TW201630714A - Layered body - Google Patents

Abstract

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

Description

Laminated body

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

In the past, for the purpose of protecting the surface of an optical material such as a color filter or a flat panel display (to prevent damage or stain resistance, etc.), a plastic film provided with a surface layer containing a synthetic resin or the like can be used. For these surface layers, scratch resistance is required as an important characteristic from the viewpoint of surface protection. Therefore, in general, the "highly crosslinked density material" described in Non-Patent Document 1 is used to impart scratch resistance. The "highly crosslinked density material" contains various prepolymerizations such as an organic decane-based or polyfunctional acrylic system. A coating composition of a substance, an oligomer or the like is formed by hardening by coating-drying-heating or UV. Further, the "hardcoat material" which is an "organic-inorganic composite material" obtained by combining various surface-modifying fillers may be further imparted by using a "hardcoat material". To increase the surface hardness of the coating film.

On the other hand, in recent years, the "light and soft" characteristics of plastic film have been utilized, not only for the display surface of personal computers or smart phones, but also for "curvature protection" such as the surface of the outer casing, or called "softness". The device is a flexible outer casing. In such use, In addition to the "surface hardness" such as the scratch resistance of the surface layer or the durability of the scratches, it is also required to be less likely to cause cracks or peeling when bent, that is, to have "flexibility".

In the case of the hard coat material, a laminate having both scratch resistance and flexibility is disclosed. Patent Literature 1 and Patent Document 2 disclose that "the hard coat layer/substrate can be adhered to each other. A hard coat film having a pencil hardness value of 4H or more, which is reduced to a practically acceptable range, such as film bending cracks and curls. Specifically, it is proposed to provide a cured resin coating layer formed by providing a film of a transparent cured resin, wherein the cured resin layer contains inorganic or organic internal crosslinked ultrafine particles, and the transparent hardened resin film is not "internal crosslinked ultrafine particles containing inorganic or organic matter" and "a cured resin coating layer containing a blend of a radical polymerization type resin and a cationic polymerization type resin, and a cured resin coating layer containing only a radical polymerization type resin, A hardened resin film layer having a two-layer structure formed in this order.

On the other hand, Patent Document 3 discloses "a hard coat film which is intended to improve the surface hardness while preventing damage to the hard coat film due to stress concentration and which is not easily damaged." Specifically, a "hard coat film" characterized in that two or more hard coat layers are formed, and the elastic layer σm of the hard coat layer formed closest to the transparent substrate is higher than the elastic modulus σs of the hard coat layer of the surface layer. .

Further, Patent Document 4 discloses "a laminate having a hard coat layer which is excellent in film adhesion and has high film strength and excellent scratch resistance". Specifically, a "layered body with a hard coat layer, which is a two-layered alternating layer of inorganic particles having different concentrations, is proposed. It is characterized in that when a layer group having a high concentration of inorganic particles is regarded as an A layer unit and a layer group having a low concentration of inorganic particles is regarded as a B layer unit, the sum of the dry film thicknesses of the A layer units ΣAh and the B layer unit The sum of the dry film thicknesses ΣBh satisfies the relationship ΣAh≧ΣBh”.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2000-052472

Patent Document 2 Japanese Patent Laid-Open Publication No. 2000-071392

Patent Document 3 Japanese Patent Laid-Open Publication No. 2000-214791

Patent Document 4 International Publication No. 2009/130975

Non-patent literature

Non-Patent Document 1 Plastic Hard Coating Application Technology, published by CMC Corporation, 2004

[Summary of the Invention]

However, the plastic film using the above-mentioned "hard-coating material" in the surface layer has a high surface hardness, that is, an elastic modulus, and a large stress is generated by slight deformation during bending, so that cracking easily occurs. On the other hand, in the structures of Patent Document 1 and Patent Document 2, "the occurrence of curling" due to shrinkage of the hard coat layer can be suppressed. Regarding the configuration of Patent Document 1, that is, "the coating layer having a modulus of elasticity of 1.0 GPa to 6.0 GPa is in the range of 0.5 GPa to 4.5 GPa. The hard coat film formed on the coating layer, and the structure of Patent Document 2, that is, "the coating layer having an elastic modulus of 2.0 GPa to 4.5 GPa is in the range of 1.5 GPa to 4.5 GPa. The inventors of the present invention have found that a sufficient "bending property" cannot be obtained by the inventors of the present invention.

On the other hand, in the structure proposed in Patent Document 3, "the elastic modulus σm of the hard coat layer formed closest to the substrate is higher than the elastic modulus σs of the hard coat layer of the surface layer." However, when the inventors confirmed these structures, it was determined that the higher the elastic modulus of the outermost layer, the more favorable the surface hardness is.

In the structure of the patent document 4, the inorganic particle concentration of the inorganic particle concentration is 30.0% by volume or more and 70.0% by volume or less, and the inorganic particle concentration is 0% by volume or more and 40.0% by volume or less of the inorganic particles. In the hard coat layer in which the low-concentration group is alternately laminated, although the surface hardness is improved, since the resin material is selected from the highly crosslinkable active light-curing resin, it is impossible to obtain a design capable of obtaining flexibility.

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

In order to solve the above problems, the inventors of the present invention have completed the following inventions by repeating the results of intensive research. That is, the present invention is as described below.

(1) A laminate which is a laminate having a surface layer laminated on a support substrate, characterized by an elastic modulus distribution in a thickness direction of the surface layer Among them, there is a minimum value at which the modulus of elasticity is higher than the modulus of elasticity of the support substrate, and an elastic modulus which is lower than the modulus of elasticity of the support substrate, and the modulus of elasticity and the most surface side of the interface side with the support substrate in the surface layer. The elastic modulus is higher than the elastic modulus of the support substrate.

(2) The laminate according to (1), wherein the maximum modulus of elasticity 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 modulus of elasticity.

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

(4) The laminate according to any one of (1) to (3), wherein, in the elastic modulus distribution in the thickness direction of the surface layer, the modulus of elasticity and the modulus of elasticity higher than the modulus of elasticity of the support substrate The thickness and the elastic modulus calculated from the elastic modulus distribution satisfy the following relationship: 10 ≦ (Tb [nm] / Ta [nm]) × (Ea [MPa]) / Eb[MPa])≦1,000...(Formula 1)

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

Tb [nm]: the average value of the thickness of the portion where the modulus of elasticity is lower than the modulus of elasticity of the supporting substrate

Ea[MPa]: the average value of the maximum elastic modulus

Eb [MPa]: the average value of the 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 satisfying the following formula: 1.2≦Rl/Rs≦20,000...(Form 2)

1nm≦Rs≦100nm...(Formula 3)

Rl [nm]: long diameter of inorganic particles

Rs [nm]: short diameter of inorganic particles

The layered body according to any one of (1) to (5) wherein, in the cross section perpendicular to the support substrate of the surface layer, the existence ratio of the anisotropically shaped inorganic particles in the thickness direction F satisfies the following conditions: Fa<Fb...(Formula 4)

Fa: the existence rate of the elastic modulus higher than the elastic modulus of the supporting substrate

Fb: the existence rate of the elastic modulus lower than the elastic modulus of the supporting substrate

According to the present invention, a laminate having both high surface hardness and flexibility can be provided. The laminate of the present invention has excellent surface hardness as compared with a homogeneous resin layer of the same thickness, and can suppress occurrence of curl due to stress concentration, cracking during bending, or peeling of the coating film.

1‧‧‧Support substrate

2‧‧‧ surface layer

3‧‧‧Layer

4‧‧‧The surface of the surface layer

5‧‧‧Measurement point of the elastic modulus at the outermost surface

6‧‧‧ Interface between surface layer and supporting substrate

7‧‧‧Measurement point of the elastic modulus at the interface side

8‧‧‧Starting point of elastic modulus measurement of supporting substrate

9‧‧‧Support substrate elastic modulus

10‧‧‧A zone that has not been measured due to the influence of the supporting substrate

11‧‧‧A zone that has not been measured due to the influence of the surface

12‧‧‧The position of the outermost surface of the surface layer

13‧‧‧Surface layer - the position of the support substrate interface

14‧‧‧Maximum modulus of elasticity

15‧‧‧ Minimum modulus of elasticity

16‧‧‧Great modulus of elasticity

17‧‧‧Average of the maximum elastic modulus

18‧‧‧Minimum elastic modulus

19‧‧‧ Average of the minimum elastic modulus

20‧‧‧The elastic modulus distribution in the thickness direction and the thickness of the elastic modulus which is higher than the elastic modulus of the supporting substrate

21‧‧‧The thickness distribution in the thickness direction and the thickness of the elastic modulus which is lower than the elastic modulus of the supporting substrate

22‧‧‧ The point closest to the interface between the surface layer and the support substrate in the point where the elastic modulus of the support substrate and the surface layer are equal

23‧‧‧ The point closest to the outermost surface in the point where the elastic modulus of the supporting substrate and the surface layer are equal

24‧‧‧Multilayer sliding die

25‧‧‧Multi-layer slot die

26‧‧‧Single layer slot die

Fig. 1 is a schematic cross-sectional view of a laminated body of the present invention and a conceptual diagram of an elastic modulus distribution in a thickness direction in a cross section.

Fig. 2 is a conceptual diagram of the elastic modulus distribution in the thickness direction, the maximum elastic modulus, and the minimum elastic modulus.

Figure 3 is a conceptual diagram of the elastic modulus distribution in the thickness direction and the maximum elastic modulus, the minimum elastic modulus, and the average of these.

Fig. 4 is a conceptual diagram showing a portion in which the elastic modulus distribution in the thickness direction and the elastic modulus are higher than the elastic modulus of the supporting substrate, and the elastic modulus is lower than the elastic modulus of the supporting substrate.

Fig. 5 is an example of a method of producing a surface layer (multilayer sliding die coating).

Fig. 6 is an example of a method of producing a surface layer (multilayer slit die coating).

Fig. 7 is an example of a method of producing a surface layer (wet-on-wet coating).

[Used to implement the aspect of the invention]

In order to achieve the above problems, the technical difficulty is the hardness (that is, the high modulus of elasticity) and the flexibility (that is, the low modulus of elasticity). In the inventions of Patent Documents 1 to 4, the balance between the hardness and the flexibility is adjusted by the elastic modulus of the material, the type of the resin, or the amount of the particles. However, these methods cannot achieve the above problems. The reason for this is that the modulus of elasticity of the material used for imparting flexibility is too high.

Then, the present inventors first reviewed in detail from the viewpoint of hardness, "the occurrence of scars caused by the pencil hardness test". As a result, it was confirmed that the state of the flaw occurring in the pencil hardness test can be classified into the following three types. That is, (1) scratches due to the outermost surface of the film, (2) scratches due to discontinuous changes in the elastic modulus of the film, and (3) scratches caused by the support substrate. That is, (1) is a flaw caused by insufficient hardness of the surface layer, (2) is a flaw caused by peeling of the interface such as peeling of the interface, and (3) is a depression caused by bending of the substrate or the like. Therefore, there are three points required for suppressing the surface layer of the flaw caused by the pencil hardness test: (I) the highest surface of the surface layer has a high modulus of elasticity, (II) the surface layer and the interface with the support substrate. Stress free deformation, (III) reduce the stress transmitted to the substrate.

Then, the inventors of the present invention conducted a review based on the above-described design pointer, and found that the surface layer satisfying the conditions described later can maintain the original hardness of the surface, and can also incorporate a material having a lower modulus of elasticity than the support substrate. That is, the present inventors have found a laminate having a surface layer having a surface hardness as described above, and suppressing occurrence of curl due to stress concentration, cracking during bending, or coating film. Stripping. The following description is made using the drawings.

First, as shown in Fig. 1, the laminate of the present invention is a laminate 3 in which a surface layer 2 is laminated on one surface of a support substrate 1. Further, the surface layer 2 has an uneven elastic modulus distribution in the thickness direction thereof. Further, if the elastic modulus of the surface layer satisfies the conditions described later, it may be a laminate in which a plurality of layers having different elastic moduli are laminated, or the elastic modulus in the thickness direction in the same layer may be different. Floor.

Further, the "elasticity of the cross-section of the laminate" in the present invention can be measured by an atomic force microscope. The degree of deformation caused by the pressing force is measured by the elastic modulus measurement of the atomic force microscope for the compression test by the probe of a very small portion. Therefore, the cantilever of a known spring constant was used, and the elastic modulus of each position in the thickness direction of the surface layer was measured. Specifically, the laminated body was cut, and the elastic modulus of each position in the thickness direction of the surface layer was measured by an atomic force microscope. Specifically, as described in the examples, the probe of the tip end of the cantilever was brought into contact with the cross section of the surface layer by using an atomic force microscope as described below, and the force curve was measured by the pressure of 55 nN. The amount of deflection of the cantilever. Moreover, the spatial resolution of the thickness direction at this time depends on the scanning range of the atomic force microscope. The number of scan lines and the number of scan lines, but under actual measurement conditions, about 50 nm is the lower limit. Details and measurement methods will be described later.

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

Cantilever: Cantilever "R150-NCL-10" made of NANOSENSORS (material Si, spring constant 48N/m, radius of curvature of the front end 150nm).

Hereinafter, a preferred aspect of the elastic modulus of the surface layer will be described.

[Supporting the elastic modulus of the substrate and the elastic modulus of the surface layer]

First, in the elastic modulus distribution in the thickness direction of the surface layer obtained by plotting the thickness of the surface layer as shown in Fig. 2 on the horizontal axis and the elastic modulus of the cross section measured by the above method as the vertical axis, It is preferable to have a portion having a higher modulus of elasticity and a lower portion having a lower modulus than the modulus of elasticity of the support substrate section. In the case where the above elastic modulus does not have a high portion, since the elastic modulus of the surface layer is insufficient, sufficient hardness may not be obtained. On the other hand, in the case where the above-described elastic modulus does not have a low portion, the flexibility, particularly the suppression of the bending crack, is insufficient, and the problem may not be achieved. Further, the "elasticity distribution in the thickness direction of the surface layer" is represented by a continuous curve in Fig. 2, but in reality, it is a set of data points measured at intervals of 100 nm. The change in the fine elastic modulus in the interval of less than 100 nm has little effect on the hardness or flexibility of the laminated body. Therefore, the influence of the change in the elastic modulus which cannot be detected by the above measurement conditions can be neglected in reality. In addition, the details of the measuring method of the "elasticity distribution in the thickness direction of the surface layer" will be described later.

[Elasto-elasticity at the outermost surface side and elastic modulus at the interface side with the support substrate]

In the present invention, the elastic modulus at the outermost surface side and the elastic modulus at the interface side are preferably higher than the elastic modulus of the support substrate. Among them, "the most surface" means the outermost surface of the surface layer. Further, "interface" means the interface between the surface layer and the support substrate (that is, the boundary line between the surface layer and the support substrate). When the elastic modulus at the outermost surface side is lower than the elastic modulus of the support substrate, even if the inner portion has a high modulus of elasticity, it may be easily damaged. Further, when the elastic modulus at the interface side is lower than the elastic modulus of the support substrate, scratches due to the support substrate may easily occur. In particular, it is particularly preferable that the elastic modulus of the outermost surface side is the highest in the surface layer. The "elasticity of the outermost surface side" means the elastic modulus of the outermost surface of the surface layer. However, in the measurement of the modulus of the cross section, since the surface layer value of the elastic modulus which is located on the line 4 of the first surface of the true outermost surface cannot be obtained, the value of the measuring point 5 which is inside the inner surface of 100 nm from the outermost surface is actually taken as "The elastic modulus of the outermost surface side". Further, the "elasticity ratio at the interface side" means the modulus of elasticity at the interface between the surface layer and the support substrate. However, in the elastic modulus measurement of the cross section, since the elastic modulus accurate interface value on the line of the first image of the true interface cannot be obtained, it is actually a surface of 100 nm from the boundary line 6 of the surface layer and the support substrate. The measured value 7 on the layer side is referred to as "the elastic modulus at the interface side".

[Maximum elastic modulus and minimum elastic modulus]

On the other hand, in the elastic modulus distribution (Fig. 2) in the thickness direction of the surface layer, "maximum elastic modulus 14" which is the maximum value of the elastic modulus in the surface layer and "minimum value which is the minimum value of the elastic modulus in the surface layer" There is a good relationship between the elastic modulus of 15". Specifically, it is the most flexible It is preferable that the ratio is 100 times or more and 10,000 times or less of the minimum elastic modulus. In the case where the relationship between the maximum elastic modulus and the minimum elastic modulus is not in the range described above, specifically, in the case of less than 100 times, any physical property having hardness or flexibility is insufficient, and it becomes difficult to achieve both. . On the other hand, when it exceeds 10,000 times, the elastic layer of the rapid change will cause the surface layer to be easily skewed, and the pencil hardness may be lowered or the film may be peeled off.

Furthermore, there is a preferred range of values 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 elastic modulus is higher than 0.1 GPa, the above-mentioned flexibility tends to be insufficient, and cracking or curling tends to occur.

The "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. Moreover, the "minimum elastic modulus" means the minimum value of the elastic modulus in the elastic modulus distribution in the thickness direction of the surface layer measured by the method described later.

[Maximum elastic modulus and relationship between minimum elastic modulus and thickness]

Further, in the structure in which the deformation of the stress is less likely to occur in the surface layer, there is a preferable relationship between the elastic modulus and the thickness. Specifically, in the elastic modulus distribution in the thickness direction of the surface layer, as shown in FIG. 3, the maximum value (maximum modulus of elasticity 16) and the modulus ratio of the modulus of elasticity higher than the modulus of elasticity 9 of the supporting substrate are present. A minimum value (very small modulus of elasticity 18) which supports a low elastic modulus of the substrate is preferable. Further, in the elastic modulus distribution in the thickness direction of the surface layer, the elastic modulus at the interface side between the surface layer and the support substrate and the elastic modulus at the outermost surface side are higher than the elastic modulus of the support substrate. Preferably. Further, in the elastic modulus distribution in the thickness direction of the surface layer, as shown in Fig. 4, the elastic modulus is higher than the elastic modulus 9 of the supporting substrate (maximum elastic modulus 16) and the elastic modulus ratio supporting group. The minimum value of the elastic modulus of the material 9 (very small elastic modulus 18) exists "interactively", and the average value of the thickness 20 of the portion where the modulus of elasticity is higher than the elastic modulus of the supporting substrate is 9 and the elasticity is higher than that of the supporting substrate. It is more preferable that the average value of the thickness 21 of the lower portion of the rate 9 satisfies the following relationship.

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

Wherein Ta[nm] is an average value of the thickness of the portion where the modulus of elasticity is higher than the modulus of elasticity of the supporting substrate, and Tb[nm] is the average value of the thickness of the portion where the modulus of elasticity is lower than the modulus of elasticity of the supporting substrate, Ea [MPa] ] is the average value of the maximum elastic modulus 17, Eb [MPa] is the average value 19 of the extremely small elastic modulus.

Wherein, the modulus of elasticity is higher than the maximum value of the elastic modulus of the supporting substrate (maximum modulus of elasticity 16), meaning that the modulus of elasticity is higher than that of the supporting substrate, and as shown in FIG. 3, the thickness of the surface layer is The maximum value in the case where the relationship with the modulus of elasticity is plotted (the inclination becomes a value of zero). Further, the elastic modulus is lower than the elastic modulus of the supporting substrate (minimum elastic modulus 18), meaning that the elastic modulus is lower than that of the supporting substrate, and as shown in Fig. 3, the thickness of the surface layer is The minimum value of the case where the relationship with the modulus of elasticity is plotted (the inclination becomes a value of zero).

Further, in the elastic modulus distribution in the thickness direction of the surface layer, the modulus of elasticity is higher than the maximum value of the elastic modulus of the supporting substrate, and the minimum value which is lower than the modulus of elasticity of the supporting substrate, which means that When the elastic modulus distribution in the thickness direction of the surface layer is measured by the method described in the embodiment, all the following requirements (1) to (4) are satisfied.

(1) At least two of the maximum value and the minimum value are respectively present.

(2) The elastic modulus with a high modulus of elasticity is not supported by the substrate.

(3) The elastic modulus maximum value of the non-supporting substrate having a low modulus of elasticity.

(4) When the maximum value and the minimum value are juxtaposed in the thickness direction, at least one of them becomes (i) maximum value-minimum value-maximum value-minimum value or (ii) minimum value-maximum value-minimum value-maximum The sequence of values.

Further, the "average value of the thickness of the portion where the modulus of elasticity is higher than the modulus of elasticity of the supporting substrate" means that the thickness of each portion of the surface layer which is higher than the modulus of elasticity of the supporting substrate is averaged. The value obtained. Further, the "average value of the thickness of the portion where the modulus of elasticity is lower than the modulus of elasticity of the support substrate" means that the thickness of each portion of the surface layer which is lower than the modulus of elasticity of the support substrate is averaged. The value obtained.

Further, the average value of the maximum elastic modulus means an average value of the maximum value of the elastic modulus in the surface layer which is higher than the elastic modulus of the supporting substrate, and the average value of the minimum elastic modulus means that the surface layer exists. It has an average value of the minimum value of the elastic modulus lower than the elastic modulus of the support substrate.

The structure of the surface layer which can achieve the elastic modulus as described above includes a "multilayer structure" in which a layer having a high modulus of elasticity (that is, a hard layer) and a layer having a low modulus of elasticity (that is, a soft layer) are alternately laminated. Or a "sloping structure" having an elastic modulus distribution due to variations in constituent components such as particles and resins, although the layer of one of the interfaces is not clearly defined. The structure of the surface layer and the method of manufacturing the same are as follows (manufacturing method of the laminated body).

The above relational expression indicates a parameter of the "flexibility" of the laminated body defined on the basis of the ratio of the modulus of elasticity of the components constituting the surface layer to the thickness. The larger the parameter, the larger the Tb, that is, the "elasticity is lower than the thickness of the support substrate, the lower the elastic modulus", or the smaller the Eb, that is, the "minimum elastic modulus", which is equivalent to the laminate. The body becomes soft. Conversely, the smaller the parameter, the greater the hardness of the laminate.

Specifically, when the relational expression is smaller than 10, the flexibility of the entire surface layer tends to be insufficient, and it is likely to cause cracks or curls. On the other hand, in the case of more than 1,000, the hardness of the entire surface layer tends to be insufficient, and in particular, there is a case where peeling of the interface or reduction in pencil hardness is caused.

If the above relationship is decomposed into component A with high modulus of elasticity and component B with low modulus of elasticity, it can be decomposed into "Ea/Ta" and "Eb/Tb", that is, "(elasticity) / (coating film thickness)" "." On the other hand, when considering the resultant force acting on the spring, the "length of the spring" is a value inversely proportional to the "spring constant". Generally, as the length increases, the value of the spring constant becomes smaller. In the case where it is considered to press in the thickness direction, the "thickness of the coating film" corresponds to the value of "the length of the spring", and the thicker the thickness, the lower the spring constant must be estimated. Therefore, the above relational expression can be judged as a preferable numerical range of "the spring constant corrected by the coating film thickness".

Hereinafter, the form of implementation of the present invention will be described in detail.

[Laminated body, and surface layer]

The "surface layer" in the present invention means a layer formed on a support substrate, and a layer including one of the surface layer and the support substrate is collectively referred to as a "layered body". That is, only on the support substrate In the case of forming a layer of one layer, the one layer is a "surface layer". Further, for example, when two or more layers are formed on the support substrate, all of the two or more layers other than the support substrate are used as one "surface layer".

The term "layer" means a portion having a finite thickness by distinguishing a portion adjacent to the thickness direction from the surface side of the laminate to the thickness direction and having a boundary surface. More specifically, it means that when the cross section of the laminated body is observed by an electron microscope (transmissive type, scanning type) or an optical microscope, it can be distinguished by the presence or absence of a discontinuous boundary surface. The laminate of the present invention may have either a planar state or a ternary shape after molding, if it has a surface layer exhibiting the above physical properties. The thickness of the entire surface layer is not particularly limited, but is preferably 1 μm or more and 50 μm or less, and more preferably 3 μm or more and 20 μm or less.

In addition to the scratch resistance, particularly the over-peel resistance and the moldability, the laminate may have antifouling properties, antireflection properties, antistatic properties, antifouling properties, and conductivity. Layers of other functions such as properties, heat ray reflectivity, near-infrared absorbing properties, electromagnetic wave shielding properties, and easy adhesion can also be imparted to the aforementioned surface layer.

[Support substrate]

The material constituting the support substrate used for the laminate of the present invention may be either a thermoplastic resin or a thermosetting resin, and may be a homo-resin, a copolymer or a blend of two or more thereof. More preferably, the resin constituting the support substrate is preferably a thermoplastic resin from the viewpoint of moldability.

As an example of the thermoplastic resin, a polyolefin resin such as polyethylene, polypropylene, polystyrene or polymethylpentene, an alicyclic polyolefin resin, a polyamide resin such as nylon 6 or nylon 66, or the like can be used. Aramid resin, polyester resin, polycarbonate resin, polyarylate resin, polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, chlorotrifluoroethylene resin, A fluororesin such as a tetrafluoroethylene-hexafluoropropylene copolymer or a vinylidene fluoride resin, an acrylic resin, a methacrylic resin, a polyacetal resin, a polyglycolic acid resin, or a polylactic acid resin. The thermoplastic resin is preferably a resin having sufficient elongation and followability. The thermoplastic resin is preferably a polyester resin, a polycarbonate resin or a methacrylic resin from the viewpoint of strength, heat resistance and transparency, and is particularly preferably a polyester resin.

The polyester resin in the present invention means a general term for a polymer having a main bond chain in which an ester bond is a main chain, and is obtained by polycondensation of an acid component and an ester thereof and a diol component. Specific examples thereof include polyethylene terephthalate, polytrimethylene terephthalate, polyethylene 2,6-naphthalenedicarboxylate, and polybutylene terephthalate. Further, these acid components or diol components may be obtained by copolymerizing other dicarboxylic acids and esters thereof with a diol component. Among these, polyethylene terephthalate or polyethylene-2,6-naphthalenedicarboxylate is particularly preferred from the viewpoints of transparency, dimensional stability, heat resistance and the like.

Further, various additives such as an antioxidant, an antistatic agent, a crystal nucleating agent, inorganic particles, organic particles, a viscosity reducing agent, a thermal stabilizer, a slip agent, an infrared absorbing agent, and an ultraviolet absorbing agent may be added to the supporting substrate. A dopant, a dopant for adjusting the refractive index, and the like. The support substrate may be either a single layer structure or a laminate structure.

On the surface of the support substrate, various surface treatments may be performed before the formation of the aforementioned surface layer. Examples of the surface treatment include pharmaceutical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high-frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, and 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 further preferable.

Further, on the surface of the support substrate, a functional layer other than the surface layer of the present invention, such as an easy-to-attach layer, an antistatic layer, an undercoat layer, an ultraviolet absorbing layer, or the like, may be provided in advance, in particular, an easy adhesion layer is provided. good.

Further, the elastic modulus of the support substrate in the present invention means the elastic modulus of the support substrate measured in accordance with the method described later. Among them, even in the case of a support substrate having no elastic modulus distribution or a support substrate having an elastic modulus distribution in the thickness direction, the elastic modulus measured according to the method described later is referred to as the elastic modulus of the support substrate.

[paint composition]

In the laminate of the present invention, a surface layer having a structure capable of achieving the physical properties can be formed by applying, drying, and curing a coating composition on a support substrate by using a method for producing a laminate described later. The "coating composition" means a liquid containing a solvent and a solute, a material coated on the above-mentioned supporting substrate, volatilized by a drying step, and formed into a surface layer by hardening. Here, the "type" of the coating composition means the kind of the solute constituting the coating composition, although part of it For different liquids. The solute includes a resin or a material which can be formed in the coating process (hereinafter referred to as a precursor), particles, and a polymerization initiator, a hardener, a catalyst, a leveling agent, an ultraviolet absorber, an antioxidant, and the like. Various additives.

In the surface layer of the present invention, it is preferable to use the above-mentioned coating composition A which can form a portion having a higher modulus of elasticity than the elastic modulus of the cross section of the supporting substrate, and a coating composition which can form a portion having a lower "elasticity". At least two coating compositions of the substance B are formed by successive application on a support substrate or simultaneous coating.

[Coating Composition A]

As the coating composition A, a hard coat material which can form a coating layer having a high modulus of elasticity can be preferably used. The elastic modulus of the coating layer single layer film is preferably from 6 GPa to 200 GPa. The specific component is preferably a highly crosslinkable binder component having a plurality of reactive sites and a particle component for imparting an elastic modulus. In particular, in the case of a coating material capable of forming a hard coat layer having a high modulus of elasticity, it is preferred to use a composite coating material of an organic material and an inorganic material called an organic-inorganic composite coating material. Examples of the organic-inorganic composite coating material include: "Dacheng Precision Chemical Co., Ltd.; (organic-inorganic composite coating material "STR-SiA")", "East Asia Synthetic Co., Ltd.; (trade name "Light" The hardened SQ series ")", "Toyo Ink Co., Ltd.; (trade name "Lioduras" (registered trademark))", etc., can be suitably used. Further, in the representative form of the organic-inorganic composite coating material, a highly crosslinkable binder containing inorganic particles and an organic compound having a high modulus of elasticity is preferred. Preferred particle components and binder components are described later.

[Coating Composition B]

As the coating composition B, a resin coating material rich in flexibility and moldability can be preferably used. The elastic modulus of the single film of the coating layer is preferably from 1 MPa to 100 MPa. Specifically, it is preferable to use a commercially available one as a scratch-repairable coating material or a formable HC (Hard Coating) coating material or an adhesive. Further, a particulate material may be contained in one of the parts.

For examples of the scratch-repairing coating material or the forming type HC coating material, "China Paint Co., Ltd. (trade name "Pholucid" series)", "AICA Industrial Co., Ltd." (trade name "Aica-" Aitron "series" and so on. In the case of the adhesive, the "Arontack" series of "East Asia Synthetic Co., Ltd." and the "SKDyne" (registered trademark) series of the comprehensive research chemical company, etc. As the oxygen adhesive, an adhesive of "Toray-Dow Corning Co., Ltd." and "Shinhide Polyoxane Co., Ltd." can be cited. Further, the preferred coating composition will be described later.

[Particle material, particle composition]

The surface layer of the laminate of the present invention preferably contains a particle component, and the coating composition A which is particularly suitable for forming the surface layer of the present invention preferably contains particles. Among them, the particles may be either inorganic particles or organic particles, and inorganic particles are preferred from the viewpoint of durability.

The number of kinds of the inorganic particles is preferably one or more and 20 or less. The number of the types of the inorganic particles is preferably one or more and 10 or less, and more preferably one or more and four or less. Among them, "inorganic particles" also include those who perform surface treatment. The surface treatment means the particle table The compound is introduced by chemical bonds (including covalent bonds, hydrogen bonds, ionic bonds, van der Waals bonds, hydrophobic bonds, etc.) or adsorption (including physical adsorption and chemical adsorption).

The type of the inorganic particles is determined according to the type of the elements constituting the inorganic particles, and the type of the surface treatment may be determined according to the type of the elements constituting the particles before the surface treatment. For example, titanium oxide (TiO ₂ ) and nitrogen-doped titanium oxide (TiO _2-x N _x ) in which a part of oxygen of titanium oxide is replaced with an anion nitrogen are different types of inorganic substances due to the difference in the elements constituting the inorganic particles. particle. Further, in the case of particles (ZnO) containing only the same elements such as Zn and O, even if there are a plurality of particles having different numbers and average particle diameters, or even if the composition ratio of Zn and O is different, these are the same kinds of particles. . Further, even if a plurality of Zn particles having different oxidation numbers are present, if the elements constituting the particles are in the same range (in this example, all the elements other than Zn are in the same range), these are the same kind of particles.

Further, in the treatment of coating, drying, hardening treatment, or evaporation, the particles contained in the coating composition suitable for forming the surface layer of the present invention may be subjected to thermal or ionizing radiation or the like to change the surface state thereof. Form, included in the aforementioned surface layer. Here, in the present invention, the particles present in the coating composition used are referred to as "particle materials", and the coating composition is formed into the surface layer formed by treatment such as coating, drying, hardening treatment or evaporation. The particles present are called "particle components."

The inorganic particles are not particularly limited, but are oxides, nitrides, borides, chlorides, carbonates, sulfates of metals or semimetals. The salt is preferably a composite oxide containing two kinds of metals and semimetals, or an inter-element is introduced between the lattices, or a lattice point is substituted with a heterogeneous element, or a lattice defect is introduced.

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

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

The particle component of the coating composition forming the surface layer of the present invention is particularly preferable in order to stably disperse cerium oxide in a good solvent of the binder raw material to perform necessary surface modification. For example, when an acrylic monomer or an oligomer is used as a binder raw material, an alkyl group, an alkenyl group, a vinyl group, a (meth)acrylic group or the like having a carbon number of 1 to 5 or less is used for the surface modification. It is preferred to introduce the surface of the particle component to the minimum necessary.

Here, the number average particle diameter of the inorganic particles means the number-based arithmetic mean length diameter described in JIS Z8819-2 (2001). In the case of any of the particle component and the particle material, the primary particles are observed by a scanning electron microscope (SEM) or a transmission electron microscope, and the diameter of each of the primary particles is taken as the particle diameter, and the average number of the particles is averaged. The value is obtained. In the case of a laminate, the number average particle diameter can be obtained by observing the surface or the cross section, and in the case of the coating composition, The sample was prepared by dropping a coating composition diluted with a solvent and drying to prepare a sample.

[Inorganic particles with anisotropic shape]

Further, the surface layer of the laminate of the present invention is particularly preferably composed of inorganic particles having an anisotropic shape. Further, in order to form a coating composition suitable for the surface layer of the present invention, it is preferred to include an inorganic particle having an anisotropic shape, and particularly preferably an inorganic particle having an anisotropic shape in the coating composition B. Among them, an inorganic particle having an anisotropic shape means a particle having a non-orthogonal shape and having a skewed shape, specifically, a beaded particle in which a pointer, a plate, or a spherical particle is combined in a chain shape. . The inorganic particles contained in the surface layer have an anisotropic shape as described above, and the flexibility of the entire layer can be maintained as it is, and the hardness of the surface layer can be imparted. Although the reason for the flexibility and the hardness is unknown, it has been confirmed that by adding the inorganic particles having an anisotropic shape, the stress in the pressing direction can be maintained as it is, and only the stress in the shearing direction is increased. Destruction caused by shearing of the laminated film.

In the case of the inorganic particles having the aforementioned anisotropic shape, there is a preferred shape. Specifically, R1/Rs which is a ratio of the long diameter R1 to the short diameter Rs of the inorganic particles is preferably 1.2 or more and 20,000 or less, and more preferably 1.5 or more and 10,000 or less. In the case where Rl/Rs is smaller than 1.2, the difference between the above-described indentation stress and shearing stress is less likely to occur, and the flexibility of the surface layer may be lowered. On the other hand, even if Rl/Rs is high, the performance of the laminate is not directly lowered. However, when Rl/Rs exceeds 20,000, it becomes difficult to perform uniform coating due to the occurrence of chattering of the coating material.

On the other hand, the short diameter Rs is preferably 1 nm or more and 100 nm or less, and more preferably 3 nm or more and 50 nm or less. When Rs is less than 1 nm, the volume ratio of the inorganic particles to the laminated body becomes small, and a sufficient hardness improving effect may not be obtained. On the other hand, when Rs exceeds 100 nm, the contribution to the above-described press-in stress is increased, and the flexibility of the surface layer may be lowered. The measurement method of the long diameter R1 and the short diameter Rs will be described later.

In addition, the difference between the above-described indentation stress and the shear stress is particularly remarkable when the binder component to be described later is a flexible binder, and thus the inorganic particles having the anisotropic shape are present in the laminate. The elastic modulus is particularly preferable than the portion where the elastic modulus of the support substrate is low. Specifically, it is preferable that the existence ratio of the inorganic particles having an anisotropic shape to be described later satisfies (Formula 4), that is, the elastic modulus of the laminated body is higher than the elastic modulus of the supporting substrate, and is higher than the laminated body. The modulus of elasticity is more than the portion of the support substrate having a lower modulus of elasticity. When the elastic modulus of the laminated body is higher than the elastic modulus of the support substrate, the existence of the inorganic particles having an anisotropic shape is large, and the above-mentioned shearing of the laminated film may not be sufficiently obtained. The suppression effect of the damage may make it difficult to make both the flexibility and the hardness of the laminate due to a decrease in the flexibility of the coating film.

An inorganic particle having an anisotropic shape selected from 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 The oxidized oxide particles are further preferably.

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

[Binder material, adhesive composition]

Suitable coating compositions for forming the surface layer of the present invention are preferably those containing a binder material. The binder means a compound having a reactive site or a higher-order compound formed by the reaction thereof. Here, the binder present in the coating composition used in the present invention is referred to as a "gluer material" and will be present on the aforementioned surface formed by subjecting the coating composition to coating, drying, hardening treatment or evaporation. The layer of adhesive is called the "adhesive component." Further, the reactive site means a site that reacts with other components by external energy such as heat or light. Preferred among such reactive sites, from the viewpoint of reactivity, alkoxyalkyl and alkoxyalkylalkyl hydrolyzed stanol groups; carboxyl groups, hydroxyl groups, epoxy groups, vinyl groups, alkenes A propyl group, an acrylonitrile group, a methacryl fluorenyl group or the like. In addition, the coating composition A which forms the surface layer of the present invention contains at least a "highly crosslinkable binder" which will be described later, and the coating composition B preferably contains at least a "softening binder" which will be described later, and may contain the same. Equivalent bonding agent.

[Highly crosslinkable binder]

Highly crosslinkable adhesive, in addition to being used as a binder component of coating composition A, in addition to adhesion or film formation From the viewpoint of improvement, it is also included in the coating composition B. Among them, a material having two or more reactive sites of 20 or less in one molecule is preferred. Further, it may be either a thermosetting resin or an ultraviolet curable resin, or a mixture of two or more kinds.

The thermosetting resin suitable for the highly crosslinkable binder comprises a hydroxyl group-containing resin and a polyisocyanate compound, and examples of the hydroxyl group-containing resin include acrylic polyols, polyether polyols, polyester polyols, and polyolefin resins. The polyol, the polycarbonate polyol, the urethane polyol, and the like may be one type or a mixture of two or more types. When the hydroxyl group-containing resin has a hydroxyl group content of from 1 to 200 mgKOH/g, it is preferable from the viewpoint of durability, hydrolysis resistance, and adhesion at the time of forming a coating film. When the valence of the hydroxyl group is smaller than 1, the hardening of the coating film is hardly performed, and the durability or strength may be lowered. On the other hand, when the hydroxyl group is larger than 200, since the hardening shrinkage is too large, the adhesion may be lowered.

The hydroxyl group-containing acrylic polyol in the present invention can be obtained by polymerizing using, for example, acrylate or methacrylate as a component. Such an acrylic resin can be easily copolymerized with a monomer containing a carboxylic acid group such as (meth)acrylic acid, itaconic acid or maleic anhydride, if necessary, by using (meth) acrylate as a component. Manufacturing. Examples of the (meth) acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, and (methyl). Butyl acrylate, isobutyl (meth)acrylate, butyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Ester, cyclohexyl (meth)acrylate, (methyl) propyl Methyl hexyl acrylate, cyclododecyl (meth) acrylate, isobornyl (meth) acrylate, and the like. Examples of such a hydroxyl group-containing acrylic polyol include "DIC Corporation; (trade name "Acrydic" (registered trademark) series)", "Dacheng Precision Chemical Co., Ltd.; (trade name "Acrit") (registered trademark) series, etc.), "Japan Catalyst Co., Ltd.; (product name "Acryset" (registered trademark) series, etc.)", "Mitsui Chemical Co., Ltd.; (trade name "Takelac" (registered trademark) UA Series), etc., can use such products.

Examples of the hydroxyl group-containing polyester polyol in the present invention include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, decanediol, and cyclohexanedimethanol. An aliphatic diol, such as succinic acid, adipic acid, sebacic acid, fumaric acid, suberic acid, azelaic acid, 1,10-fluorene dicarboxylic acid, cyclohexanedicarboxylic acid, etc. An aliphatic polyester polyol obtained by reacting a monobasic acid as an essential raw material component; or an aliphatic diol such as ethylene glycol, propylene glycol or butylene glycol, and for example, terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid An aromatic polyester polyol obtained by reacting an aromatic dibasic acid as an essential raw material component.

Examples of such a hydroxyl group-containing polyester polyol include "DIC Co., Ltd.; (trade name "Polylite" (registered trademark) series)", "Kuraray Co., Ltd.; (trade name "Kuraray polyol") (registered trademark) series, etc.), "Wutian Pharmaceutical Industry Co., Ltd.; (trade name "Talkelac" (registered trademark) U series)", can use these products.

The polyolefin-containing polyol having a hydroxyl group in the present invention is a diene having 4 to 12 carbon atoms such as butadiene or isoprene. A polymer having a hydroxyl group among copolymers of a polymer and a copolymer, a diene of 4 to 12 carbon atoms, and an α-olefin of 2 to 22 carbon atoms. The method of containing a hydroxyl group is not particularly limited, and may be, for example, a method of reacting a diene monomer with hydrogen peroxide. Further, the remaining double bonds may be hydrogenated and saturated and aliphatic. Examples of such a hydroxyl group-containing polyolefin-based polyol include "Japan Soda Co., Ltd.; (trade name "NISSO-PB" (registered trademark) G series, etc.)", "Idemitsu Kosan Co., Ltd.; The product name "Poly bd" (registered trademark) series, "Epol" (registered trademark) series, etc." can be used.

For the polycarbonate polyol containing a hydroxyl group in the present invention, for example, a polycarbonate polyol obtained by using only dialkyl carbonate and 1,6-hexanediol can be used. From the point of lower crystallinity, the diol is obtained by copolymerization of 1,6-hexanediol with 1,4-butanediol, 1,5-pentanediol or 1,4-cyclohexanedimethanol. Polycarbonate polyols are preferred.

As such a hydroxyl group-containing polycarbonate polyol, "Asahi Kasei Chemicals Co., Ltd.; (trade name "T5650J", "T5652", "T4671", "T4672") may be mentioned as a copolymerized polycarbonate polyol. ")), "Ube Industries Co., Ltd.; (trade name "ETERNACLL" (registered trademark) UM series, etc.)", can use these products.

The hydroxy group-containing urethane polyol of the present invention can be obtained, for example, by reacting a polyisocyanate compound with a compound having at least two hydroxyl groups in one molecule and reacting a hydroxyl group to an isocyanate group in an excess ratio. Examples of the polyisocyanate compound used at this time include hexamethylene diisocyanate, toluene diisocyanate, and Xylene diisocyanate, isophorone diisocyanate, and the like. Further, examples of the compound containing at least two hydroxyl groups in one molecule include polyhydric alcohols, polyester diols, polyethylene glycol, polypropylene glycol, and polycarbonate diol.

The polyisocyanate compound used in the thermosetting resin of the present invention means a resin containing an isocyanate group or a monomer or oligomer containing an isocyanate group. Examples of the compound containing an isocyanate group include methylene bis-4-cyclohexyl isocyanate, trimethylolpropane adduct of toluene diisocyanate, and trimethylolpropane adduct of hexamethylene diisocyanate. Trimethylolpropane adduct of isophorone diisocyanate, isocyanurate body of toluene diisocyanate, isocyanurate body of hexamethylene diisocyanate, hexamethylene isocyanate A (poly)isocyanate such as a biuret or a block of the above isocyanate. The polyisocyanate compound used for such a thermosetting resin is exemplified by "Mitsui Chemical Co., Ltd.; (trade name "Takenate" (registered trademark) series)", "Japanese Polyurethane Industry Co., Ltd. Limited" Company; (trade name "Coronate" (registered trademark) series, etc.)", "Asahi Kasei Chemicals Co., Ltd.; (trade name "Duranate" (registered trademark) series, etc.)", "DIC Co., Ltd.; (trade name " Burnock" (registered trademark) series, etc.".

On the other hand, in the case of a suitable ultraviolet curable resin in a highly crosslinkable binder, a polyfunctional acrylate monomer, an oligomer, an alkoxydecane, an alkoxydecane hydrolyzate, or an alkoxydecane oligomer A polymer, a urethane acrylate oligomer or the like is preferable, and a polyfunctional acrylate monomer, an oligomer, or a urethane acrylate oligomer is more preferable.

Examples of the polyfunctional acrylate monomer include polyfunctional acrylates having two or more (meth)acryloxy groups in one molecule, and modified polymers thereof. As a specific example, neopentyl alcohol tri(meth)acrylate, neopentyltetrakis(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol can be used. Alcohol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentyl Tetraol triacrylate hexamethylene diisocyanate urethane polymer or the like. These monomers may be used alone or in combination of two or more.

In addition, the commercially available polyfunctional acrylic composition includes "Mitsubishi Co., Ltd.; (product name "Diabeam" (registered trademark) series)", "Japan Synthetic Chemical Industry Co., Ltd."; (trade name "SHIKOH" (registered trademark) series, etc.)", "Changbu Industry Co., Ltd.; (product name "Denacol" (registered trademark) series, etc.)", "Xinzhongcun Chemical Co., Ltd.; (trade name "NK" "Ester" series, etc.", "DIC Co., Ltd.; (trade name "UNIDIC" (registered trademark), etc.)", "East Asia Synthetic Co., Ltd.; ("Aronix" (registered trademark) series, etc.)", "Nippon Oil Co., Ltd.; ("Blemmer" (registered trademark) series, etc.)", "Nippon Chemical Co., Ltd.; (trade name "KAYARAD" (registered trademark) series, etc.)", "Kyoeisha Chemical Co., Ltd.; These products can be used for the product name "Light Ester" series, etc."

[soft adhesive]

The soft adhesive can be suitably used as the binder component of the coating composition B. With 4 or less in 1 molecule The material of the reactive portion is preferably a form which is inactivated such as an active reactive site of the acrylic polymer. Preferred materials for the softening adhesive are exemplified below.

The preferred form of the coating composition B includes "a coating composition for forming a scratch-repairing resin layer", a "formable HC coating material" having a breaking elongation of about 5 to 50%, and an "adhesive". "."

In the case of a coating composition for forming a scratch-repairable resin layer, it is particularly preferable to include a resin or a precursor containing the following fragments in a solute: (1) comprising a polycaprolactone-containing fragment, a polycarbonate segment, and A fragment of at least one of the group consisting of the alkyl diol fragments and (2) a fragment of a urethane bond. These various fragments can be confirmed by TOF-SIMS, FT-IR, and the like.

On the other hand, as the adhesive, it can be suitably used: a rubber-based adhesive which is most commonly used by rubber and an adhesive, and an acrylic which imparts various functions to a copolymer of an acrylic polymer. "Adhesive"; any of "polyoxygenated adhesives" having excellent temperature characteristics and chemical resistance but relatively high cost, from the viewpoint of compatibility with high modulus of elasticity and cost "Acrylic adhesive" is especially good.

[solvent]

The coating composition A and the coating composition B are preferably contained in a solvent. The number of the types of the solvent is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, and still more preferably 1 or more and 6 or less. The term "solvent" means a substance which is almost completely evaporated during the drying step after coating and which is removed from the coating film and is liquid at normal temperature and normal pressure.

Among them, the type of the solvent is determined in accordance with the molecular structure constituting the solvent. That is, even if the composition of the same element is the same and the type and number of the functional groups are the same, those having a different bond relationship (structural isomers) or any configuration other than the aforementioned structural isomers are adopted in a three-dimensional space. Those that cannot be accurately overlapped (stereoisomers) are still used as solvents of different kinds. For example, 2-propanol and n-propanol are used as different solvents.

[Other additives]

The coating composition A and the coating composition B are preferably a polymerization initiator, a curing agent, and a catalyst. The polymerization initiator and the catalyst are used to promote the hardening of the surface layer. The polymerization initiator is preferably one which undergoes polymerization, condensation or crosslinking reaction by anion, cation, radical polymerization or the like in order to initiate or accelerate the components contained in the coating composition.

Various types of polymerization initiators, hardeners, and catalysts can be used. Further, the polymerization initiator, the curing agent, and the catalyst may be used singly or in combination with a plurality of polymerization initiators, hardeners, and catalysts. Further, an acidic catalyst, a thermal polymerization initiator or a photopolymerization initiator may be used in combination. Examples of the acidic catalyst include an aqueous hydrochloric acid solution, formic acid, acetic acid, and the like. Examples of the thermal polymerization initiator include a peroxide and an azo compound. Further, examples of the photopolymerization initiator include an alkylphenone compound, a sulfur-containing compound, a mercaptophosphine oxide compound, and an amine compound.

In the photopolymerization initiator, an alkylphenyl ketone compound is preferred from the viewpoint of hardenability. Specific examples of the alkyl phenyl ketone compound include 1-hydroxy-cyclohexyl-phenyl-ketone and 2,2-dimethoxy-1,2-diphenylethan-1-one. 2-methyl-1-(4-methylthiophenyl)-2-N- Polinylpropan-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-N- Phenylphenyl)-1-butane, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Phenyl)phenyl]-1-butane, 1-cyclohexyl-phenyl ketone, 2-methyl-1-phenylpropan-1-one, 1-[4-(2-ethoxy)-benzene Alkyl-2-hydroxy-2-methyl-1-propan-1-one, bis(2-phenyl-2-oxoacetic acid)oxydiethylene, and a polymer of these materials.

Further, the progress state of the polymerization reaction by the thermal polymerization initiator or the photopolymerization initiator can be controlled by the amount of heat or light applied, and the surface layer is formed by successive coating, by The next layer is applied in an incomplete state in which polymerization is carried out, and a mixed layer having intermediate properties can be produced without forming a clear interface.

Moreover, as long as the effect of the present invention is not inhibited, a coating agent, an ultraviolet absorber, a lubricant, an antistatic agent, or the like may be added to the coating composition A and the coating composition B for forming the surface layer. Thereby, the surface layer may contain a leveling agent, an ultraviolet absorber, a lubricant, an antistatic agent, and the like. Examples of the leveling agent include an acrylic copolymer, a polyfluorene-based or a fluorine-based leveling agent. Specific examples of the ultraviolet absorber include benzophenone type, benzotriazole type, oxalic acid aniline type, and three And a blocking amine-based UV absorber. Examples of the antistatic agent include metal salts such as a lithium salt, a sodium salt, a potassium salt, a phosphonium salt, a phosphonium salt, a magnesium salt, and a calcium salt.

[Manufacturing method of laminated body]

The manufacturing method of the laminated body of the present invention is preferably carried out by using a coating method in which at least the above-described coating composition A and coating composition B are successively or simultaneously coated-dried-hardened on the above-mentioned supporting substrate. .

Here, "coating successively" or "sequential coating" means that a coating composition of a different type is coated, dried, and cured by coating, drying, and hardening one coating composition to form a surface layer. The surface layer formed in "sequential coating" can control the size or gradient of the elastic modulus of the surface side-substrate side, and the elastic modulus of the substrate and the surface layer by appropriately selecting the type and amount of the coating composition used. the size of. Although the "layer coating" formed by "sequential coating" usually forms a "multilayer structure" having a plurality of interfaces, the coating layer is controlled by appropriately selecting the type, composition, drying conditions, and curing conditions of the coating composition. Separation of material types ‧ diffusion, can form a pseudo-tilted structure. The elastic modulus distribution in the surface layer can be changed stepwise or continuously by the layer structure as described above.

Another manufacturing method is a method in which two or more kinds of coating compositions are simultaneously applied, dried, and cured on a support substrate. The number of the types of the coating composition is not particularly limited as long as it is two or more types. The term "simultaneous coating" or "simultaneous coating" means that two or more liquid films are applied onto a support substrate in a coating step, followed by drying and curing. The "surface coating" formed in "simultaneous coating" can form a "sloping structure" having no clear interface.

In the present manufacturing method, in the case where the above-mentioned coating composition is applied successively, the coating method is preferably by dip coating method, roller coating method, wire bar coating method, concave coating method or die coating method (US Patent) The specification of No. 2681294 is equivalent to coating a substrate or the like to form a surface layer.

In the case where the above two or more kinds of the coating compositions are simultaneously applied, the "multilayer sliding die coating" (Fig. 5) in which the liquid film is sequentially laminated and applied in the state before coating may be used, or in the base. "Multilayer slit die coating" (Fig. 6) in which a layer is applied while the material is applied, or a "liquid coating" is formed on the support substrate, and the other layer is "wet coated" in an undried state. (Fig. 7) and so on.

Next, the liquid film coated on the support substrate or the like is dried. In order to completely remove the solvent from the obtained laminate, it is preferred to heat the liquid film in the drying step.

Examples of the drying method include heat transfer drying (adhering to a hot object), convection heat transfer (hot air), radiation heat transfer (infrared light), and other (microwave, induction heating). Among them, in the production method of the present invention, it is preferred to use convection heat transfer or radiation heat transfer based on the necessity of uniformly making the drying speed uniform even in the width direction.

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

Further, in the case of hardening by the active energy ray, it is preferable to use an electron beam (EB line) and/or an ultraviolet ray (UV line) from the viewpoint of versatility. Further, in the case of curing by ultraviolet rays, it is preferable that the oxygen concentration is reduced as much as possible on the outermost surface, and it is more preferable to harden in a nitrogen atmosphere (nitrogen substitution). In the case where the oxygen concentration is high, the hardening of the outermost surface is hindered, and the hardening of the surface sometimes becomes insufficient. On the other hand, in the layer which forms the inside of the surface layer, on the contrary, by promoting the oxygen barrier, the next coating layer becomes easy to permeate, and it is easy to form the aforementioned mixed layer having intermediate physical properties, which is preferable. .

Moreover, the type of the ultraviolet lamp used when irradiating ultraviolet rays may be, for example, a discharge lamp method, a flash mode, a laser method, an electrodeless lamp method, or the like. In the case of ultraviolet curing using a high-pressure mercury lamp of a discharge lamp type, the illuminance of ultraviolet rays is 100 to 3,000 mW/cm ² , preferably 200 to 2,000 mW/cm ² , more preferably 300 to 1,500 mW/cm ² . , ultraviolet irradiation is preferred, and a cumulative amount of ultraviolet rays to become 100 ~ 3,000mJ / cm ^2, preferably 200 ~ 2,000mJ / cm ^2, more preferably 300 ~ 1,500mJ / cm ² of ultraviolet irradiation condition is preferred . Among them, the illuminance of ultraviolet light means the intensity of illumination per unit area, which varies with the light output, the efficiency of the luminescence spectrum, the diameter of the illuminating bulb, the design of the mirror, and the distance between the object to be illuminated and the source. However, the illuminance does not change with the conveying speed. Further, the cumulative amount of ultraviolet light means the amount of irradiation energy per unit area, which is the total amount reaching the surface. The amount of accumulated light is inversely proportional to the irradiation speed under the light source, and is proportional to the number of times of illumination and the number of lamps.

[Example of use]

Since the laminated body of the present invention has excellent surface hardness and flexibility, it can be widely used for members having curved surfaces, such as an electrochemical product, an automobile interior member, a building member, and the like.

For example, it can be suitably used for: plastic molded products such as glasses, sunglasses, cosmetic cases, food containers, etc.; smart phone case, touch panel, keyboard, TV, air conditioner, remote control, etc.; building; instrument panel , car navigation systems, touch panels, rearview mirrors and other vehicle interiors; and various surfaces of various printed materials.

[Examples]

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

<The blending of the coating composition A>

[Coating composition A1]

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

‧Organic-inorganic composite HC coating material 80.0 parts by mass

("Aica-Aitron" Z-729-18 AICA Industrial Co., Ltd.)

‧ Ethyl acetate 20.0 parts by mass.

[Coating composition A2]

‧ dipentaerythritol hexaacrylate 18.8 parts by mass

‧Particle additive C1 (cerium oxide particle dispersion) 44.4 parts by mass

("MEK-AC-2140Z" Nissan Chemical Industry Co., Ltd.)

‧ ethyl acetate 35.6 parts by mass

‧Photoradical polymerization initiator 1.2 parts by mass

("Irgacure" (registered trademark) 184 BASF JAPAN Co., Ltd.).

[Coating composition A3]

‧ dipentaerythritol hexaacrylate 38.8 parts by mass

‧ ethyl acetate 60.0 parts by mass

‧Photoradical polymerization initiator 1.2 parts by mass

("Irgacure" (registered trademark) 184 BASF JAPAN Co., Ltd.).

[Coating composition A4]

‧ dipentaerythritol hexaacrylate 36.8 parts by mass

("Aica-Aitron" Z-729-18 AICA Industrial Co., Ltd.)

‧Particle additive C3 2.0 parts by mass

‧ ethyl acetate 60.0 parts by mass

‧Photoradical polymerization initiator 1.2 parts by mass

("Irgacure" (registered trademark) 184 BASF JAPAN Co., Ltd.).

<The blending of the coating composition B> <Synthesis of urethane acrylate> [Toluene solution of urethane acrylate 1]

50 parts by mass of toluene, 50 parts by mass of hexamethylene diisocyanate, isocyanurate modified type (manufactured by Mitsui Chemicals, Inc.) Takenate D-170N), 76 parts by mass of polycaprolactone modified hydroxyethyl acrylate (Placcel FA5 manufactured by Daicel Chemical Industry Co., Ltd.), 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone The ether was mixed and kept at 70 ° C for 5 hours. Then, 79 parts by mass of toluene was added to obtain a toluene solution of urethane acrylate 1 having a solid concentration of 50% by mass.

[A solution of urethane acrylate 2 in toluene]

50 parts by mass of an isocyanurate modified body of hexamethylene diisocyanate (Takenate D-170N manufactured by Mitsui Chemicals Co., Ltd., isocyanate group content: 20.9% by mass), and 53 parts by mass of polyethylene glycol Monoacrylate (Blemmer AE-150 (hydroxyl price: 264 (mgKOH/g)) manufactured by Nippon Oil Co., Ltd., 0.02 parts by mass of dibutyltin laurate, and 0.02 parts by mass of hydroquinone monomethyl ether. Next, at 70 After the reaction was completed, the reaction was carried out for 5 hours. After the completion of the reaction, 102 parts by mass of methyl ethyl ketone (hereinafter referred to as MEK) was added to the reaction liquid to obtain a urethane acrylate 2 having a solid concentration of 50% by mass. Toluene solution.

[Coating composition B1]

The following materials were mixed and diluted with ethyl acetate to obtain a coating composition B1.

‧ urethane acrylate 1 (solid content concentration 50% by mass) - toluene solution 4.9 parts by mass

‧ urethane acrylate 2 (solid content concentration 50% by mass) - toluene solution 4.9 parts by mass

‧ ethyl acetate 90.05 parts by mass

‧Photoradical polymerization initiator 0.15 parts by mass

("Irgacure" (registered trademark) 184 BASF JAPAN Limited Company).

[Coating composition B2]

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

‧ Self-healing paint 7.1 parts by mass

("Pholucid" NO.521C China Coatings Co., Ltd.)

‧ ethyl acetate 92.86 parts by mass.

[Coating composition B3]

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

‧Acrylic adhesive 16.7 parts by mass

("SK Dyne" 1439U Comprehensive Research Chemical Co., Ltd.)

‧ ethyl acetate 83.26 parts by mass

‧ hardener 0.08 parts by mass

(hardener E-50C Comprehensive Research Chemical Co., Ltd.).

[Coating composition B4]

‧ urethane acrylate 1 (solid content concentration 50% by mass) - toluene solution 4.85 parts by mass

‧ urethane acrylate 2 (solid content concentration 50% by mass) - toluene solution 4.85 parts by mass

‧Particle additive C2 0.1 parts by mass

‧ ethyl acetate 90.05 parts by mass

‧Photoradical polymerization initiator 0.15 parts by mass

("Irgacure" (registered trademark) 184 BASF JAPAN Co., Ltd.).

[Coating composition B5]

‧ urethane acrylate 1 (solid content concentration 50% by mass) - toluene solution 4.85 parts by mass

‧ urethane acrylate 2 (solid content concentration 50% by mass) - toluene solution 4.85 parts by mass

‧Particle additive C3 0.1 parts by mass

‧ ethyl acetate 90.05 parts by mass

‧Photoradical polymerization initiator 0.15 parts by mass

("Irgacure" (registered trademark) 184 BASF JAPAN Co., Ltd.).

[Coating composition B6]

‧ urethane acrylate 1 (solid content concentration 50% by mass) - toluene solution 4.85 parts by mass

‧ urethane acrylate 2 (solid content concentration 50% by mass) - toluene solution 4.85 parts by mass

‧Particle additive C4 0.1 parts by mass

‧ ethyl acetate 90.05 parts by mass

‧Photoradical polymerization initiator 0.15 parts by mass

("Irgacure" (registered trademark) 184 BASF JAPAN Co., Ltd.).

[Coating composition B7]

‧ urethane acrylate 1 (solid content concentration 50% by mass) - toluene solution 4.85 parts by mass

‧ urethane acrylate 2 (solid content concentration 50% by mass) - toluene solution 4.85 parts by mass

‧Particle additive C5 0.1 parts by mass

‧ ethyl acetate 90.05 parts by mass

‧Photoradical polymerization initiator 0.15 parts by mass

("Irgacure" (registered trademark) 184 BASF JAPAN Co., Ltd.).

[Coating composition B8]

‧ urethane acrylate 1 (solid content concentration 50% by mass) - toluene solution 4.85 parts by mass

‧ urethane acrylate 2 (solid content concentration 50% by mass) - toluene solution 4.85 parts by mass

‧Particle additive C6 0.1 parts by mass

‧ ethyl acetate 90.05 parts by mass

‧Photoradical polymerization initiator 0.15 parts by mass

("Irgacure" (registered trademark) 184 BASF JAPAN Co., Ltd.).

[Coating composition B9]

‧ urethane acrylate 1 (solid content concentration 50% by mass) - Toluene solution 4.85 parts by mass

‧ urethane acrylate 2 (solid content concentration 50% by mass) - toluene solution 4.85 parts by mass

‧Particle additive C7 0.1 parts by mass

‧ ethyl acetate 90.05 parts by mass

‧Photoradical polymerization initiator 0.15 parts by mass

(IIrgacure (registered trademark) 184 BASF JAPAN Co., Ltd.).

[Coating composition B10]

‧ urethane acrylate 1 (solid content concentration 50% by mass) - toluene solution 4.85 parts by mass

‧ urethane acrylate 2 (solid content concentration 50% by mass) - toluene solution 4.85 parts by mass

‧Particle additive C8 0.1 parts by mass

‧ ethyl acetate 90.05 parts by mass

‧Photoradical polymerization initiator 0.15 parts by mass

("Irgacure" (registered trademark) 184 BASF JAPAN Co., Ltd.).

<Particle Additive C>

For the particle additive C, the following particle dispersions were used, respectively. In addition, the details of the shape of each particle component are as shown in Table 1.

Particle additive C1: cerium oxide particle dispersion ("MEK-AC-2140Z" Nissan Chemical Industry Co., Ltd.)

Particle additive C2: boehmite dispersion (column boehmite sol, manufactured by Kawasaki Precision Chemical Co., Ltd.)

Particle additive C3: Boehmite dispersion (column boehmite sol, manufactured by Kawasaki Precision Chemical Co., Ltd.)

Particle Additive C4: Layered Citrate ("Lucentite SPN" Co-op Chemical) 1% by weight IPA dispersion

Particle additive C5: chain cerium oxide particle dispersion ("MEK-ST-UP" Nissan Chemical Industry Co., Ltd.)

Particle additive C6: Boehmite dispersion (fibrous boehmite sol, manufactured by Kawasaki Precision Chemical Co., Ltd.)

Particle additive C7: cerium oxide particle dispersion ("MEK-ST-L", Nissan Chemical Industry Co., Ltd.)

Particle additive C8: cerium oxide particle dispersion ("MEK-ST-2040", Nissan Chemical Industry Co., Ltd.)

<Manufacturing method of laminated body>

"Lumirror" (registered trademark) U48 (manufactured by Toray Industries, Inc.) having a thickness of 50 μm was applied to a PET resin film which is a support substrate. On the support substrate, the coating compositions A and B were subjected to coating by adjusting the thickness so that the thickness of the surface layer after drying became a predetermined film thickness, and then the drying step and the curing step were carried out under the following conditions. The surface layer is formed on the support substrate by sequentially applying a series of coating, drying, and hardening operations.

In addition, the preparation method of the above-mentioned laminated body corresponding to each Example ‧ comparative example, the coating composition used, and the theoretical film thickness of each layer are described in Table 1.

"Step of drying UV curing 1"

Air supply temperature and humidity: Temperature: 80 ° C Wind speed: coated side: 5 m / s, reverse coated side: 5 m / s Wind direction: coated side: parallel to the surface of the substrate, reverse coated side: perpendicular to Surface retention time of the substrate: 2 minutes "UV hardening 1 hardening step" Accumulated light amount: 120 mJ/cm ² Oxygen concentration: 200 ppm or less.

"Step of drying UV hardening 2"

Air supply temperature and humidity: Temperature: 80 ° C Wind speed: coated side: 5 m / s, reverse coated side: 5 m / s Wind direction: coated side: parallel to the surface of the substrate, reverse coated side: perpendicular to Surface retention time of the substrate: 2 minutes "hardening step of UV hardening 2" Accumulated light amount: 120 mJ/cm ² Oxygen concentration: atmospheric environment.

"Thermal hardening 1 drying ‧ hardening step"

Air supply temperature and humidity: Temperature: 80 ° C Wind speed: coated side: 5 m / s, reverse coated side: 5 m / s Wind direction: coated side: parallel to the surface of the substrate, Reverse coated side: perpendicular to the surface of the substrate: 2 minutes

The laminates of Examples 1 to 19 and Comparative Examples 1 to 6 were prepared in accordance with the above methods.

<Evaluation of laminated body>

The performance evaluation shown below was carried out about the produced laminate, and the results obtained are shown in Tables 2 to 4. In the case of the specific statement, in the respective examples and comparative examples, the measurement was performed three times for each sample change position, and the average value thereof was used.

[Measurement of Elasticity by Atomic Force Microscopy]

The laminates of Examples 1 to 19 and Comparative Examples 1 to 6 were embedded and hardened with an epoxy resin for electron microscopy (Queto 1812 manufactured by Nisshin EM Co., Ltd.), and then cut into sections by a cryosection method. As a measuring surface, it is fixed to a dedicated sample fixing table. AFM "MFP-3DSA-J" manufactured by Asylum Technology and cantilever "R150-NCL-10 (material Si, spring constant 48N/m, radius of curvature of the front end 150nm) made by NANOSENSORS) are used for the surface layer and the supporting substrate. For the profile, the force curve was measured in contact mode (the movement speed of the cantilever was 2 μm/s and the maximum indentation load was 2 μN).

The Force-Ind curve obtained from the power curve is analyzed according to the theory of Hertz attached to the software "IgorPro 6.22A MFP3D101010+1313" attached to the AFM device, and the elastic modulus distribution in the thickness direction is obtained. Furthermore, Tip Geometry = Sphere, Radius = 150 nm, Select = Fused Silica, v TiP = 0.17, ETip = 74.9 GPa, v Sample = 0.33, the low value of the Force tab = 10%, and the high value of the Force tab = 90%.

[Determination of the elastic modulus distribution in the thickness direction of the section]

The surface image of the layered body prepared by the above method was measured by a Tapping mode and a resolution of 512 × 512 pixels. Then, from the obtained surface image, the magnification is adjusted to the thickness of the surface layer to be within the viewing angle. At this time, the surface layer-supporting substrate interface is observed to be a bright line or a dark line due to the inconsistency of the elastic modulus of the boundary portion of the surface layer and the supporting substrate, and the center of the bright line or the dark line is used as the thickness direction of the surface layer. The baseline is measured. Further, in the same manner, in the same manner, the center of the bright line or the dark line generated by the inconsistency in the elastic modulus of the surface layer and the embedding resin is used as the measurement reference line in the thickness direction of the surface layer. In the following measurement, the "distance from the outermost surface" means the distance from the center of the bright line or the dark line in the outermost surface, and the "distance to the outermost surface" means the surface to the aforementioned surface. The distance between the center of the light line or the dark line. Similarly, the case of "distance from the surface layer to the support substrate interface" means the distance from the center of the bright line or the dark line in the aforementioned interface, "the distance from the surface layer to the support substrate interface", Refers to the distance to the center of the bright or dark line in the aforementioned interface.

The distance from the surface layer-supporting substrate interface to the outermost surface is taken as the total thickness of the surface layer. Then, from the measurement point of the lattice point of the resolution of 512 × 512, the data group on the straight line in which the surface layer is longitudinally cut is selected. Further, from the angle formed by the straight line dividing the surface layer to which the data group belongs and the normal line of the laminated body, the distance from the surface layer-supporting substrate interface of each data point in the thickness direction is calculated, and the thickness direction is Distance approx The modulus of elasticity was measured by the above method in a manner of 100 nm intervals to obtain an elastic modulus distribution in the thickness direction. At this time, the distance from the thickness direction of the surface layer-support substrate interface is less than 100 nm (symbol 10 of Fig. 1), and the distance from the outermost surface is less than 100 nm (symbol 11 of Fig. 1), because it is easy Except for the interface and surface, it is excluded from the measurement point. Further, in the case where the measurement is carried out by the above method, the lower limit of the distance between the measurement points which can be actually set is determined by the thickness of the surface layer and the resolution. Specifically, it is about 500 parts of the thickness of the surface layer. For example, if the thickness of the surface layer is 50 μm, the spatial resolution is about 100 nm. Although the analysis capability can be further improved in the setting of the device, the above-described about 100 nm is a practically measurable value based on the curvature of the cantilever and the number of measurement points.

Then, in terms of the elastic modulus of the outermost surface side and the interface side, the surface layer is located at a position 100 nm from the outermost surface (symbol 5 of FIG. 1) and a position of 100 nm inside the interface (1st) The points of the symbol 7) are randomly selected, and the average value of the measurement results at the respective five points is taken as the elastic modulus of the outermost surface side and the interface side.

[Measurement of elastic modulus of support substrate]

For the support substrate, the modulus of the cross section was also measured in the same manner. Regarding the measurement position, in the support substrate, the point from the distance between the support substrate and the surface layer at a distance of 100 nm from the support substrate side (for example, symbol 8 in FIG. 1) is taken as the starting point along the thickness direction of the support substrate. (The direction opposite to the direction in which the surface layer exists) The elastic modulus was measured at intervals of 100 nm. Measured from the interface between the support substrate and the surface layer to the same thickness as the surface layer (for example, if the thickness of the surface layer When the thickness is 3 μm, the modulus of elasticity is measured at a distance of 100 nm to a distance of 3 μm from the interface between the support substrate and the surface layer, and the average value thereof is used as the elastic modulus of the support substrate.

[Calculation of parameters from the elastic modulus distribution in the thickness direction]

According to the thickness direction parameters obtained by the above method, the average value (Ta) of the thickness of the portion having the highest elastic modulus, the minimum elastic modulus, and the elastic modulus higher than the elastic modulus of the supporting substrate is calculated according to the following method, respectively. The average value (Tb) of the thickness of the portion where the elastic modulus of the support substrate is lower, the average value (Ea) of the maximum elastic modulus, and the average value (Eb) of the extremely small elastic modulus.

First, among the obtained elastic ratios, the measurement position in the thickness direction belongs to the measurement points in the surface layer, and the value of the maximum modulus of elasticity is the maximum modulus of elasticity, and the value of the modulus of elasticity is the minimum value as the minimum modulus of elasticity. Then, the elastic modulus is extracted from the measurement points in the surface layer, and all the values larger than the elastic modulus of the support substrate are extracted from the maximum values, and the average value is obtained to obtain Ea. The Eb was calculated in the same manner except that the maximum value was replaced by the extraction minimum value and a value smaller than the elastic modulus of the support substrate was used.

Next, by the elastic modulus distribution in the thickness direction and the elastic modulus of the supporting substrate, the portion where the elastic modulus is higher than the elastic modulus of the supporting substrate and the portion where the elastic modulus is lower than the elastic modulus of the supporting substrate are calculated. This concept is shown in Fig. 3. Specifically, the coordinates of the intersection of the value of the "elasticity of the supporting substrate" and the "elasticity distribution of the thickness direction" are calculated by the following method. As described above, since the "elasticity distribution in the thickness direction" is a collection of discrete data points at intervals of 100 nm, the extraction satisfies "one The elastic modulus is lower than the elastic modulus of the support substrate, and the elastic modulus of the other substrate is higher than the elastic modulus of the support substrate. The two points adjacent to each other satisfy the two points satisfying the above conditions and the support group are calculated. The coordinates of the intersection of the straightness of the material's modulus of elasticity (hereinafter referred to as the coordinates of the intersection). Then, from the coordinates of the calculated intersections, the distance in the thickness direction between the intersections is calculated as "the thickness of the portion where the elastic modulus is higher than the elastic modulus of the support substrate" and "the elastic modulus is lower than the elastic modulus of the support substrate. Partial thickness". Furthermore, the thickness of the interface side with the support substrate is the distance from the coordinate of the intersection of the surface layer-support substrate interface (symbol 13 of FIG. 4) to the shortest distance (symbol 22 of FIG. 4). "The thickness of the portion where the modulus of elasticity is higher than the modulus of elasticity of the supporting substrate". Further, the thickness on the outermost surface side is the distance from the intersection of the outermost surface (symbol 12 of FIG. 4) to the shortest distance (symbol 23 of FIG. 4) as "the elastic modulus is higher than the elastic modulus of the support substrate. Partial thickness". Further, the calculated elastic modulus is equal to the thickness of the portion where the elastic modulus of the support substrate is lower than the elastic modulus of the portion of the support substrate, and the elastic modulus is calculated as the elasticity of the support substrate. The average value (Ta) of the thickness of the portion where the rate is high and the average value (Tb) of the thickness of the portion where the modulus of elasticity is lower than the modulus of elasticity of the supporting substrate.

[Measurement of Shape of Inorganic Particles with Anisotropic Shape]

The shape of the inorganic particles contained in the cross section of the surface layer was measured by observing the cross section using a transmission electron microscope (TEM). The shape of the inorganic particles was measured in accordance with the following method. First, ultrathin sections of the cross section of the laminated body were photographed by TEM at a magnification of 200,000 times. Then the image is converted to grayscale by the image processing software EasyAccess Ver6.7.1.23, so that the brightest part and the darkest part can be included in the 8bit. Adjust the white balance in the way of the tone curve. Furthermore, the contrast is adjusted in such a way that the boundaries of the inorganic particles can be clearly distinguished. Then, using the software (image processing software ImageJ/developer: National Institutes of Health (NIH)), the above-mentioned boundary is binarized on the boundary, and each inorganic is extracted by the Analize Particles function. The region in which the particle is located, thereby taking the area of the region as a long diameter by the fact that Fit Ellipse is approximated to be elliptical, and the Minor value as the short diameter. The above analysis was carried out for 50 inorganic particles, and the maximum diameter of the long diameter was the long diameter R1, and the minimum value of the short diameter was the short diameter Rs.

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

Then, from the observation of the same transmission electron microscope (TEM), the calculation of the existence rate of the inorganic particles was carried out. First, the ultrathin section of the section of the laminate was photographed by TEM at a magnification of 50,000 times. Then, using the image processing software EasyAccess Ver6.7.1.23, the image is converted into grayscale, and the white balance is adjusted such that the brightest portion and the darkest portion are included in the 8-bit tone curve. Further, the contrast is adjusted so that the boundary of the inorganic particles can be clearly distinguished, and the rotation of the surface layer-supporting substrate interface (symbol 13 of Fig. 4) is performed horizontally, and the cutting is performed. Then, by the method of [calculation of the parameter of the elastic modulus distribution in the thickness direction], the obtained "the thickness of the elastic modulus is higher than the elastic modulus of the supporting substrate" and the "elasticity ratio" The value of the thickness of the portion supporting the low elastic modulus of the substrate is such that the image is subdivided into strips in a direction parallel to the interface. Then use the software (image processing software ImageJ / developer: National Institutes of Health (NIH)), the aforementioned The boundary is used to binarize the pixels on the border, and the area of each inorganic particle is extracted by the Analize Particles function, thereby calculating the area of the region. In the same manner, the area formed by the cut strip image was calculated, and the area ratio of the inorganic particles in the strip shape was calculated as the existence ratio of the inorganic particles. In the existence ratio calculated as described above, the average value of the values obtained from the strips of the "elasticity ratio of the portion higher than the elastic modulus of the support substrate" is regarded as the elastic ratio ratio support group. The existence ratio of the high elastic modulus of the material is Fa; the average value of the value obtained from the strip shape of the "elasticity is lower than the thickness of the support substrate" is regarded as the elastic ratio of the support group. The existence rate of the low elastic modulus of the material is Fb.

[Measurement of Surface Hardness of Surface Layer by Pencil Hardness Test Method]

After the laminated body was placed in a normal state (24 ° C, relative humidity: 65%) for 12 hours, the scratch hardness (pencil method) according to JIS K 5600-5-4 (1999) was used in the same environment. The surface hardness of the surface layer was measured.

[Scratch resistance of surface layer]

After the laminated body was placed under normal conditions (24 ° C, relative humidity 65%) for 12 hours, for the surface having the surface layer, a steel wool (# 0000) having a load of 1,000 g/cm ^{2 was} formed vertically, at 5 cm. When the length is scraped back and forth 10 times, the approximate number of visually visible scars is described, and the following classification is performed.

5 points: 0

4 points: 1 or more and less than 5

3 points: 5 or more and less than 10

2 points: 10 or more and less than 20

1 point: 20 or more.

[Flexibility of laminated body]

After the laminated body was placed in a normal state (24 ° C, relative humidity: 65%) for 12 hours, the bending resistance (cylindrical mandrel) described in JIS K 5600-5-1 (1999) was observed in the same environment. Method 1 implementation evaluation. For the mandrel, the diameters of 2, 3, 4, and 5 mm were used, and visually determined, the classification was as follows, by not observing the crack and the minimum diameter of the peeling of the coating film. In addition, the same evaluation was carried out under the conditions of the bending (mountain bending) condition in which the surface of the surface layer was outside and the bending (valley bending) in which the surface of the surface layer was inside.

5 points: 2mmφ without cracks, peeling

4 points: 2mmφ cracked, peeled, 3mmφ without cracks, peeling

3 points: 3mmφ cracked, peeled, 4mmφ without cracks, peeling

2 points: 4mmφ cracked, peeled, 5mmφ without cracks, peeling

1 point: 5mmφ has cracks and peeling.

[Curling of laminated body]

The laminated body thus prepared was placed in a normal state (24 ° C, relative humidity: 65%) for 12 hours, and then cut into a square shape of 10 cm square, and placed on a horizontal surface. Then, the distance between the 4 积 point of the laminated body and the horizontal plane is measured, and according to the average of the numerical values, it is classified into 5 levels.

5 points: less than 1mm

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

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

2 points: 20mm or more

1 point: It becomes a tube and cannot be measured.

[The adhesion of the surface layer]

After the laminate was placed in a normal state (24 ° C, relative humidity 65%) for 12 hours, the surface having the surface layer was cut into 100 squares of 1 mm ² and Nichiban Co., Ltd. was attached thereto. "Sellotape" (registered trademark), using a rubber roller, and pressing back and forth three times with a load of 19.6N, and peeling off in a 90-degree direction, according to the number of remaining layers of the conductive layer, 5 levels of evaluation (5: 96 ~ 100 1, 4:81~95, 3:71~80, 2:61~70, 1:0~60).

[Industrial availability]

The laminate according to the present invention can also be used to impart the same functions to the respective surfaces of plastic molded articles, home electric appliances, buildings, vehicle interiors, and various printed materials.

1‧‧‧Support substrate

2‧‧‧ surface layer

3‧‧‧Layer

4‧‧‧The surface of the surface layer

5‧‧‧Measurement point of the elastic modulus at the outermost surface

6‧‧‧ Interface between surface layer and supporting substrate

7‧‧‧Measurement point of the elastic modulus at the interface side

8‧‧‧Starting point of elastic modulus measurement of supporting substrate

9‧‧‧Support substrate elastic modulus

10‧‧‧A zone that has not been measured due to the influence of the supporting substrate

11‧‧‧A zone that has not been measured due to the influence of the surface

12‧‧‧The position of the outermost surface of the surface layer

13‧‧‧Surface layer - the position of the support substrate interface

Claims (6)

A laminated body which is a laminated body having a surface layer laminated on a supporting substrate, wherein a modulus of elasticity in a thickness direction of the surface layer has a maximum value of an elastic modulus higher than a modulus of elasticity of the supporting substrate and The elastic modulus is a minimum value lower than the elastic modulus of the supporting substrate, and the elastic modulus at the interface side with the supporting substrate and the elastic modulus at the outermost surface side of the surface layer are higher than the elastic modulus of the supporting substrate. The laminate according to claim 1, wherein in the elastic modulus distribution in the thickness direction of the surface layer, the maximum elastic modulus 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 modulus of elasticity is 0.1 GPa or less in the elastic modulus distribution in the thickness direction of the surface layer. The laminate according to any one of claims 1 to 3, wherein in the elastic modulus distribution in the thickness direction of the surface layer, the elastic modulus is higher than the elastic modulus of the support substrate, and the elastic modulus is higher than the elastic modulus of the support substrate. The minimum value of the low rate interacts, and the thickness and the elastic modulus calculated from the elastic modulus distribution satisfy the following relationship: 10 ≦ (Tb [nm] / Ta [nm]) × (Ea [MPa]) / Eb [MPa]) 1,000 (Formula 1) Ta [nm]: the average value of the thickness of the portion where the modulus of elasticity is higher than the elastic modulus of the supporting substrate Tb [nm]: the thickness of the portion of the elastic modulus lower than the elastic modulus of the supporting substrate Average value Ea [MPa]: average value of maximum elastic modulus Eb [MPa]: average value of extremely small elastic modulus. The laminate according to any one of claims 1 to 4, wherein the surface layer comprises inorganic particles having an anisotropic shape satisfying the formula: 1.2 ≦ Rl / Rs ≦ 20,000 (Formula 2) 1 nm ≦Rs ≦ 100 nm (Formula 3) Rl [nm]: long diameter of inorganic particles Rs [nm]: short diameter of inorganic particles. The laminate according to any one of claims 1 to 5, wherein in the cross section perpendicular to the support substrate of the surface layer, the existence ratio F of the anisotropically shaped inorganic particles in the thickness direction satisfies the following conditions: Fa<Fb (Formula 4) Fa: The existence ratio of the portion where the modulus of elasticity is higher than the modulus of elasticity of the support substrate Fb: the existence ratio of the portion where the modulus of elasticity is lower than the modulus of elasticity of the support substrate.