direction, there is at least one permutation of (i) maxima-maxima-maxima-minima or (ii) minima-maximum-minima-maxima.

In addition, "the average value of the thickness of the part whose modulus of elasticity is higher than the modulus of elasticity of the support base material" refers to a value obtained by averaging the thickness of each part in which the modulus of elasticity existing in the surface layer is higher than the modulus of elasticity of the support base material. In addition, "the average value of the thickness of the part whose modulus of elasticity is lower than the modulus of elasticity of the support base material" refers to the value obtained by averaging the thickness of each part where the modulus of elasticity existing in the surface layer is lower than the modulus of elasticity of the support base material.

In addition, the average value of the maximum elastic modulus is the average value of the maximum values having a higher elastic modulus than the elastic modulus of the supporting substrate present in the surface layer, and the average value of the minimum elastic modulus is the average value of the minimum values having a lower elastic modulus than the elastic modulus of the supporting substrate present in the surface layer.

As the configuration of the surface layer that realizes the elastic modulus as described above, a layer with a high elastic modulus, that is, a hard layer, and a layer with a low elastic modulus, that is, a soft layer are alternately laminated to form a “multilayer structure” or any one without a clear interface. Although it is a layer, "inclined structure" etc. which have a distribution in elastic modulus by bias of constituent components, such as particle|grains and resin, are mentioned. Details of the structure of the surface layer and its manufacturing method will be described later in the section of [Production method of laminated body].

The relational expression described above is a parameter representing the "flexibility" of the layered product defined on the basis of the ratio of the elastic modulus and thickness of the components constituting the surface layer. The increase in this parameter corresponds to a relatively large increase in Tb, that is, "thickness of the portion where the modulus of elasticity is lower than the modulus of elasticity of the supporting base material," or a relatively small decrease in Eb, or "minimum modulus of elasticity," both of which correspond to the softness of the laminate. do. Conversely, a decrease in this parameter corresponds to an increase in the hardness of the laminate.

Specifically, when the above-mentioned relational expression is smaller than 10, the flexibility of the entire surface layer tends to be insufficient, and cracks and curls tend to occur in some cases. On the other hand, when it is larger than 1,000, the hardness of the entire surface layer tends to be insufficient, and in particular, peeling at the interface or decrease in pencil hardness may be caused.

When the above relational expression is decomposed into component A having a high elastic modulus and component B having a low elastic modulus, it can be decomposed into "Ea/Ta" and "Eb/Tb", that is, "(elastic modulus)/(coating film thickness)". On the other hand, when considering the resultant force acting on the spring, the "length of the spring" is a value in inverse proportion to the "spring constant", and in general, the value of the spring constant decreases as the length increases. Here, when considering press-in in the thickness direction, the "thickness of the coating film" is a value corresponding to the "length of the spring", and the thicker the thickness, the lower the spring constant. Therefore, it can be considered that the relational expression described above is a preferable numerical range of "spring constant corrected by the film thickness".

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described in detail.

[laminate and surface layer]

The "surface layer" in the present invention refers to a layer formed on a supporting substrate, and a combination of all of a series of layers including the surface layer and the supporting substrate is referred to as a "laminate". That is, when only one layer is formed on the supporting substrate, the one layer becomes the "surface layer". In addition, for example, when two or more layers are formed on a support base material, all the said two or more layers except a support base material shall be called one "surface layer."

Here, "layer" refers to a site that can be distinguished by having a boundary surface with a site adjacent to the thickness direction from the surface side of the laminate and has a finite thickness. More specifically, it refers to what is distinguished by the presence or absence of a discontinuous interface when cross-section of the said layered product is observed with an electron microscope (transmission type, scanning type) or an optical microscope. The laminate of the present invention may have either a flat state or a three-dimensional shape after molding, 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 repeated scratch resistance and moldability, which are the problems of the present invention, the laminate has antifouling properties, antireflection properties, antistatic properties, antifouling properties, conductivity, heat ray reflectance, near-infrared ray absorption, electromagnetic wave shielding properties, and easy adhesion. You may have a layer having other functions, such as, and these functions may be provided to the said surface layer.

[support material]

The material constituting the supporting base material used in the laminate of the present invention may be either a thermoplastic resin or a thermosetting resin, may be a homoresin, or may be a copolymerization or a blend of two or more types. More preferably, the resin constituting the supporting base material is preferably a thermoplastic resin in terms 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 polyarrays. Fluorine resins such as polyacetal resins, polyphenylene sulfide resins, tetrafluoroethylene resins, trifluoroethylene resins, trifluoroethylene chloride resins, tetrafluoroethylene-hexafluoropropylene copolymers, and vinylidene fluoride resins, acrylic resins , methacrylic resin, polyacetal resin, polyglycolic acid resin, polylactic acid resin and the like can be used. The thermoplastic resin is preferably a resin having sufficient stretchability and trackability. From the viewpoints of strength, heat resistance and transparency, the thermoplastic resin is more preferably a polyester resin, polycarbonate resin, or methacrylic resin, and a polyester resin is particularly preferred.

The polyester resin in the present invention is a general term for a polymer having an ester bond as a main bond chain of the main 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, and polybutylene terephthalate. Furthermore, what copolymerized these with another dicarboxylic acid and its ester or diol component as an acid component or a diol component may be used. Among these, polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferred in terms of transparency, dimensional stability, heat resistance and the like.

In addition, various additives such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducing agents, heat stabilizers, lubricants, infrared absorbers, ultraviolet absorbers, dope agents for adjusting the refractive index, etc. are added to the supporting substrate. There may be. The supporting substrate may have either a single layer configuration or a laminated configuration.

It is also possible to give various surface treatments to the surface of a support base material before forming the said surface layer. Examples of 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.

It is also possible to previously provide functional layers such as an easy-adhesive layer, an antistatic layer, an undercoat layer, and an ultraviolet ray absorbing layer separately from the surface layer of the present invention on the surface of the supporting base material, and it is particularly preferable to provide an easy-adhesive 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, the modulus of elasticity measured by the method described below is referred to as the modulus of elasticity of the supporting base material even if it is a supporting base material having no elastic modulus distribution or a supporting base material having an elastic modulus distribution in the thickness direction.

[Paint Composition]

In the laminate of the present invention, a surface layer having a structure capable of achieving the above-described physical properties can be formed by applying, drying, and curing a coating composition on a supporting substrate using a method for manufacturing a laminate described later. Here, "painting composition" is a liquid containing a solvent and a solute, and refers to a material capable of forming a surface layer by applying onto the above-described support substrate and volatilizing, removing, and curing the solvent in a drying step. Here, the "type" of the coating composition refers to liquids in which even some of the types of solutes constituting the coating composition are different. These solutes include resins or materials capable of forming them in the application process (hereinafter referred to as precursors), particles, and various additives such as polymerization initiators, curing agents, catalysts, leveling agents, ultraviolet absorbers, and antioxidants.

The surface layer of the present invention is composed of at least two types of coating compositions, the above-described coating composition A capable of forming "a portion having a high elastic modulus compared to the elastic modulus of the cross section of the supporting substrate" and coating composition B capable of forming a "portion having a low elastic modulus" It is preferable to form by sequential application or simultaneous application on a supporting substrate.

[Coating Composition A]

As the coating composition A, a hard coat porcelain that forms a coating layer having a high modulus of elasticity can be preferably used. As the modulus of elasticity of the coating layer monolayer film, it is preferable to have a modulus of elasticity of 6 GPa to 200 GPa. As specific components, it is preferable to have a highly cross-linkable binder component containing a large number of reactive sites and a particle component for imparting an elastic modulus. As a porcelain capable of forming a hard coating layer having a particularly high elastic modulus, it is preferable to use a composite porcelain of an organic material and an inorganic material, which is called an organic-inorganic hybrid porcelain. As an example of organic-inorganic hybrid porcelain, "Taishei Fine Chemical Co., Ltd.; (organic-inorganic hybrid coating material “STR-SiA”)” or “Toagosei Co., Ltd.; (trade name "light curing type SQ series")" or "Toyo Ink Co., Ltd.; (trade name "Rioduras" (registered trademark))" and the like, and it is possible to use these materials suitably. Further, as a representative form of the organic-inorganic hybrid porcelain, it is preferable to include inorganic particles having a high elastic modulus and a highly crosslinkable binder containing an organic compound. Preferred particle components and binder components are described later.

[Paint Composition B]

As the coating composition B, a resin ceramic material having excellent flexibility and moldability can be suitably used. As the elastic modulus of the coating layer single film, it is preferable to have an elastic modulus of 1 MPa to 100 MPa. Specifically, those commercially available as scratch-repairing porcelain, moldable HC (Hard Coating) porcelain, or adhesive can be suitably used. Part of it may also contain particulate material.

Examples of scratch-repairing porcelain and moldable HC porcelain include "Chugoku Paint Co., Ltd.; (trade name "Porcid" series)" or "Aika Kogyo Co., Ltd.; (trade name “Aikaitron” series)” and the like. In addition, as an example of an adhesive, as an acrylic adhesive, "Toagosei Co., Ltd.; “Aaron Tag” series”, “Soken Kagaku Co., Ltd.; "SK Dyne" (registered trademark) series" etc. Examples of silicone adhesives include adhesives of "Toray Dow Corning Co., Ltd." and "Shin-Etsu Silicone Co., Ltd.", respectively. More preferable paint components are described later.

[Particle Material, Particle Component]

The surface layer of the layered product of the present invention preferably contains particle components, and 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 preferable from the viewpoint of durability.

As the number of types of inorganic particles, 1 or more types and 20 or less types are preferable. As for the number of types of inorganic particles, 1 or more types and 10 types or less are more preferable, and 1 or more types and 4 types or less are especially preferable. Here, "inorganic particles" include those subjected to surface treatment. This surface treatment is to introduce a compound onto the particle surface by chemical bonding (including covalent bonding, hydrogen bonding, ionic bonding, van der Waals bonding, hydrophobic bonding, etc.) or adsorption (including physical adsorption and chemical adsorption). point to

Here, the type of inorganic particles is determined by the types of elements constituting the inorganic particles, and in the case of performing any kind of surface treatment, it is determined by the types of elements constituting the particles before surface treatment. For example, since the elements constituting the inorganic particles are different from titanium oxide (TiO ₂ ) and nitrogen-doped titanium oxide (TiO _{2 - x} N _x ) in which a part of titanium oxide's oxygen is replaced with anion nitrogen, They are different types of inorganic particles. In addition, as long as the particles (ZnO) contain the same element, for example, only Zn and O, even if a plurality of particles having different number average particle diameters exist, and even if the composition ratio of Zn and O is different, these are the same type of particles. . In addition, even if there are a plurality of Zn particles with different oxidation numbers, they are the same type of particles as long as the elements constituting the particles are the same (in this example, as long as all elements other than Zn are the same).

In addition, the particles included in the coating composition suitable for forming the surface layer of the present invention are in a form in which their surface state is changed by heat or ionizing radiation in a treatment such as coating, drying, curing treatment, or deposition, and the surface layer included in Here, the particles present in the coating composition used in the present invention are referred to as "particle material", and the particles present in the surface layer formed by coating, drying, curing treatment, or deposition of the coating composition are referred to as "particle component". .

The inorganic particles are not particularly limited, but are preferably oxides, nitrides, borides, chlorides, carbonates, or sulfates of metals or semimetals, and complex oxides containing two types of metals or semimetals or two elements between the lattice may be introduced, lattice points may be substituted with a different type of element, or lattice defects may be introduced.

More preferably, the inorganic particles are oxide particles obtained by oxidizing 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. do.

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 semi-metal 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 forming the surface layer of the present invention, those having surface modification necessary for stably dispersing silica in a good solvent for the binder raw material are particularly preferred. For example, when using an acrylic monomer or oligomer as a binder raw material, as a surface modification, an alkyl group having 1 to 5 carbon atoms, an alkenyl group, a vinyl group, a (meth)acrylic group, or the like is introduced into the surface of the minimum required particle component. It is desirable to be

Here, the number average particle diameter of inorganic particles means the number standard arithmetic average length diameter described in JIS Z8819-2 (2001). In any of the particle components and particle materials, primary particles are observed using a scanning electron microscope (SEM), transmission electron microscope, etc., and the diameter of the circumscribed circle of each primary particle is taken as the particle diameter, and the average value based on the number is obtained. point to the value In the case of a laminate, the number average particle diameter can be obtained by observing the surface or cross section, and in the case of a coating composition, a sample can be prepared and observed by dropping a coating composition diluted with a solvent and drying.

[Inorganic particles having an anisotropic shape]

Furthermore, it is particularly preferable that the surface layer of the laminate of the present invention contains inorganic particles having an anisotropic shape. In addition, the coating composition suitable for forming the surface layer of the present invention preferably contains inorganic particles having an anisotropic shape, and in particular, it is preferable to include inorganic particles having an anisotropic shape in the coating composition B. Here, inorganic particles having an anisotropic shape means particles whose shape is not spherical but biased, and specifically means beads-shaped particles in which needle-shaped, plate-shaped, or spherical particles are chained together. . When the inorganic particles included in the surface layer have an anisotropic shape as described above, hardness of the surface layer can be imparted while maintaining the flexibility of the entire laminate. Although the cause of coexistence of flexibility and hardness is not clear, it has been confirmed that by adding inorganic particles having an anisotropic shape, only the stress in the shear direction increases while the stress in the press-fitting direction is maintained. It is presumed to be able to suppress the destruction.

A preferable shape exists in the inorganic particle which has the said anisotropic shape. Specifically, Rl/Rs, which is the ratio of the major diameter Rl to the minor 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. When R1/Rs is smaller than 1.2, the above-described difference between indentation stress and shear stress is less likely to occur, and the flexibility of the surface layer may decrease. On the other hand, even if Rl/Rs is high, the performance of the laminate does not immediately deteriorate. However, when Rl/Rs exceeds 20,000, thixotropic properties occur in the porcelain, making it difficult to apply uniformly.

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 not satisfied with 1 nm, the volume ratio of the inorganic particles occupied in the layered product decreases, and sufficient hardness improvement effect may not be obtained. On the other hand, when Rs exceeds 100 nm, the contribution to the above-mentioned indentation stress increases, and the flexibility of the surface layer may decrease. The method for measuring the major diameter Rl and the minor diameter Rs will be described later.

In addition, the above-mentioned difference between the indentation stress and the shear stress is particularly remarkable when the binder component described later is a flexible binder, so that the inorganic particles having an anisotropic shape have a lower modulus of elasticity of the layered product than that of the supporting base material. It is particularly preferred that the presence of a large amount in the portion. Specifically, the frequency of existence of inorganic particles having an anisotropic shape described later satisfies (Equation 4), that is, the elastic modulus of the laminate is higher than the elastic modulus of the supporting base material than the part where the elastic modulus of the laminate is higher than the elastic modulus of the supporting base material. More in the lower part is desirable. When the frequency of existence of inorganic particles having an anisotropic shape in a portion where the modulus of elasticity of the layered product is higher than that of the supporting base material is high, the effect of suppressing breakage of the layered film due to shear cannot be sufficiently obtained, or the coating film Since the flexibility is lowered, it may be difficult to achieve both flexibility and hardness of the laminate.

Inorganic particles having an anisotropic shape are oxide particles obtained by oxidizing 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. It is more preferable to be

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 semi-metal 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) 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 binding agent 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 called "binder material", and the binder present in the surface layer formed by coating, drying, curing treatment, or deposition of the coating composition is called "binder component". In addition, a reactive site|part refers to the site|part which reacts with another component by external energy, such as heat or light. Preferable examples of these reactive sites include an alkoxysilyl group and a silanol group obtained by hydrolysis of an alkoxysilyl group, a carboxyl group, a hydroxyl group, an epoxy group, a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group from the viewpoint of reactivity. . In addition, it is preferable that the coating composition A suitable for forming the surface layer of the present invention contains at least a "highly cross-linkable binder" described later, and the coating composition B preferably contains at least a "flexible binder" described later, and these binders may be contained at the same time.

[Highly cross-linkable binder]

The highly crosslinkable binder can be suitably used mainly as a binder component of the coating composition A, and may be included in the coating composition B from the viewpoint of improving adhesion or film formation. A material having 2 or more and 20 or less reactive sites in one molecule is preferable. Moreover, either of a thermosetting resin and an ultraviolet curable resin may be sufficient, and a blend of two or more types may be sufficient.

The thermosetting resin suitable for the highly crosslinkable binder includes a resin containing a hydroxyl group and a polyisocyanate compound, and the resin containing a hydroxyl group includes acrylic polyol, polyether polyol, polyester polyol, polyolefin polyol, polycarbonate polyol, and urethane. Polyol etc. are mentioned, These may be 1 type or a blend of 2 or more types. If the hydroxyl value of the resin containing a hydroxyl group is in the range of 1 to 200 mgKOH/g, it is preferable from the viewpoints of durability, hydrolysis resistance, and adhesion when used as a coating film. When the hydroxyl value is less than 1, curing of the coating film hardly proceeds, and durability or strength may decrease. On the other hand, since cure shrinkage is too large when hydroxyl group is larger than 200, adhesiveness may be reduced.

The acrylic polyol containing a hydroxyl group in the present invention is obtained by polymerization using, for example, an acrylic acid ester or a methacrylic acid ester as a component. Such an acrylic resin can be easily produced by, for example, copolymerizing a carboxylic acid group-containing monomer such as (meth)acrylic acid, itaconic acid, or maleic anhydride with (meth)acrylic acid ester as a component as needed. As (meth)acrylic acid ester, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth) ) acrylate, 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, and the like. As an acrylic polyol containing such a hydroxyl group, it is DIC Corporation, for example; (trade name "Acridic" (registered trademark) series, etc.), Daisei Fine Chemical Co., Ltd.; (trade name "Acryte" (registered trademark) series, etc.), Nippon Shokubai Co., Ltd.; (trade name "Acryset" (registered trademark) series, etc.), Mitsui Chemical Co., Ltd.; (trade name "Takerac" (registered trademark) UA series), etc., and these products 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; An aliphatic poly reacted as an essential raw material component with aliphatic dibasic acids such as succinic acid, adipic acid, sebacic acid, fumaric acid, suberic acid, azelaic acid, 1,10-decamethylene dicarboxylic acid, and cyclohexanedicarboxylic acid. Examples thereof include aromatic polyester polyols obtained by reacting ester polyols, aliphatic glycols such as ethylene glycol, propylene glycol, and butanediol with aromatic dibasic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid as essential raw material components. .

As polyester polyol containing such a hydroxyl group, DIC Corporation; (trade name "Polylite" (registered trademark) series, etc.), Kuraray Co., Ltd.; (trade name "Kurare Polyol" (registered trademark) series, etc.), Takeda Yakuhin Kogyo Co., Ltd.; (trade name "Takerac" (registered trademark) U series), and products thereof can be used.

As the polyolefin-based polyol containing a hydroxyl group in the present invention, polymers and copolymers of diolefins having 4 to 12 carbon atoms such as butadiene and isoprene, diolefins having 4 to 12 carbon atoms and α-olefins having 2 to 22 carbon atoms Among the copolymers of , it is a compound containing a hydroxyl group. The method of containing the hydroxyl group is not particularly limited, but there is, for example, a method of reacting a diene monomer with hydrogen peroxide. In addition, you may make it saturated aliphatic by hydrogenating the remaining double bond. As polyolefin type polyol containing such a hydroxyl group, Nippon Soda Co., Ltd.; (trade name "NISSO-PB" (registered trademark) G series, etc.), Idemitsu Kosan Co., Ltd.; (trade name "Poly bd" (registered trademark) series, "Epol" (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. Since the crystallinity is lower, polycarbonate polyol obtained by copolymerizing 1,6-hexanediol with 1,4-butanediol, 1,5-pentanediol or 1,4-cyclohexanedimethanol as a diol It is preferable to use

As a polycarbonate polyol containing such a hydroxyl group, Asahi Kasei Chemicals Co., Ltd. which is a copolymerization polycarbonate polyol; (trade names "T5650J", "T5652", "T4671", "T4672", etc.), Ube Kosan Co., Ltd.; (trade name "ETERNACLL" (registered trademark) UM series, etc.), and these products can be used.

The urethane polyol containing a hydroxyl group in the present invention is obtained, for example, by reacting 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. As a polyisocyanate compound used in that case, hexamethylene diisocyanate, toluene diisocyanate, m-xylene diisocyanate, isophorone diisocyanate, etc. are mentioned. Moreover, as a compound containing at least 2 hydroxyl group in 1 molecule, polyhydric alcohol, polyester diol, polyethylene glycol, polypropylene glycol, polycarbonate diol, etc. are mentioned.

As a polyisocyanate compound used for the thermosetting resin in this invention, resin containing an isocyanate group, and the monomer or oligomer containing an isocyanate group are pointed out. Examples of the compound containing an isocyanate group include methylenebis-4-cyclohexyl isocyanate, a trimethylolpropane adduct of tolylene diisocyanate, a trimethylolpropane adduct of hexamethylene diisocyanate, and a trimethylolpropane of isophorone diisocyanate. (poly)isocyanates such as adducts, tolylene diisocyanate isocyanurate, hexamethylene diisocyanate isocyanurate, hexamethylene isocyanate biuret, and blocks of the isocyanates. As a polyisocyanate compound used for such a thermosetting resin, Mitsui Chemicals Co., Ltd.; (trade name "Takenate" (registered trademark) series, etc.), Nippon Polyurethane Kogyo Co., Ltd.; (trade name "Coronate" (registered trademark) series, etc.), Asahi Kasei Chemicals Co., Ltd.; (trade name "Duranate" (registered trademark) series, etc.), DIC Corporation; (trade name "Bernock" (registered trademark) series, etc.).

On the other hand, as suitable ultraviolet curable resins in the highly crosslinkable binder, polyfunctional acrylate monomers, oligomers, alkoxysilanes, alkoxysilane hydrolysates, alkoxysilane oligomers, urethane acrylate oligomers and the like are preferable, and polyfunctional acrylate monomers and oligomers , urethane acrylate oligomers are more preferred.

Examples of the polyfunctional acrylate monomer include polyfunctional acrylates having two or more (meth)acryloyloxy groups in one molecule and modified polymers thereof. As specific examples, 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, etc. can be used. These monomers can be used singly or in combination of two or more.

Moreover, as a polyfunctional acrylic composition marketed, it is Mitsubishi Rayon Co., Ltd.; (trade name "Diabeam" (registered trademark) series, etc.), Nippon Kosei Kagaku Kogyo Co., Ltd.; (trade name "SHIKOH" (registered trademark) series, etc.), Nagase Sangyo Co., Ltd.; (trade name "Denacol" (registered trademark) series, etc.), Shin Nakamura Chemical Co., Ltd.; (trade name "NK Ester" series, etc.), DIC Corporation; (trade name "UNIDIC" (registered trademark), etc.), Toagosei Co., Ltd.; (“Aronix” (registered trademark) series, etc.), Nichiyu Co., Ltd.; (“Blemmer” (registered trademark) series, etc.), Nippon Kayaku Co., Ltd.; (trade name "KAYARAD" (registered trademark) series, etc.), Kyoeisha Chemical Co., Ltd.; (trade name "Light Ester" series, etc.), etc., and these products can be used.

[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 per molecule is preferable, and a form in which active reactive sites are inactivated may be used, such as in an acrylic polymer. Preferable 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 porcelain" having an elongation at break of about 5 to 50%, and an "adhesive".

As a coating composition forming a scratch-repairing resin layer, (1) a segment containing at least one selected from the group consisting of a polycaprolactone segment, a polycarbonate segment, and a polyalkylene glycol segment as a solute, (2) urethane It is particularly preferred to include a resin or precursor comprising a segment of linkage. Each of these segments can be confirmed by TOF-SIMS, FT-IR, or the like.

On the other hand, as the pressure-sensitive adhesive, "rubber-based pressure-sensitive adhesive" made of the most general-purpose rubber and tackifier, "acrylic pressure-sensitive adhesive" capable of imparting various functions with a copolymer of acrylic polymer, having excellent temperature characteristics and chemical resistance, but high cost Although it is possible to use any "silicone-type adhesive" suitably, it is especially preferable to use an "acrylic-type adhesive" from the viewpoint of compatibility with a high elastic modulus layer and cost.

[menstruum]

The coating composition A and the coating composition B preferably contain a solvent. The number of solvents is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, still more preferably 1 or more and 6 or less. Here, "solvent" refers to a substance that is liquid at normal temperature and normal pressure, which can be removed from the coating film by evaporating almost the entire amount in the drying step after application.

Here, the type of solvent is determined by the molecular structure constituting the solvent. That is, those with the same elemental composition and the same type and number of functional groups have different bonding relationships (structural isomers), and those that are not structural isomers but do not overlap completely no matter what configuration they take in three-dimensional space (stereoisomers) Treat it as a different kind of solvent. For example, 2-propanol and n-propanol are treated as different solvents.

[Other additives]

It is preferable that the said coating composition A and coating composition B contain a polymerization initiator, a hardening|curing agent, and a catalyst. A polymerization initiator and catalyst are used to accelerate curing of the surface layer. The polymerization initiator is preferably one capable of initiating or accelerating a polymerization, condensation or crosslinking reaction of components included in the coating composition by anionic, cationic, radical polymerization or the like.

A variety of polymerization initiators, curing agents and catalysts can be used. In addition, the polymerization initiator, curing agent and catalyst may be used alone, respectively, or a plurality of polymerization initiators, curing agent and catalyst may be used simultaneously. Moreover, you may use together an acidic catalyst, a thermal polymerization initiator, and a photoinitiator. As an example of an acidic catalyst, aqueous hydrochloric acid, formic acid, acetic acid, etc. are mentioned. Examples of thermal polymerization initiators include peroxides and azo compounds. Moreover, examples of the photopolymerization initiator include alkylphenone-based compounds, sulfur-containing compounds, acylphosphine oxide-based compounds, and amine-based compounds.

As a photoinitiator, an alkylphenone type compound is preferable from a curable viewpoint. Specific examples of the alkylphenone compound include 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-(4-methylthio Phenyl)-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-phenylpropan-1-one, 1-[ 4-(2-ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2-phenyl-2-oxoacetic acid)oxybisethylene and their materials for high molecular weight anger, and the like.

Further, the progress of the polymerization reaction by the thermal polymerization initiator or the photopolymerization initiator can be controlled by the amount of heat or light added, and when the surface layer is formed by sequential application, the next layer is applied with the progress of polymerization incomplete. By application, it is possible to make a mixed layer having intermediate physical properties without forming a clear interface.

In addition, as long as the effect of the present invention is not impaired, a leveling agent, a UV absorber, a lubricant, an antistatic agent, and the like may be added to the coating composition A and coating composition B used to form the surface layer. Thereby, the surface layer may contain a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, and the like. As an example of a leveling agent, an acrylic copolymer or a silicone-type, fluorine-type leveling agent is mentioned. Specific examples of the ultraviolet absorber include benzophenone-based, benzotriazole-based, oxalate anilide-based, triazine-based, and hindered amine-based ultraviolet absorbers. Examples of the antistatic agent include metal salts such as lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, and calcium salts.

[Method of manufacturing laminated body]

It is more preferable to use the manufacturing method in which at least the above-mentioned coating composition A and the above-mentioned coating composition B are formed by applying-drying-curing at least the above-mentioned coating composition B on the above-mentioned support substrate sequentially or simultaneously as the manufacturing method of the laminate of this invention.

Here, "applying sequentially" or "sequential application" means to form a surface layer by applying, drying, and curing one type of coating composition, and subsequently applying, drying, and curing another type of coating composition. there is. The surface layer formed in "sequential application" can control the magnitude and gradient of the elasticity modulus between the surface side and the base material side, and the magnitude of the elastic modulus between the base material and the surface layer, by appropriately selecting the type and number of coating compositions to be used. The surface layer formed by "sequential application" usually has a "multilayer structure" having a plurality of interfaces, but by appropriately selecting the type and composition of the coating composition, drying conditions, and curing conditions, the material species between the coating layers are separated and diffused. It is also possible to control and form a pseudo inclined structure. With the layer structure as described above, the elastic modulus distribution in the surface layer can be changed stepwise or continuously.

As another manufacturing method, it is a method of forming by coating, drying, and curing two or more types of coating compositions "simultaneously" on a support base material. The number of types of coating composition is not particularly limited as long as it is two or more types. Here, “simultaneous application” or “simultaneous application” intends to apply two or more types of liquid films on a supporting substrate in the application step, and then to dry and cure them. The surface layer formed in "simultaneous application" forms a "gradient structure" without a clear interface.

In the present manufacturing method, the coating method, when the above-described coating composition is sequentially applied, is a dip coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method (US Patent No. 2681294 specification), etc. It is preferable to form a surface layer by applying to a support substrate or the like by

In addition, in the case of simultaneous application of two or more types of coating compositions described above, "multilayer slide die coating" (FIG. 5) in which liquid films are applied after sequentially stacking liquid films in a state before application, or "multilayer slide die coating" (FIG. 5) laminated simultaneously with application on a substrate slot die coating” (FIG. 6), and “wet-on-wet coating” (FIG. 7) in which another layer is laminated in an undried state after forming one layer of liquid film on a support substrate. .

Subsequently, the liquid film applied on the support substrate or the like is dried. In addition to completely removing the solvent from the obtained laminate, it is preferable to accompany the heating of the liquid film in the drying step.

Regarding the drying method, electrothermal drying (adherence to a high-temperature object), convective heat transfer (hot air), radiant heat transfer (infrared rays), others (microwave, induction heating) and the like can be cited. Among these, in the production method of the present invention, a method using convective heat transfer or radiant heat transfer is preferable because of the need to accurately uniformize the drying speed even in the width direction.

Further, an additional hardening operation (hardening step) by irradiation with heat or energy rays may be performed. In the curing step, when curing by heat using the coating composition A and the coating composition B, it is preferably from room temperature to 200 ° C. or less, and from the viewpoint of the activation energy of the curing reaction, 80 ° C. or more and 200 ° C. or less are more preferred, In order to form a mixed layer having intermediate physical properties described above, it is more preferably 80°C or more and 100°C or less.

Moreover, when hardening with an active energy ray, it is preferable that it is an electron beam (EB ray) and/or an ultraviolet ray (UV ray) from a general purpose point. In the case of curing with ultraviolet rays, the oxygen concentration is preferably as low as possible, and curing in a nitrogen atmosphere (nitrogen purge) is more preferable from the point of being able to prevent oxygen inhibition on the outermost surface. When the oxygen concentration is high, curing of the outermost surface may be inhibited, resulting in insufficient curing of the surface. On the other hand, in the layer forming the inside of the surface layer, oxygen inhibition is promoted on the contrary, so that the next coated layer becomes easier to permeate, and it is easier to form a mixed layer having the above-mentioned intermediate physical properties, so it is preferable.

Moreover, as a kind of ultraviolet lamp used when irradiating an ultraviolet-ray, a discharge lamp system, a flash system, a laser system, an electrodeless lamp system etc. are mentioned, for example. When ultraviolet curing is performed using a high-pressure mercury lamp, which is a discharge lamp method, the ultraviolet ray intensity is 100 to 3,000 mW/cm 2 , preferably 200 to 2,000 mW/cm 2 , and more preferably 300 to 1,500 mW/cm 2 . It is preferable to irradiate, and it is preferable to irradiate with ultraviolet rays under the condition that the cumulative amount of ultraviolet rays 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 . . Here, the illuminance of ultraviolet light is the intensity of irradiation received per unit area, and varies depending on lamp output, emission spectrum efficiency, diameter of a light emitting valve, design of a reflector, and distance of a light source from an object to be irradiated. However, the illuminance does not change depending on the conveyance speed. In addition, the cumulative amount of ultraviolet light is irradiation energy received per unit area, and is the total amount of photons reaching the surface. The accumulated light amount is in inverse proportion to the irradiation speed passing under the light source and is proportional to the number of times of irradiation and the number of lamps.

[Examples of use]

The laminate of the present invention can be widely used for members having curved surfaces, such as electrical appliances, automobile interior members, building members, etc., in order to achieve both excellent surface hardness and flexibility.

For example, plastic molded products such as eyeglasses/sunglasses, dressing boxes, and food containers, smartphone housings, touch panels, keyboards, home appliances such as TV/air conditioner remote controls, buildings, dashboards, car navigation touch panels, and rooms. It can be suitably used for interior parts of vehicles such as mirrors and surfaces of various printed materials.

Example

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

<Combination of coating composition A>

[Coating Composition A1]

The following materials were mixed and diluted using ethyl acetate to obtain coating composition A1.

・Organic-inorganic hybrid HC porcelain 80.0 parts by mass

("Aika Aitron" Z-729-18 Aika High School Co., Ltd.)

- 20.0 parts by mass of ethyl acetate.

[Coating Composition A2]

18.8 parts by mass of dipentaerythritol hexaacrylate

Particle additive C1 (silica particle dispersion) 44.4 parts by mass

("MEK-AC-2140Z" Nissan Kagaku High School Co., Ltd.)

・Ethyl acetate 35.6 parts by mass

1.2 parts by mass of radical photopolymerization initiator

(“Irgacure” (registered trademark) 184 BASF Japan Co., Ltd.).

[Coating Composition A3]

38.8 parts by mass of dipentaerythritol hexaacrylate

・Ethyl acetate 60.0 parts by mass

1.2 parts by mass of radical photopolymerization initiator

(“Irgacure” (registered trademark) 184 BASF Japan Co., Ltd.).

[Coating Composition A4]

36.8 parts by mass of dipentaerythritol hexaacrylate

("Aika Aitron" Z-729-18 Aika High School Co., Ltd.)

・Particle additive C3 2.0 parts by mass

・Ethyl acetate 60.0 parts by mass

1.2 parts by mass of radical photopolymerization initiator

(“Irgacure” (registered trademark) 184 BASF Japan Co., Ltd.).

<Combination of coating composition B>

<Synthesis of urethane acrylate>

[Toluene solution of urethane acrylate 1]

50 parts by mass of toluene, isocyanurate-modified type of hexamethylene diisocyanate (Takenate D-170N manufactured by Mitsui Chemical Co., Ltd.) 50 parts by mass, polycaprolactone-modified hydroxyethyl acrylate (Daicel Chemical Industry Co., Ltd. 76 parts by mass of Flaxel FA5 by Shikigai Co., Ltd., 0.02 part by mass of dibutyltin laurate, and 0.02 part by mass of hydroquinone monomethyl ether were mixed, and maintained 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 form of hexamethylene diisocyanate (Mitsui Chemical Co., Ltd. Takenate D-170N, isocyanate group content: 20.9 mass%) 50 parts by mass, polyethylene glycol monoacrylate (Nichiyu Co., Ltd. 53 parts by mass of Lemmer AE-150 (hydroxyl value: 264 (mgKOH/g)), 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether were added, and the reaction was carried out by holding at 70° C. for 5 hours. After completion of the reaction, 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 coating composition B1.

- 50% by mass solid content concentration of urethane acrylate 1 - toluene solution 4.9 parts by mass

- Solid content concentration of urethane acrylate 2 50% by mass - toluene solution 4.9 parts by mass

・Ethyl acetate 90.05 parts by mass

・ Radical photopolymerization initiator 0.15 parts by mass

(“Irgacure” (registered trademark) 184 BASF Japan Co., Ltd.).

[Coating Composition B2]

The following materials were mixed and diluted using ethyl acetate to obtain coating composition B2.

・Self-healing paint 7.1 parts by mass

("Forcid" NO.521C Chugoku Paint Co., Ltd.)

· 92.86 parts by mass of ethyl acetate.

[Coating Composition B3]

The following materials were mixed and diluted with ethyl acetate to obtain coating composition B3.

・Acrylic adhesive 16.7 parts by mass

("SK Dine" 1439U Soken Kagaku Co., Ltd.)

・Ethyl acetate 83.26 parts by mass

・0.08 parts by mass of curing agent

(Hardener E-50C Soken Chemical Co., Ltd.).

[Coating Composition B4]

- Solid content concentration of urethane acrylate 1 50% by mass - toluene solution 4.85 parts by mass

- 50% by mass solid content concentration of urethane acrylate 2 - 4.85 parts by mass of toluene solution

・Particle additive C2 0.1 parts by mass

・Ethyl acetate 90.05 parts by mass

・ Radical photopolymerization initiator 0.15 parts by mass

(“Irgacure” (registered trademark) 184 BASF Japan Co., Ltd.).

[Coating Composition B5]

- Solid content concentration of urethane acrylate 1 50% by mass - toluene solution 4.85 parts by mass

- 50% by mass solid content concentration of urethane acrylate 2 - 4.85 parts by mass of toluene solution

・Particle additive C3 0.1 parts by mass

・Ethyl acetate 90.05 parts by mass

・ Radical photopolymerization initiator 0.15 parts by mass

(“Irgacure” (registered trademark) 184 BASF Japan Co., Ltd.).

[Coating Composition B6]

- Solid content concentration of urethane acrylate 1 50% by mass - toluene solution 4.85 parts by mass

- 50% by mass solid content concentration of urethane acrylate 2 - 4.85 parts by mass of toluene solution

・Particle additive C4 0.1 parts by mass

・Ethyl acetate 90.05 parts by mass

・ Radical photopolymerization initiator 0.15 parts by mass

(“Irgacure” (registered trademark) 184 BASF Japan Co., Ltd.).

[Coating Composition B7]

- Solid content concentration of urethane acrylate 1 50% by mass - toluene solution 4.85 parts by mass

- 50% by mass solid content concentration of urethane acrylate 2 - 4.85 parts by mass of toluene solution

・Particle additive C5 0.1 parts by mass

・Ethyl acetate 90.05 parts by mass

・ Radical photopolymerization initiator 0.15 parts by mass

(“Irgacure” (registered trademark) 184 BASF Japan Co., Ltd.).

[Coating Composition B8]

- Solid content concentration of urethane acrylate 1 50% by mass - toluene solution 4.85 parts by mass

- 50% by mass solid content concentration of urethane acrylate 2 - 4.85 parts by mass of toluene solution

・Particle additive C6 0.1 part by mass

・Ethyl acetate 90.05 parts by mass

・ Radical photopolymerization initiator 0.15 parts by mass

(“Irgacure” (registered trademark) 184 BASF Japan Co., Ltd.).

[Coating Composition B9]

- Solid content concentration of urethane acrylate 1 50% by mass - toluene solution 4.85 parts by mass

- 50% by mass solid content concentration of urethane acrylate 2 - 4.85 parts by mass of toluene solution

・Particle additive C7 0.1 parts by mass

・Ethyl acetate 90.05 parts by mass

・ Radical photopolymerization initiator 0.15 parts by mass

(“Irgacure” (registered trademark) 184 BASF Japan Co., Ltd.).

[Paint Composition B10]

- Solid content concentration of urethane acrylate 1 50% by mass - toluene solution 4.85 parts by mass

- 50% by mass solid content concentration of urethane acrylate 2 - 4.85 parts by mass of toluene solution

・Particle additive C8 0.1 part by mass

・Ethyl acetate 90.05 parts by mass

・ Radical photopolymerization initiator 0.15 parts by mass

(“Irgacure” (registered trademark) 184 BASF Japan Co., Ltd.).

<Particle Additive C>

As the particle additive C, each of the following particle dispersions was used. Table 1 shows details of the shape of each particle component.

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 Chemicals 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) 1wt% IPA Dispersion

Particle additive C5: chain-shaped silica particle dispersion ("MEK-ST-UP" Nissan Chemical Industries, Ltd.)

Particle additive C6: boehmite dispersion (fibrous boehmite sol manufactured by Kawaken Fine Chemicals 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 manufacturing laminated body>

As a support substrate, "Lumiror" (registered trademark) U48 (manufactured by Toray Industries, Ltd.) having a thickness of 50 mu m and having an easy-adhesive paint applied on a PET resin film was used. Coating compositions A and B were applied on the supporting substrate using a wire bar by adjusting the number so that the thickness of the surface layer after drying had a specified film thickness, and then a drying step and a curing step were performed under the following conditions. A surface layer was formed on the supporting substrate by sequentially repeating these series of application, drying, and curing.

In addition, Table 1 shows the manufacturing method of the laminate corresponding to each Example and Comparative Example, the coating composition to be used, and the theoretical film thickness of each layer.

"The drying process of UV curing 1"

Blowing Temperature and Humidity: Temperature: 80℃

Wind speed: coated surface side: 5 m/sec, semi-coated surface side: 5 m/sec

Wind direction: coated surface side: parallel to the surface of the substrate, uncoated surface side: perpendicular to the surface of the substrate

Dwell time: 2 minutes

"The curing process of UV curing 1"

Accumulated light amount: 120mJ/cm2

Oxygen concentration: 200 ppm or less.

"The drying process of UV curing 2"

Blowing Temperature and Humidity: Temperature: 80℃

Wind speed: coated surface side: 5 m/sec, semi-coated surface side: 5 m/sec

Wind direction: coated surface side: parallel to the surface of the substrate, uncoated surface side: perpendicular to the surface of the substrate

Dwell time: 2 minutes

"The curing process of UV curing 2"

Accumulated light amount: 120mJ/cm2

Oxygen concentration: atmospheric atmosphere.

"Drying and curing process of heat curing 1"

Blowing Temperature and Humidity: Temperature: 80℃

Wind speed: coated surface side: 5 m/sec, semi-coated surface side: 5 m/sec

Wind direction: coated surface side: parallel to the surface of the substrate, uncoated surface side: perpendicular to the surface of the substrate

Dwell time: 2 minutes

The laminates of Examples 1 to 19 and Comparative Examples 1 to 6 were produced by the above method.

<Evaluation of laminate>

About the produced laminated body, the performance evaluation shown next was performed, and the obtained result is shown in Tables 2-4. Except where otherwise indicated, in each Example and Comparative Example, measurement was performed three times with respect to one sample by changing the location, and the average value was used.

[Measurement of elastic modulus by atomic force microscope]

After embedding the laminates of Examples 1 to 19 and Comparative Examples 1 to 6 with an epoxy resin (Quetol 812 manufactured by Nissin EM Co., Ltd.) and curing, cross-sections were cut out by the freezing microtome method, and the cross-sections were measured As cotton, it was fixed to a dedicated sample holder. Using Asylum Technology's AFM "MFP-3DSA-J" and NANOSENSORS' cantilever "R150-NCL-10 (material Si, spring constant 48 N/m, tip radius of curvature 150 nm)", the surface layer and support base material For the cross section, the force curve (moving speed of the cantilever 2 μm/s, maximum indentation load 2 μN) was measured in the contact mode.

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

[Measurement of elastic modulus distribution in the 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 method described above. Subsequently, the magnification was adjusted so that the thickness of the surface layer converged within the viewing angle from the obtained surface image. At this time, the surface layer-supporting substrate interface was observed as a bright line or dark line from the elastic modulus mismatch at the boundary between the surface layer and the supporting substrate, and the center of this bright or dark line was taken as the measurement reference line in the thickness direction of the surface layer. Similarly, for the outermost surface, the center of a bright line or a dark line generated due to an elastic modulus mismatch 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 measurements, in the case of "distance from the outermost surface", the distance from the above-mentioned outermost surface to the center of the bright line or dark line is referred to, and in the case of "distance to the outermost surface", the above-mentioned It means the distance from the outermost surface to the center of the bright line or dark line. Similarly, in the case of "distance from the surface layer-supporting substrate interface", the distance from the center of the bright line or dark line at the above-mentioned interface is referred to, and in the case of "distance to the surface layer-supporting substrate interface", the above It refers to the distance to the center of the bright line or dark line in one interface.

The above-described distance between the surface layer-supporting substrate interface and the outermost surface was taken as the total thickness of the surface layer. Subsequently, a data group on a straight line terminating the surface layer was selected from measurement points in the form of lattice points with a resolution of 512 × 512. In addition, the distance in the thickness direction from the surface layer-supporting substrate interface of each data point is calculated from the angle formed by the normal line of the laminate and the straight line terminating the surface layer to which the above data group belongs, and the distance in the thickness direction is approximately 100 nm apart. The elastic modulus distribution in the thickness direction was obtained by measuring the modulus of elasticity by the method described above so as to be obtained. At this time, the point at which the distance from the surface layer-supporting substrate interface in the thickness direction is less than 100 nm (reference numeral 10 in FIG. 1) and the point at which the distance from the outermost surface is less than 100 nm (reference numeral 11 in FIG. 1) are It was excluded from the measurement because it is easily affected by interfaces and surfaces. In addition, when the measurement is performed by the above method, the lower limit of the distance between each measurement point that can be set practically is determined from the thickness and resolution of the surface layer. Specifically, it is about 1/500 of the thickness of the surface layer, and for example, when the thickness of the surface layer is 50 μm, its spatial resolution is about 100 nm. Although it is possible to further increase the resolution according to the settings of the device, the above-mentioned about 100 nm is a realistically measurable value based on the curvature of the cantilever and the number of measurement points.

Next, as the modulus of elasticity on the outermost surface side and the interface side, it is present at a position 100 nm inside from the outermost surface in the surface layer (reference numeral 5 in Fig. 1) and a position 100 nm inside from the interface (reference numeral 7 in Fig. 1) It was randomly selected from the point of doing, and the average value of the measurement results at each of 5 locations was used as the elastic modulus of the outermost surface side and the interface side.

[Measurement of elastic modulus of supporting substrate]

The elastic modulus of the cross section was similarly measured for the supporting base material. Regarding the measurement position, in the supporting substrate, from a point at a distance of 100 nm from the interface between the supporting substrate and the surface layer to the supporting substrate side (for example, numeral 8 in FIG. 1) in the thickness direction of the supporting substrate (where the surface layer exists) The elastic modulus was measured at intervals of 100 nm in a direction opposite to the direction. The elastic modulus is measured from the interface between the supporting 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, the elastic modulus is measured at intervals of 100 nm from the interface between the supporting substrate and the surface layer to a distance of 3 μm) measurement), and the average value thereof was taken as the modulus of elasticity of the supporting base material.

[Calculation of Parameters from Elastic Modulus Distribution in the Thickness Direction]

Based on the parameters in the thickness direction obtained by the above-described method, the maximum modulus of elasticity, the minimum modulus of elasticity, the average value of the thicknesses of the portions where the modulus of elasticity is higher than the modulus of elasticity of the supporting substrate (Ta), and the average value of the thickness of the portions where the modulus of elasticity is lower than the modulus of elasticity of the supporting substrate (Tb) ), the average value of the maximum elastic modulus (Ea) and the average value of the minimum elastic modulus (Eb) were calculated by the following methods, respectively.

Among the elastic moduli obtained earlier, among the measurement points whose measurement positions in the thickness direction belonged to the surface layer, the value with the largest elastic modulus was made the maximum elastic modulus, and the value with the smallest elastic modulus was made the minimum elastic modulus. Then, from the measurement points belonging to the surface layer, the points at which the elastic modulus is the maximum were extracted, and from these maximum values, all values greater than the elastic modulus of the supporting substrate were extracted, and Ea was obtained as the average value. For Eb, the local minimum value was extracted instead of the local maximum value, and it was calculated in the same manner except that a value smaller than the elastic modulus of the supporting base material was used.

Subsequently, from the elastic modulus distribution in the thickness direction and the elastic modulus of the supporting base material, a portion having an elastic modulus higher than the elastic modulus of the supporting base material and a portion having an elastic modulus lower than the elastic modulus of the supporting base material were calculated. Although the concept is shown in FIG. 3, specifically, the coordinates of the intersection of the numerical value of the "elastic modulus of the supporting base material" and the "elastic modulus distribution in the thickness direction" were calculated by the following method. As described above, "the elastic modulus distribution in the thickness direction" is a set of discrete data points at intervals of 100 nm, so "one elastic modulus is lower than the elastic modulus of the supporting base material, and the other elastic modulus is higher than the elastic modulus of the supporting base material" Two adjacent points satisfying the conditions were extracted, and the coordinates of the intersection of the straight line connecting the two points satisfying the above conditions and the straight line representing the elastic modulus of the supporting base material (hereinafter referred to as the coordinates of the intersection) were calculated. Then, the distance in the thickness direction between the intersections was calculated from the calculated coordinates of each intersection point, and it was set as "thickness of a portion having an elastic modulus higher than the elastic modulus of the supporting substrate" and "thickness of a portion having an elastic modulus lower than the elastic modulus of the supporting substrate". In addition, the thickness on the interface side with the supporting substrate is the distance from the surface layer-supporting substrate interface (symbol 13 in FIG. 4) to the coordinates of the intersection point with the shortest distance (symbol 22 in FIG. The thickness of the portion higher than the modulus of elasticity of the supporting base material”. In addition, the thickness of the outermost surface side refers to the distance from the outermost surface (reference numeral 12 in FIG. 4 ) to the intersection point with the shortest distance (reference numeral 23 in FIG. thickness”. Further, 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 value of the portion where the elastic modulus is lower than the elastic modulus of the supporting substrate, respectively, the thickness average value Ta and the elastic modulus of the portion where the elastic modulus is higher than the elastic modulus of the supporting substrate are obtained. The thickness average value (Tb) of the part lower than the elastic modulus of the supporting base material was calculated.

[Measurement of the shape of inorganic particles having an anisotropic shape]

By observing the cross section using a transmission electron microscope (TEM), the shape of the inorganic particles included in the cross section of the surface layer was measured. 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 photographed by TEM at a magnification of 200,000 times. Subsequently, the image was converted to grayscale using the image processing software EasyAccess Ver6.7.1.23, and the white balance was adjusted so that the brightest and darkest parts converged to an 8-bit tone curve, and furthermore, the boundaries of inorganic particles could be clearly distinguished. Contrast was adjusted. Subsequently, using software (image processing software ImageJ/development institute: National Institute of Health (NIH), USA), pixels are binarized with the above boundary as a boundary, and individual inorganic particles are analyzed by the Analize Particles (particle analysis) function. The formed region was extracted, and the major value when the area of the region was approximated by an ellipse with Fit Ellipse was obtained as the major diameter and the minor value as the minor diameter. The above analysis was performed on 50 individual inorganic particle systems, and the maximum value of the major diameter was defined as the major diameter Rl, and the minimum value of the minor diameter was designated as the minor diameter Rs.

[Measurement of existence frequency of inorganic particles having anisotropic shapes]

Subsequently, the frequency of existence of the inorganic particles was calculated from cross-sectional observation with the same transmission electron microscope (TEM). First, an ultrathin section of the cross section of the laminate was photographed by TEM at a magnification of 50,000 times. Next, with the image processing software EasyAccess Ver 6.7.1.23, the image was converted to gray scale, and the white balance was adjusted so that the brightest and darkest parts converged to an 8-bit tone curve. In addition, the contrast was adjusted so that the boundaries of the inorganic particles could be clearly distinguished, and rotation and trimming were performed so that the surface layer-supporting substrate interface (reference numeral 13 in Fig. 4) was leveled. Subsequently, "thickness of a portion having an elastic modulus higher than the elastic modulus of the supporting substrate" and "thickness of a portion having an elastic modulus lower than the elastic modulus of the supporting substrate" obtained by the method of [Calculation of parameters from elastic modulus distribution in the thickness direction] described above Depending on the value, the image was subdivided into rectangles in the direction parallel to the interface. Next, using software (image processing software ImageJ/development institute: National Institute of Health (NIH), USA), pixels are binarized based on the above-mentioned boundaries, and individual inorganic particles are analyzed by the Analize Particles (particle analysis) function. The region formed was extracted, and the area of the region was calculated therefrom. Similarly, the area formed by the cut-out rectangular image was calculated, and the area ratio of the inorganic particles occupied in the rectangular shape was calculated as the existence frequency of the inorganic particles. Among the frequencies calculated as described above, the average value of the values obtained from the rectangle formed by the "thickness of the portion whose elastic modulus is higher than the elastic modulus of the supporting base material" is the elastic modulus of the elastic modulus higher than the elastic modulus of the supporting base material. The average value of the values obtained from the rectangle formed by the "thickness of the portion having an elastic modulus lower than the elastic modulus of the supporting substrate" was taken as the frequency Fb of a portion having an elastic modulus lower than the elastic modulus of the supporting substrate.

[Measurement of surface hardness by pencil hardness test method of surface layer]

After the produced laminate was left to stand for 12 hours under conditions (24°C, 65% relative humidity), in the same environment according to the scratch hardness (pencil method) described in JIS K 5600-5-4 (1999) , the surface hardness of the surface layer was measured.

[Scratch resistance of surface layer]

After the produced laminate was left to stand for 12 hours under conditions (24° C., 65% relative humidity), steel wool (#0000) with a load of 1,000 g/cm 2 was applied vertically to the surface having the surface layer, and 5 cm of The estimated number of flaws visible to the naked eye when the length was reciprocated by 10 was described, and the following class was performed.

5 points: 0

4 points: more than 1 but less than 5

3 points: 5 or more but less than 10

2 points: more than 10 but less than 20

1 point: 20 or more.

[Flexibility of laminate]

After the produced laminate was left to stand for 12 hours under conditions (24°C, 65% relative humidity), in the same environment, type 1 of bending resistance (cylindrical mandrel method) described in JIS K 5600-5-1 (1999) was obtained. Evaluation was carried out by Mandrels with 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 peeling of the coating film were not observed visually. In addition, the same evaluation was carried out under the condition of folding so that the surface having the surface layer is on the outside (mountain fold) and the condition of folding so that the surface having the surface layer is on the inside (valley folding).

5 points: 2 mmφ crack, no peeling

4 points: 2 mmφ cracks, peeling, 3 mmφ cracks, no peeling

3 points: 3 mmφ cracks, peeling, 4 mmφ cracks, no peeling

2 points: 4 mmφ cracks, peeling, 5 mmφ cracks, no peeling

1 point: 5 mmφ crack, peeling present.

[Curl property of laminate]

After leaving the produced layered product to stand for 12 hours under conditions (24°C, 65% relative humidity), it was cut out into a square shape of 10 cm square and left standing on a horizontal surface. Subsequently, the distances between the points at the four corners of the laminate and the horizontal plane were measured, and the values were averaged to classify into five levels.

5 points: less than 1 mm

4 points: 1 mm or more and less than 10 mm

3 points: 10 mm or more and less than 20 mm

2 points: 20 mm or more

1 point: It becomes cylindrical and cannot be measured.

[Adhesion of surface layer]

After the produced laminate was left to stand for 12 hours under conditions (24° C., 65% relative humidity), 100 cross-cuts of 1 mm 2 were placed on the surface having the surface layer, and Nichiban Co., Ltd. “cello tape” ( registered trademark) was attached thereon, and using a rubber roller, three reciprocations at a load of 19.6 N were pressed, followed by peeling in the direction of 90 degrees, and 5-level evaluation (5: 96 pieces) by the number of remaining conductive layers. 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 to impart the same function to the respective surfaces of plastic molded products, home appliances, buildings or vehicle interiors, and various printed materials.

1 support material
2 surface layer
3 laminate
4 The outermost surface of the superficial layer
5 Measurement points of elastic modulus on the outermost surface side
6 Interface between the surface layer and the supporting substrate
7 Measurement points of elastic modulus on the interface side
8 Starting point of elastic modulus measurement of supporting substrate
9 Modulus of elasticity of the supporting substrate
10 Area where measurement is not performed from the influence of the supporting base material
11 Area where measurement is not performed from the influence of the surface
12 Position of the outermost surface of the surface layer
13 Position of surface layer-support substrate interface
14 Maximum modulus of elasticity
15 Minimum modulus of elasticity
16 Maximum modulus of elasticity
17 Average value of maximal elastic modulus
18 Minimal modulus of elasticity
19 Average value of minimum elastic modulus
20 Distribution of the modulus of elasticity in the thickness direction and thickness of the portion where the modulus of elasticity is higher than the modulus of elasticity of the supporting substrate
21 Distribution of the modulus of elasticity in the thickness direction and thickness of the portion where the modulus of elasticity is lower than the modulus of elasticity of the supporting base material
22 Among the points where the modulus of elasticity of the supporting substrate and the surface layer are equal, the point closest to the interface between the surface layer and the supporting substrate
23 Among the points where the modulus of elasticity of the supporting substrate and the surface layer are equal, the point closest to the outermost surface
24 multi-layer slide die
25 multi-layer slot die
26 single layer slot die

Claims (6)

It is a laminate in which a surface layer is laminated on a support substrate, and in the distribution of the elastic modulus in the thickness direction of the surface layer, there is a maximum value having a higher modulus of elasticity than the modulus of elasticity of the supporting substrate and a minimum value having a lower modulus of elasticity than the modulus of elasticity of the supporting substrate, and in the surface layer A layered product characterized in that both the modulus of elasticity at the interface side with the supporting substrate and the modulus of elasticity at the outermost surface side are higher than the modulus of elasticity of the supporting substrate. 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 times or more and 10,000 times or less of the minimum elastic modulus. 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. According to claim 1 or 2, in the elastic modulus distribution in the thickness direction of the surface layer, a maximum value having an elastic modulus higher than the elastic modulus of the supporting base material and a minimum elastic modulus lower than the elastic modulus of the supporting base material exist alternately, calculated from the elastic modulus distribution A layered product characterized in that the thickness and modulus of elasticity to be used satisfy the following relationship.
10≤(Tb[nm]/Ta[nm])×(Ea[MPa])/Eb[MPa])≤1,000... (Equation 1)
Ta [nm]: average value of the thickness of the part where the modulus of elasticity is higher than the modulus of elasticity of the supporting substrate
Tb [nm]: average value of the thickness of the part where the modulus of elasticity is lower than the modulus of elasticity of the supporting substrate
Ea [MPa]: average value of maximum elastic modulus
Eb [MPa]: average value of minimum elastic modulus The laminate according to claim 1 or 2, wherein the surface layer contains inorganic particles having an anisotropic shape that satisfies the following.
1.2≤Rl/Rs≤20,000... (Equation 2)
1nm≤Rs≤100nm... (Equation 3)
Rl [nm]: major diameter of inorganic particles
Rs [nm]: short diameter of inorganic particles The layered product according to claim 5, wherein the frequency of existence F in the thickness direction of the inorganic particles having an anisotropic shape in a cross section perpendicular to the supporting substrate of the surface layer satisfies the following condition.
Fa<Fb... (Equation 4)
Fa: Existence frequency of a part where the modulus of elasticity is higher than the modulus of elasticity of the supporting substrate
Fb: Existence frequency of a part where the modulus of elasticity is lower than the modulus of elasticity of the supporting base material

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