JP2019025739A - Laminate and resin film - Google Patents

Abstract

To provide a laminate hardly deteriorating function of a hard coat layer such as scratch resistance or weather resistance, and capable of being transferred in a plane uniformly.SOLUTION: There is provided a laminate 22 having a resin layer 24 on at least one side surface of a supporting substrate 23 and satisfying following condition 1 and condition 2. Condition 1: Indentation elastic modulus of a surface by a minute hardness meter of the resin layer is 1 GPa or more. Condition 2: All of following formula 1 to 3 are satisfied, when 180° peel force between the resin layer and the supporting substrate is F (N/m), Young modulus of the resin layer after peeling is E (Pa), breaking elongation is L (-), and resin layer thickness is T (m). Formula 1 E L T/F≥15 Formula 2 5×10≤T≤1.8×10Formula 3 F≥1 Further as condition 3, in an elastic modulus distribution in a thickness direction at a cross section vertical to the supporting substrate 23, total thickness of an area lower than elastic modulus of 0.5 GPa is 20 to 80% of resin layer thickness.SELECTED DRAWING: Figure 4

Description

  The present invention relates to a laminate that can impart scratch resistance and various functions to other articles, and a resin film.

  In general, the surface of plastics or metal is more easily damaged than glass. Therefore, in plastics and metal moldings that are required to maintain the glossiness and transparency of the surface when used as a product, a layer that imparts scratch resistance to the surface (hereinafter referred to as a hard coat layer). ) May be provided. Furthermore, the hard coat layer may be used for imparting a molded product with functions other than scratch resistance, such as functions such as weather resistance, gas barrier properties, and anti-blocking properties.

  This hard coat layer is generally formed by directly applying and curing on the surface of plastics and metal constituting the molded body, or by attaching a plastic film on which a hard coat layer has been formed in advance, or forming the molded body. It is provided by molding integrally with plastics or metal. In addition, when direct application is impossible due to the heat resistance, processing temperature, and solvent resistance of the material that constitutes the molded body, and functions other than scratch resistance, such as optical functional layers and design layers, etc. There is also a method in which a hard coat layer is formed on a substrate film different from that constituting the molded body and transferred to the surface of the molded body.

  In addition to the molded body as described above, in applications such as electronic devices and displays, in order to reduce process materials, reduce the thickness of products, and improve the flexibility of product forms, in addition to scratch resistance, optical properties, Instead of using a hard coat film having various functions such as electrical characteristics, a method of transferring a hard coat layer having a function has been studied.

  In this way, as a method of creating a functional layer including a hard coat layer on a base film and transferring it from the base film, Patent Document 1 states that “on one surface of a peelable base sheet, a hard ionization A hard coat transfer foil characterized by laminating a hard coat layer made of a radiation curable resin and a hard coat layer made of a soft ionizing radiation curable resin in this order has been proposed.

  Further, Patent Document 2 discloses “2” as a release polyester film for transfer having a releasing property such that when a transfer product including a hard coat layer is peeled off, a crack (cracking) phenomenon does not occur in the transfer product. A release polyester comprising a release layer containing (1) a modified wax having a softening point of 60 ° C. or higher and 105 ° C. or lower, (2) a binder resin component, and (3) a crosslinking component on at least one surface of an axially stretched polyester film. A release polyester film for transfer, which is a film and has a peeling force of the hard coat layer to the release layer of 4.0 mN / mm or more and 20 mN / mm or less.

Japanese Patent Laid-Open No. 3-130199 JP 2014-162045 A

  An essential problem in the transfer of the hard coat layer including such a functional layer is to transfer uniformly in the surface without impairing the functions of the hard coat layer such as scratch resistance and weather resistance. In order to solve this problem, the technique of Patent Document 1 can surely impart scratch resistance to the molded body by transfer. However, as the inventors have confirmed, other techniques required for the hard coat layer before and after the transfer are confirmed. It was found that the functions, such as solvent resistance and dye transfer resistance, are greatly reduced. This is because fine cracks at a level that can be observed with an electron microscope occur due to deformation of the hard coat layer during transfer, which is impossible with the naked eye.

  Moreover, although the technique of patent document 2 was certainly effective in suppressing the fine crack to the hard-coat layer at the time of peeling, it is an incomplete hardening state and required abrasion resistance is not obtained. Further, in order to obtain the required wear resistance, it is necessary to heat and cure the adherend again after transfer, which requires complicated work and heat resistance of the adherend. Furthermore, when the present inventors confirmed, when it hardens | cures completely before peeling and transfers, a fine crack will arise like patent document 1, and, thereby, functions, such as solvent resistance and barrier property, may fall significantly. all right. From the above points, it is difficult to solve the essential problems in the transfer of the hard coat layer including the functional layer with the conventional technology.

In order to solve the above-described problems, the present inventors have intensively studied and, as a result, completed the following invention. That is, the present invention is as follows.
1. A laminate having a resin layer on at least one surface of a support substrate, wherein the laminate satisfies the following conditions 1 and 2.
Condition 1: The indentation modulus of the surface of the resin layer measured by a microhardness meter is 1 GPa or more. Condition 2: The 180 ° peeling force between the resin layer and the supporting substrate is F (N / m), and the Young's modulus of the resin layer after peeling is When E (Pa), breaking elongation is L (-), and resin layer thickness is T (m), all of the following formulas 1 to 3 are satisfied Formula 1 E · L · T / F ≧ 15
Formula 2 5 × 10 ⁻⁷ ≦ T ≦ 1.8 × 10 ⁻⁵
Formula 3 F ≧ 1
2. The following condition 3 is satisfied in the elastic modulus distribution in the thickness direction in a cross section perpendicular to the support base of the resin layer: The laminated body as described in.
Condition 3: In the elastic modulus distribution in the thickness direction, the total thickness of the region below the elastic modulus of 0.5 GPa is 20% or more and 80% or less of the total thickness of the resin layer. The standard deviation of the elastic modulus distribution in the range of 3 μm square, measured by an atomic force microscope, is 30 MPa or more with respect to the surface (surface B) on which the resin layer is in contact with the surface of the support substrate. 1. Or 2. The laminated body as described in.
4.1. ~ 3. A resin film obtained by peeling a supporting substrate from the laminate according to any one of the above.

  According to the present invention, the functions of the hard coat layer such as scratch resistance and weather resistance are not easily lost from the laminate, and the surface can be uniformly transferred.

It is a graph which shows the example of the thickness direction elastic modulus distribution of a resin layer. It is a graph which shows the example of the thickness direction elastic modulus distribution of a resin layer. It is a graph which shows the example of the thickness direction elastic modulus distribution of a resin layer. It is sectional drawing which shows the example of the layer structure of a resin layer. It is sectional drawing which shows the example of the layer structure of a resin layer. It is sectional drawing which shows the example of the layer structure of a resin layer. It is sectional drawing which shows an example (multilayer slide die coating) of the die-coating method used for this invention. It is sectional drawing which shows an example (multilayer slot die coating) of the die-coating method used for this invention. It is sectional drawing which shows an example (wet-on-wet coat) of the die-coating method used for this invention.

  In order to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by making the physical properties of the support substrate and the resin layer have a specific relationship. That is, it is a laminate having a resin layer on at least one surface of the support substrate, and it is preferable that the following conditions 1 and 2 are satisfied.

  Here, condition 1 is that the indentation elastic modulus of the surface of the resin layer measured by a microhardness meter is 1 GPa or more, condition 2 is that the 180 ° peeling force between the resin layer and the supporting substrate is F (N / m), and the resin layer after peeling When the Young's modulus is E (Pa), the breaking elongation is L (-), and the resin layer thickness is T (m), all of the following formulas 1 to 3 are satisfied.

Formula 1 E · L · T / F ≧ 15
Formula 2 5 × 10 ⁻⁷ ≦ T ≦ 1.8 × 10 ⁻⁵
Formula 3 F ≧ 1.

As described above, the indentation elastic modulus of the resin layer by the microhardness meter is preferably 1 GPa or more, and more preferably 3 GPa or more. In Formula 1, E · L · T / F ≧ 15 is preferable, E · L · T / F ≧ 60 is more preferable, and E · L · T / F ≧ 100 is particularly preferable. In Formula 2, 1 × 10 ⁻⁶ ≦ T ≦ 15 × 10 ⁻⁶ is more preferable.

  Indentation elastic modulus by microhardness meter, Young's modulus of resin layer after peeling (hereinafter referred to as E), elongation at break (hereinafter referred to as L) of resin layer after peeling, resin layer thickness (hereinafter referred to as T), resin A method for measuring the 180 ° peeling force (hereinafter referred to as F) between the layer and the supporting substrate will be described later.

  The magnitude of the indentation elastic modulus measured by the micro hardness tester corresponds to the hardness of the resin layer surface, the magnitude of the Young's modulus E corresponds to the difficulty of deforming the entire resin layer, and the magnitude of the breaking elongation L is the whole resin layer. The magnitude of the peel force F corresponds to the magnitude of the force for peeling off the resin layer.

When the indentation elastic modulus on the surface of the resin layer is less than 1 GPa, scratch resistance may be insufficient. Further, the indentation elastic modulus on the surface of the resin layer is preferably as high as possible, but in reality, about 10 GPa is the limit. In the above formula 1, E, L, and F are particularly limited as long as the above formula 1 is satisfied. However, E is limited to about 10 × 10 ⁻¹⁰ Pa to about 1 × 10 ⁻⁷ Pa and L is about 0.001 to about 10 based on a combination of realistic materials. .

  The above formula 1 E · L · T / F using Young's modulus E, breaking elongation L, resin layer thickness T and peel force F can be peeled evenly and without cracks when the resin layer is peeled off. If E · L · T / F is less than 15 in Eq. 1, it may be broken at the time of peeling or cracked, and the function required for the resin layer may not be obtained. is there.

In the above-mentioned formula 2, if T is smaller than 5 × 10 ⁻⁷ m, the scratch resistance may be insufficient, and if T is larger than 1.8 × 10 ⁻⁵ m, the molded article of the resin layer In some cases, the followability to the surface is insufficient. A method for measuring T will be described later.

  In Formula 3 described above, when F is less than 1 N / m, the adhesion between the resin layer and the supporting base material becomes insufficient, and may float or wrinkle in the process.

  Further, in the resin layer, the elastic modulus distribution in the thickness direction in a cross section perpendicular to the supporting base material preferably has a distribution within a specific range, and specifically satisfies the following condition 3.

  Thus, satisfying the preferable range of the indentation elastic modulus and all the formulas 1 to 3 means that the hard coat layer excellent in shape and excellent in quality can be transferred in-plane uniformly. Yes.

  The elastic modulus distribution in the thickness direction of the resin layer is obtained by measuring the ease of deformation at each point in the thickness direction of the resin layer. As will be described later in the elastic modulus distribution in the thickness direction of the resin layer, the total thickness of the region where the elastic modulus is below a specific value occupies a specific range of the total thickness of the resin layer. This indicates that the region easily deformed occupies a specific thickness range, and as a result, the resin layer can exhibit, for example, appropriate flexibility and scratch resistance.

  Here, in condition 3, in the elastic modulus distribution in the thickness direction of the resin layer, the total thickness of the region where the elastic modulus is less than 0.5 GPa is preferably 20% or more and 80% or less of the total thickness of the resin layer, and preferably 40% or more and 70 % Is more preferable, and if the total thickness of the region below the elastic modulus of 0.5 MPa is less than 20%, the effect of suppressing cracks may be insufficient at the time of transfer, and if it exceeds 80%, scratch resistance May be insufficient.

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

Atomic force microscope: MFP-3DSA-J manufactured by Asylum Technology
Cantilever: A cantilever “R150-NCL-10 manufactured by NANOSENSORS (material Si, spring constant 48 N / m, radius of curvature of the tip 150 nm).

  The elastic modulus distribution of the resin layer of the laminate is not particularly limited as long as the elastic modulus distribution in the thickness direction satisfies the above condition 3, but from the viewpoint of scratch resistance, Thus, the resin layer having a high surface side and a low supporting substrate side, more preferably a resin layer having a high surface side and a base material side and a low resin layer center portion as shown in FIG. More preferably, from the viewpoint of avoiding stress concentration in the resin layer, it is preferable that the elastic modulus distribution of the resin layer gradually changes in the thickness direction as shown in FIG.

  The composition of the resin layer of the laminate is not particularly limited as long as the elastic modulus distribution in the thickness direction satisfies the condition 3 described above, but the resin composition is preferably different in the thickness direction. . The resin composition in the thickness direction may be composed of a plurality of layers in which the resin layer has a clear interface as shown in FIG. 4, or even if the composition gradually changes in one layer as shown in FIG. However, the latter is preferred from the viewpoint of suppressing stress concentration in the resin layer and preventing peeling in the resin layer. The definition of layers and how to achieve them will be described later.

  Furthermore, the surface (hereinafter referred to as “surface B”) in contact with the resin layer in the support substrate can control the formula 1 of condition 2 in a preferable range and the aforementioned F, and the in-plane of the resin layer thickness. It is preferable to have a specific elastic modulus distribution in terms of uniformity and quality improvement. The standard deviation of the elastic modulus distribution on the surface B is the extent of the distribution of the ease of deformation of the surface B surface, and the larger the value, the different the ease of deformation within the surface.

  Specifically, the standard deviation of the elastic modulus distribution in the range of 3 μm square measured by an atomic force microscope on the surface B is preferably 30 MPa or more, and more preferably 40 MPa or more. A method for measuring the elastic modulus distribution of the surface B will be described later.

  The standard deviation described here indicates the spread width of the elastic modulus distribution, that is, the variation of the elastic modulus, and a specific calculation method will be described later. The larger the standard deviation, the greater this effect.

  The support base material of the laminate preferably satisfies the above-mentioned condition 1 by combination with the resin layer, and more preferably, if the elastic modulus distribution of the surface B can be made as described above, its configuration and material Although not particularly limited, it is preferable to use a support substrate having a release layer on the surface B. Details of the supporting substrate, details of the release layer, and achievement method will be described later.

[Mode of the Invention]
Hereinafter, embodiments of the present invention will be specifically described.

[Laminated body and resin layer]
The resin layer in the present invention refers to a layer formed on a support base material and can be peeled off from the support base material. Even if the layer is formed on the support substrate, a layer that cannot be peeled, for example, a release layer described later, is not included in the resin layer and is a part of the support substrate. The criteria for determining whether or not peeling is possible is evaluated by the cross-cut method described in JIS K5600-5-6: 1999. Impossible. A laminated body including all of the resin layer and the supporting base material is used. When only one layer is formed on the supporting substrate, the one layer becomes a resin layer, and when two or more layers are formed on the supporting substrate, the two excluding the supporting substrate. One or more layers are defined as one resin layer.

  Here, the layer refers to a portion having a finite thickness that can be distinguished by having a boundary surface and a portion adjacent to each other in the thickness direction from the surface side of the laminate toward the thickness direction. More specifically, when the cross section of the said laminated body is cross-sectional-observed with an electron microscope (a transmission type, a scanning type) or an optical microscope, it points out what is distinguished by the presence or absence of a discontinuous interface. Therefore, even if the composition changes in the thickness direction of the resin layer, if there is no boundary surface between them, it is handled as one layer.

  The laminate of the present invention may be in a planar state or a three-dimensional shape as long as it has a resin layer exhibiting the aforementioned physical properties. The thickness of the entire resin layer is preferably 0.5 μm or more and 20 μm or less, and more preferably 1 μm or more and 15 μm or less.

  The resin layer has gloss, fingerprint resistance, moldability, designability, scratch resistance, antifouling, solvent resistance, antireflection, antistatic, conductivity, heat ray reflection, near infrared absorption, electromagnetic wave shielding, easy adhesion Other functions may be provided.

  Further, one or more layers may be formed on the resin layer, for example, a functional layer having the above-mentioned function, an adhesive layer, an electronic circuit layer, a printed layer, an optical adjustment layer, and other functional layers. May be provided.

[Supporting substrate]
The resin constituting the support substrate used in the laminate of the present invention may be either a thermoplastic resin or a thermosetting resin, may be a homo resin, may be a copolymer or a blend of two or more types. Good. The resin constituting the supporting base material is preferable if the moldability is good, and a thermoplastic resin is more preferable in that respect.

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

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

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

  Various surface treatments can be performed before forming the resin layer. Examples of the surface treatment include chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment and ozone oxidation treatment. Among these, glow discharge treatment, ultraviolet irradiation treatment, corona discharge treatment and flame treatment are preferred, and glow discharge treatment and ultraviolet treatment are more preferred. In addition, a plurality of functional layers such as an easy adhesion layer, an antistatic layer, an undercoat layer, and an ultraviolet absorption layer can be provided in advance on the surface of the support base.

  The surface of the supporting substrate, that is, the surface in contact with the resin layer (surface B) in the supporting substrate preferably has a standard deviation and an average value of a specific elastic modulus distribution as described above. Although the achievement method will not be specifically limited if the said conditions are satisfy | filled, it is preferable to use the support base material which has a release layer in the surface B of a support base material. Here, in the case of only the supporting substrate (without the release layer), the surface of the supporting substrate is the surface B, and when the release layer is provided on the supporting substrate, the surface of the release layer is the surface. B. Details of the release layer will be described later.

[Manufacturing method of release layer / release layer]
It is preferable that the above-mentioned supporting base material has a release layer that satisfies the above-described conditions on a surface B that is in contact with the resin layer on at least one surface. The release layer may be composed of a plurality of layers from the viewpoint of imparting adhesion, antistatic properties, solvent resistance, and the like.

  The thickness of the release layer is not particularly limited as long as the surface B in contact with the resin layer can have the standard deviation of the specific elastic modulus distribution and the average value, but the in-plane uniformity, quality, From the surface of peeling force, it is preferably 10 to 500 nm, and more preferably 20 to 200 nm.

  The material of the release layer is not particularly limited as long as the surface B in contact with the resin layer can have the standard deviation and the average value of the specific elastic modulus distribution described above, but depending on the release layer resin composition described later. It is preferably formed, and it is preferably formed on the surface of the supporting substrate by coating, drying, and curing by a method for producing a release layer described later.

  The material for the release layer resin composition is not particularly limited as long as the surface B in contact with the resin layer can have the standard deviation and the average value of the specific elastic modulus distribution described above. However, the material is not limited. A resin, a long-chain alkyl group-containing resin, a fluorine-based resin, a silicone-based resin, a mixture of organic and silicone-based resins or a copolymer resin is preferable.

  The release layer is not particularly limited as long as the surface B in contact with the resin layer can have the standard deviation and average value of the specific elastic modulus distribution described above, but the release layer coating composition is not particularly limited. Preferably, the coating layer is formed by coating by a dip coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method (US Pat. No. 2,681,294), and the gravure coating method or the die coating method is used. preferable.

  Next, the coating layer coated on the support substrate or the like is dried. In addition to completely removing the solvent from the resulting coating layer, the drying step is preferably accompanied by heating of the coating film from the viewpoint of accelerating the curing of the coating film.

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

  Furthermore, you may perform the further hardening operation (hardening process) by irradiating a heat | fever or an energy ray. When curing with heat in the curing step, the temperature is preferably from room temperature to 200 ° C, more preferably from 100 ° C to 200 ° C, and even more preferably from 130 ° C to 200 ° C, from the viewpoint of the activation energy of the curing reaction. It is as follows.

Moreover, when hardening with an energy ray, it is preferable that it is an electron beam (EB ray) and / or an ultraviolet-ray (UV ray) from a versatility point. Examples of the ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method. In the case of UV curing using a high-pressure mercury lamp that is a discharge lamp method, the illuminance of UV is 100 to 3,000 (mW / cm ² ), preferably 200 to 2,000 (mW / cm ² ), and more preferably 300 to 3,000. It is preferable to irradiate with ultraviolet rays under the condition of 1,500 (mW / cm ² ), and the cumulative amount of ultraviolet rays is 100 to 3,000 (mJ / cm ² ), preferably 200 to 2,000 (mJ / cm ² ), more preferably 300 to 1,500 (mJ / cm ² ). Here, the ultraviolet illuminance is the irradiation intensity received per unit area, and changes depending on the lamp output, the emission spectral efficiency, the diameter of the light emitting bulb, the design of the reflector, and the light source distance to the irradiated object. However, the illuminance does not change depending on the conveyance speed. Further, the UV integrated light amount is irradiation energy received per unit area, and is the total amount of photons reaching the surface. The integrated light quantity is inversely proportional to the irradiation speed passing under the light source, and is proportional to the number of irradiations and the number of lamps.

  As described above, it is preferable to form a release layer on the support base by drying and curing the coating layer formed on the support substrate.

[Manufacturing method of laminate]
The production method of the laminate of the present invention is not particularly limited as long as it can form a resin layer that satisfies the above-described conditions 1 and 2, more preferably, the above-described condition 3, on the support substrate. The manufacturing method which can form the resin layer from which a resin composition differs in the thickness direction on the mold release layer of a preferable support base material is preferable. In order to form resin layers having different resin compositions in the thickness direction, a method for producing a laminate in which at least two kinds of coating compositions are applied sequentially or simultaneously, and then dried and cured to form a resin layer. It is preferable that the method of manufacturing a laminate in which at least two or more kinds of coating compositions are applied simultaneously is more preferable.

  Here, “sequentially apply” or “sequential application” means that one type of coating composition is applied to form a coating layer, and then dried-cured, and then a different type of coating composition is applied in the same manner. It is intended to form a resin layer composed of a plurality of layers by drying and curing. The coating method is not particularly limited, but can be appropriately selected from a dip coating method, a roller coating method, a wire bar coating method, a gravure coating method, a die coating method (US Pat. No. 2,681,294). The resin layer formed in the “sequential application” can form a resin layer having a different resin composition in the thickness direction in the resin layer by appropriately selecting the type and number of coating compositions to be used. The drying and curing methods will be described later.

  “Simultaneously apply” or “simultaneous application” means that two or more types of coating compositions are applied on a supporting substrate to form a coating film having two or more coating layers on the supporting substrate. Then, it is a method of forming by drying and curing. The coating method is not particularly limited as long as a coating film having two or more coating layers can be formed on the supporting substrate, but two or more kinds of coating compositions are coated on the supporting substrate by a die coating method, and two layers are applied. The method of forming the coating film which has the above application layer is preferable.

  Here, the coating layer refers to a “liquid layer” formed by an individual coating composition applied on a supporting substrate, and the “coating layer” refers to the entire coating layer formed on the supporting substrate. The coating layer is changed from a liquid to a solid through the above-described drying / curing steps, whereby the above-described resin layer is formed. The definition of the coating composition will be described later.

  In the above-mentioned die coating method capable of simultaneous application, each coating composition is discharged in layers through a die slot, and is applied after laminating on a slide surface to form a coating film composed of a plurality of coating layers. By forming a “multilayer slide die coat” (FIG. 7) to be formed or supplying a plurality of coating compositions to a die having a plurality of slots, a coating film composed of a plurality of coating layers is formed simultaneously with coating on the substrate. “Multilayer slot die coat” (FIG. 8), “wet-on-wet coat” in which a coating layer is formed by laminating another coating layer in an undried state after forming a coating layer on a supporting substrate. (FIG. 9) etc., and any method may be used.

  Hereinafter, examples of various die coating methods and coating layers will be described with reference to the drawings.

  FIG. 7 is a cross-sectional view of simultaneous application of four layers as an example of a multilayer slide die coat. The coating composition forming each coating layer is supplied to the slot 45 on the most upstream side of the four-layer slide die 44, the second slot 46 from the upstream side, the third slot 47 from the upstream side, and the slot 48 on the most downstream side. And discharged onto the slide surface 49. Since the slide surface 49 is inclined, the discharged coating compositions are stacked in the process of flowing down on the slide surface. The support base material is conveyed from the upstream side 51 toward the downstream side 52, and the coating composition flowing down the slide surface 49 by the die lip 50 is applied onto the support base material, and four coating layers are formed on the support base material. The coating film which has is formed.

  FIG. 8 is a cross-sectional view of simultaneous application of two layers as an example of a multilayer slot die coat. The coating composition forming each coating layer is supplied to the upstream slot 54 and the downstream slot 55 of the two-layer slot die 53. These coating compositions are discharged from the slot and then merge at the die lip portion 56.

  The support base material is coated on the support base material by the die lip portion 56 that is conveyed from the upstream side 57 toward the downstream side 58, and a coating film having two coating layers is formed.

  FIG. 9 is a cross-sectional view showing an example of a wet-on-wet coat. In this example, the coating composition for forming each coating layer is supplied to the upstream single-layer slot die 59 and the downstream single-layer slot die 60. First, the coating composition discharged from the upstream single-layer slot die 59 is applied onto the support base material transported from the upstream side 61 toward the downstream side 62 of the support base material, so that one coating layer is formed. The coating film which has is formed. Next, the coating composition discharged from the downstream single-layer slot die 60 is applied onto the coating film applied from the single-layer slot die 59 to form a coating film having two coating layers.

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

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

  Subsequent to the drying step, a further curing operation (curing step) may be performed by irradiation with heat or active energy rays.

As the active energy rays, electron beams (EB rays) and / or ultraviolet rays (UV rays) are preferable from the viewpoint of versatility. In the case of curing with ultraviolet rays, oxygen concentration is preferably as low as possible because oxygen inhibition can be prevented, and curing in a nitrogen atmosphere (nitrogen purge) is more preferable. When the oxygen concentration is high, the hardening of the outermost surface is inhibited, the hardening of the surface becomes weak, and the toughness may be lowered. Examples of the ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method. When using a high-pressure mercury lamp is a discharge lamp type, illuminance of ultraviolet rays is preferably 100~3,000mW / cm ^2, more preferably 200~2,000mW / cm ^2, more preferably the 300~1,500mW / cm ² It is preferable to perform ultraviolet irradiation under the following conditions. Integrated quantity of ultraviolet light is preferably 100~3,000mJ / cm ^2, more preferably 200~2,000mJ / cm ^2, is further preferably irradiated with ultraviolet rays under the condition that the 300~1,500mJ / cm ² preferable. Here, the illuminance of ultraviolet rays is the irradiation intensity received per unit area, and changes depending on the lamp output, the emission spectral efficiency, the diameter of the light emitting bulb, the design of the reflector, and the light source distance to the irradiated object. However, the illuminance does not change depending on the conveyance speed. Further, the UV integrated light amount is irradiation energy received per unit area, and is the total amount of photons reaching the surface. The integrated light quantity is inversely proportional to the irradiation speed passing under the light source, and is proportional to the number of irradiations and the number of lamps.

[Coating composition for resin layer]
The method for producing the laminate of the present invention is not particularly limited, but the laminate of the present invention is obtained through a step of applying a coating composition to at least one of the above-mentioned support substrates, and drying and curing as necessary. Can do.

  Here, the “coating composition” is a liquid composed of a solvent and a solute, and is a material capable of forming a resin layer by applying it on the above-mentioned supporting substrate and evaporating, removing, and curing in the step of drying the solvent. Point to. Here, the “type” of the coating composition refers to liquids that are different in part even in the type of solute constituting the coating composition. This solute is a resin or a material that can form them in the coating process (hereinafter referred to as a precursor), particles, and polymerization initiators, curing agents, catalysts, leveling agents, ultraviolet absorbers, antioxidants, etc. Consists of various additives.

[Coating composition]
The coating composition used in the method for producing a laminate of the present invention is not particularly limited as long as it is a liquid that can be applied on a supporting substrate by the aforementioned production method and can form the aforementioned resin layer. However, in order to form resin layers having different resin compositions in the thickness direction by the above-described production method, it is preferable to use at least two kinds of coating compositions.

  Of the two or more types of coating compositions used in the method for producing a laminate of the present invention, at least one type preferably contains a solvent, a binder raw material, a photopolymerization initiator, a particle dispersion, other additives, and the like. It is possible to achieve the function by controlling according to each material type, physical property, and addition amount.

[Binder raw material]
The binder raw material is a material that is soluble in a solvent and can be included in a coating composition, and can cure the coating film by volatilization of the solvent, polymerization of itself, and a crosslinking reaction. Call it. Of the two or more types of coating compositions used in the method for producing a laminate of the present invention, at least one type preferably includes a binder material, and all of the two types of coating compositions include a binder material. Is more preferable. The binder raw material is not particularly limited, but may be one kind or a mixture of two or more kinds.

  In the method for producing a laminate of the present invention described above, the binder raw material can be polymerized by using an active energy ray by itself or a photopolymerization initiator that can be cleaved by the active energy ray, and the coating film can be cured. Are preferred.

  Specifically, when using ultraviolet rays as an active energy ray and using a photopolymerization initiator in combination, a preferable binder raw material is a polyfunctional (meth) acrylate monomer, a (meth) acrylate oligomer, or an alkoxysilane having a (meth) acryl group. , Alkoxysilane hydrolyzate having (meth) acrylic group, alkoxysilane oligomer having (meth) acrylic group, acrylic polymer having (meth) acrylic group, urethane polymer having (meth) acrylic group, (meth) An epoxy polymer having an acrylic group and a silicone polymer having a (meth) acryl group.

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

  In addition, commercially available polyfunctional acrylic compositions include Mitsubishi Rayon Co., Ltd. (trade name “Diabeam” (registered trademark) series, etc.), Nagase Sangyo Co., Ltd. (trade name “Denacol” (registered trademark) series, etc.) Shinnakamura Chemical Co., Ltd .; (trade name “NK Ester” series, etc.), DIC Corporation; (trade name “Unidic” (registered trademark), etc.), Toagosei Co., Ltd. (“Aronix” (registered trademark)) Series, etc.), NOF Corporation; (“Blemmer” (registered trademark) series, etc.), Nippon Kayaku Co., Ltd .; (trade name “KAYARAD” (registered trademark) series, etc.), Kyoeisha Chemical Co., Ltd .; (product name “ Light ester "series and the like), and these products can be used.

  The acrylic polymer having a (meth) acryl group is preferably synthesized by a polymerization reaction of a polyfunctional acrylate monomer (eg, polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate). Examples of the urethane polymer include melamine polyurethane. As the silicone polymer, a cohydrolyzate of a silane compound (eg, tetraalkoxysilane, alkyltrialkoxysilane) and a silane coupling agent having a reactive group (eg, epoxy, methacryl) is preferably used. Various polymers that do not contain unsaturated groups, have a weight average molecular weight of 5,000 to 200,000, and a glass transition temperature of 20 to 200 ° C. can be used.

[Particulate material, particle component]
The resin layer of the laminate of the present invention may contain a particle component. Here, the particles may be either inorganic particles or organic particles, but inorganic particles are preferred from the viewpoint of scratch resistance.

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

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

  Here, the particles present in the coating composition used in the present invention are “particulate material”, and the coating composition is present in the resin layer formed by a process such as coating, drying, curing or vapor deposition. The particles are called “particle components”.

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

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

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

[solvent]
The coating composition used in the method for producing a laminate of the present invention may contain a solvent. In order to form a coating film uniformly in a plane and to gradually change the composition in one layer, a solvent is used. It is preferable to contain. The number of solvent types is preferably 1 or more and 20 or less, more preferably 1 or more and 10 or less, still more preferably 1 or more and 6 or less, and particularly preferably 1 or more and 4 or less.

  Here, the “solvent” refers to a substance that is liquid at room temperature and normal pressure, which can be evaporated in substantially the entire amount in the drying step after application.

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

  Furthermore, when it contains a solvent, it is preferable that it is a solvent which shows the following characteristics.

[Other components in the coating composition]
Moreover, it is preferable that a coating composition contains a polymerization initiator, a hardening | curing agent, and a catalyst. The polymerization initiator and the catalyst are used for promoting the curing of the resin layer. As the polymerization initiator, those capable of initiating or accelerating polymerization, condensation or crosslinking reaction by anion, cation, radical polymerization reaction or the like of components contained in the coating composition are preferable.

  Various polymerization initiators, curing agents and catalysts can be used. In addition, the polymerization initiator, the curing agent, and the catalyst may be used alone, or a plurality of polymerization initiators, curing agents, and catalysts may be used simultaneously. Furthermore, an acidic catalyst or a thermal polymerization initiator may be used in combination. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid and the like. Examples of the thermal polymerization initiator include peroxides and azo compounds. Examples of the photopolymerization initiator include alkylphenone compounds, sulfur-containing compounds, acylphosphine oxide compounds, amine compounds, and the like. Examples of the crosslinking catalyst that promotes the urethane bond formation reaction include dibutyltin dilaurate and dibutyltin diethylhexoate.

  In addition, the coating composition may include other crosslinking agents such as melamine crosslinking agents such as alkoxymethylol melamine, acid anhydride crosslinking agents such as 3-methyl-hexahydrophthalic anhydride, and amine crosslinking agents such as diethylaminopropylamine. It can also be included.

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

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

  As described above, it is preferable to form the resin layer by drying and curing the coating layer formed on the support substrate or the release layer.

[Usage]
The laminate of the present invention can be suitably used for a molded body made of plastics or metal, for example, taking advantage of scratch resistance, followability to the surface shape, and the like. Furthermore, the resin film formed by peeling the supporting substrate from the laminate of the present invention can be suitably used as a protective film for a molded body, for example.

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

[Supporting substrate]
[Preparation of release layer coating composition]
[Coating composition A for release layer]
The following materials were mixed and diluted with an n-heptane / toluene mixed solvent (mass mixing ratio 50/50) to obtain a release layer coating composition A having a solid content concentration of 2 mass%.

(X62-9201A: manufactured by Shin-Etsu Chemical Co., Ltd.) 70 parts by mass (X62-9201B: manufactured by Shin-Etsu Chemical Co., Ltd.) 30 parts by mass.

[Coating composition B for release layer]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a release layer coating composition B having a solid content concentration of 2 mass%.

(X62-9201A: manufactured by Shin-Etsu Chemical Co., Ltd.) 50 parts by mass (X62-9201B: manufactured by Shin-Etsu Chemical Co., Ltd.) 50 parts by mass.

[Coating composition C for release layer]
The following materials were mixed and diluted with n-heptane / toluene (mass mixing ratio 50/50) to obtain a release layer coating composition C having a solid content concentration of 2 mass%.

(Syl-Off LTC752 Coating: manufactured by Toray Dow Corning Co., Ltd.) 100 parts by mass (Syl-Off BY 24-850 Additive: manufactured by Toray Dow Corning Co., Ltd.) 5 parts by mass.

[Coating composition D for release layer]
The following materials were mixed and diluted with an n-heptane / toluene mixed solvent (mass mixing ratio 50/50) to obtain a release layer coating composition D having a solid content concentration of 2 mass%.

    (Tesfine 305: Hitachi Chemical Co., Ltd. solid content concentration 50 mass%).

[Creation of support base materials a to e with release layers]
A 50 μm thick polyester film (trade name “Lumirror” (registered trademark) R60, manufactured by Toray Industries, Inc.) is coated with the release layer coating compositions A to D so that the coating thickness after drying is 0.1 (μm). Was applied by gravure coating and dried and cured at 120 ° C. for 30 seconds to obtain supporting substrates a to d.

[Preparation of coating composition for resin layer]
[Synthesis of Urethane (Meth) acrylate A1]
50 parts by mass of toluene, isocyanurate-modified type of hexamethylene diisocyanate (“Takenate” (registered trademark) D-170N manufactured by Mitsui Chemicals), polycaprolactone-modified hydroxyethyl acrylate (Placcel FA5 manufactured by Daicel Chemical Industries, Ltd.) 76 parts by mass, 0.02 parts by mass of dibutyltin laurate and 0.02 parts by mass of hydroquinone monomethyl ether were mixed and held at 70 ° C. for 5 hours. Thereafter, 79 parts by mass of toluene was added to obtain a toluene solution of urethane (meth) acrylate A1 having a solid content concentration of 50% by mass.

[Synthesis of urethane (meth) acrylate C1]
Isocyanurate modified form of hexamethylene diisocyanate (“Takenate” (registered trademark) D-170N, manufactured by Mitsui Chemicals, Inc., isocyanate group content: 20.9% by mass), 50 parts by mass, polyethylene glycol monoacrylate (manufactured by NOF Corporation) "Blemmer" (registered trademark) AE-150, hydroxyl value: 264 (mgKOH / g)) 53 parts by mass, dibutyltin laurate 0.02 parts by mass and hydroquinone monomethyl ether 0.02 parts by mass were charged. And it reacted by hold | maintaining at 70 degreeC for 5 hours. After completion of the reaction, 102 parts by mass of methyl ethyl ketone (hereinafter sometimes referred to as MEK) was added to the reaction solution to obtain a methyl ethyl ketone solution of urethane (meth) acrylate C1 having a solid content concentration of 50% by mass.

[Coating composition A for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition A having a solid content of 30% by mass.
-Solid content concentration of urethane acrylate C1-90 parts by mass of toluene solution-5 parts by mass of tricyclodecane dimethanol diacrylate-1.0 part by mass of radical photopolymerization initiator ("Irgacure" (registered trademark) 184 BASF Japan Made by Co., Ltd.).

[Coating composition B for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition B having a solid content of 30% by mass.
-Solid content concentration of polymer acrylate resin 50 mass% 90 parts by mass of butyl acetate / ethyl acetate solution ("Unidic" V-6850 DIC Corporation solid content concentration 50 mass%)
-Photoradical polymerization initiator 1.0 mass part ("Irgacure" (trademark) 184 BASF Japan Ltd. make).

[Coating composition C for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition C having a solid content concentration of 30% by mass.
・ 25 parts by mass of polyfunctional acrylate monomer (“KAYARAD” (registered trademark) PET-30 manufactured by Nippon Kayaku Co., Ltd.)
Silica particle dispersion 50 parts by mass (MEK-AC-2140Z Nissan Chemical Industries, Ltd. solid content concentration 46% by mass)
・ Alumina particle dispersion 5 parts by mass (NANOBYK-3601 manufactured by Big Chemie Japan KK, solid content concentration 97% by mass)
-Photoradical polymerization initiator 1.0 mass part ("Irgacure" (trademark) 184 BASF Japan Ltd. make).

[Coating composition D for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition D having a solid content of 30% by mass.
-Solid content concentration of urethane (meth) acrylate A1-50 mass parts-toluene solution-50 mass parts of solid content concentration of urethane (meth) acrylate C1-50 mass parts of methyl ethyl ketone solution-Photo radical polymerization initiator 1.0 mass (“Irgacure” (registered trademark) 184 manufactured by BASF Japan Ltd.).

[Create laminate]
[Production Method 1 of Laminate]
Using a continuous coating apparatus having a single-layer slot die coater, the discharge flow rate from the slot was adjusted so that the resin layer thickness shown in Table 1 was obtained for the combination of the support substrate and the coating composition shown in Table 1. It was applied and then dried and cured. Drying and curing conditions are as follows.

(Drying conditions)
Ventilation temperature and humidity: Temperature: 80 ° C., Relative humidity: 1% or less Wind speed: Application surface side: 5 m / sec, Anti-application surface side: 5 m / sec Air direction: Application surface side: Parallel to the substrate surface, anti-application Surface side: perpendicular to the surface of the substrate Drying time: 2 minutes (curing conditions)
Irradiation output: 400 W / cm ²
Integrated light quantity: 120 mJ / cm ²
Oxygen concentration: 0.1 volume% or less.

[Lamination body production method 2]
Using the continuous coating apparatus having the two-layer slot die coater described in FIG. 8, the resin layer thickness of the two layers described in Table 1 is obtained for the combination of the supporting base material described in Table 1 and the two types of coating compositions. As described above, the flow rate from each slot on the upstream side and downstream side was adjusted and applied, followed by drying and curing. The conditions for drying and curing are the same as those in Method 1 for producing the laminate.

  The laminated body of Examples 1-10 and Comparative Examples 1-5 was created with the above method. The method for producing the laminate and the thickness of the resin layer corresponding to each example and comparative example are shown in Table 1.

[Physical property evaluation of laminates]
About the laminated body produced in Examples 1-10 and Comparative Examples 1-5, physical property evaluation shown below was implemented and the obtained result was put together in Table 2. Unless otherwise specified, the measurement was performed three times by changing the location of one sample in each example and comparative example, and the average value was used. Furthermore, based on the physical property evaluation results, the calculated formulas 1 to 3 are shown in Table 2.

[Measurement of indentation elastic modulus of resin layer surface by micro hardness tester]
The indentation elastic modulus on the surface of the resin layer was measured using a nanoindenter “ENT-2100” manufactured by Elionix Corporation. One drop of “Aron Alpha” (registered trademark) professional impact resistance manufactured by Toagosei Co., Ltd. is applied to the side opposite to the side of the laminate on which the resin layer is provided. The sample was fixed to the sample fixing table and measured. For the measurement, a triangular pyramid diamond indenter (Berkovich indenter) having a ridge angle of 115 ° was used. The measurement data was processed by “ENT-2100” dedicated analysis software (version 6.18), and the indentation elastic modulus (GPa) was measured.

Measurement mode: Load-unloading test Maximum load: 100 mN
Holding time when the maximum load is reached: 1 second Loading speed, unloading speed: 10 mN / sec.

[Thickness of resin layer (T)]
The thickness of the resin layer was measured by observing a cross section using an electron microscope (SEM). The thickness of each layer was read with software (image processing software ImageJ) from an image obtained by photographing a slice of the laminate with a SEM at a magnification of 3,000 times. The average value obtained by measuring the layer thickness of 30 points in total was taken as the measured value of the thickness of the resin layer.

[Elastic modulus of resin layer: E, elongation at break: L]
The elastic modulus E and elongation at break L of the resin layer after peeling were tested by cutting the laminate into a 10 mm wide × 150 mm long rectangle with no cracks at the ends, peeling the resin layer from the support substrate A piece. Using a tensile tester (Orientec Tensilon UCT-100), the distance between the initial tensile chucks was set to 50 mm, the tensile speed was set to 300 mm / min, and a tensile test was performed at a measurement temperature of 23 ° C.

  When the distance between chucks is a (mm), the load b (N) applied to the thickness T (m) sample is read, and the strain: x (%) and the stress: y (Pa) are calculated from the following equations. A stress-strain curve was created.

Strain: x = ((a-50) / 50) × 100
Stress: y = b / (T × 10 × 10 ⁻³ ).

The elastic modulus: E (Pa) of the resin layer was determined from the following equation by confirming the linear region (strain: x _{1 to} x ₂ , stress: y _{1 to} y ₂ ) from the stress strain curve described above.

Elastic modulus: E = (y ₁ −y ₂ ) / (x ₁ −x ₂ ) × 100
As the elongation at break L, the strain when the stress was 0 in the applied strain curve described above was used.

[180 ° peeling force between resin layer and supporting substrate: F]
The surface of one side of the pressure-sensitive adhesive film (Panak Corporation Panaclean PD-S1 25 μm product) peeled off is bonded to the surface of the resin layer of the laminate so that no air bubbles enter, and then 10 mm wide × 150 mm long Cut out in a rectangular shape without cracks at the end, and peel off the separator on the other side of the adhesive film to prevent bubbles from entering (188 μm Toray Industries, Inc. “Lumilar” (registered trademark) T60) Pasted on.

  The portion of the PET film where the resin layer is not affixed is fixed with a tensile tester so that the longitudinal direction matches the tensile direction of the tensile tester, and the laminate on the side where the PET film is fixed to the tensile tester A part of the body support substrate was peeled off, bent 180 °, and fixed to the other side of the tensile tester. Subsequently, the resistance value (N) when peeled 180 degrees at a rate of 300 (mm / min) was measured using a tensile tester in an environment of 23 ° C. and 65% RH. The resistance value (N) was divided by the width (m) of the supporting substrate and the resin layer, and converted to 180 ° peeling force F (N / m).

[Measurement of elastic modulus distribution in thickness direction of resin layer]
About the laminated body produced in Examples 1-10 and Comparative Examples 1-5, after embedding and hardening with the epoxy resin for electron microscopes (Quetol812 by Nissin EM), the cross section was cut out by the freezing microtome method, the said cross section Was fixed to a dedicated sample fixing base as a measurement surface. Using an AFM “MFP-3DSA-J” manufactured by Asylum Technology and a cantilever “R150-NCL-10 (material Si, spring constant 48 N / m, radius of curvature of the tip 150 nm) manufactured by NANOSENSORS” A force curve (cantilever moving speed 2 μm / s, maximum indentation load 2 μN) was measured on the cross section in the Contact mode.

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

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

  The distance between the aforementioned resin layer-supporting substrate interface and the outermost surface was taken as the total thickness of the resin layer. Next, a data group on a straight line running through the resin layer was selected from lattice point-like measurement points with a resolution of 512 × 512. Further, the distance in the thickness direction from the resin layer-supporting substrate interface of each data point is calculated from the angle formed by the straight line that cuts through the resin layer to which the data group belongs and the normal line of the laminate, and the total resin layer is calculated. The measurement interval in the thickness direction was adjusted so that at least 8 measurement points were obtained with respect to the thickness, and the elastic modulus was measured by the above-described method to obtain the elastic modulus distribution in the thickness direction.

  At this time, the point where the distance in the thickness direction from the resin layer-supporting substrate interface is less than 50 nm and the point from the outermost surface that is less than 50 nm are excluded from the measurement because they are easily affected by the interface and the surface. .

[Measurement of elastic modulus of surface B of support substrate and calculation of standard deviation of elastic modulus distribution]
The elastic modulus of the surface B is measured in Peak Force QNM mode using AFM (DurationIcon made by Burker Corporation), and the obtained force curve is used with the attached analysis software “NanoScope Analysis V1.40”, JKR contact Analysis based on the theory was performed to obtain the elastic modulus distribution.

Specifically, according to the PeakForceQNM mode manual, after configuring the cantilever warpage sensitivity, spring constant, and tip curvature, measurement was performed under the following conditions, and the obtained DMT Modulus channel data was obtained from the elasticity of the B surface. Adopted as a rate. The spring constant and the tip curvature vary depending on the individual cantilever. However, as a range that does not affect the measurement, the spring constant is 0.3 (N / m) or more and 0.5 (N / m) or less, the tip curvature radius is 15 ( nm) A cantilever satisfying the following conditions was adopted and used for measurement. The measurement conditions are shown below.
Measuring device: Atomic force microscope (AFM) manufactured by Burker Corporation
Measurement mode: PeakForceQNM (force curve method)
Cantilever: SCANASYS-AIR from Bruker AXS
(Material: Si, spring constant K: 0.4 (N / m), tip radius of curvature R: 2 (nm))
Measurement atmosphere: 23 ° C, measurement range in air: 3 (μm) square resolution: 512 × 512
Cantilever moving speed: 10 (μm / s)
Maximum indentation load: 10 (nN).

  Next, the data of the obtained DMT Modulus channel was analyzed with the analysis software “NanoScope Analysis V1.40” and processed with Roughness, and the value of Image Raw Mean on the Results tab was calculated as the elastic modulus of the surface B. did. Further, each class value and observation frequency of the obtained elastic modulus histogram were taken into a spreadsheet software “Microsoft Office Excel 2010”, and the STDEVP function was used to calculate the standard deviation of the elastic modulus distribution.

[Characteristic evaluation of laminates]
About the laminated body and the resin layer, the following characteristic evaluation was implemented and the obtained result is shown in Table 3. Unless otherwise specified, the measurement was performed three times by changing the location of one sample in each example and comparative example, the average value was obtained, and the first decimal place was rounded off.

[Evaluation of scratch resistance of resin layer surface]
About the laminated body produced in Examples 1-10 and Comparative Examples 1-5, using a steel wool of # 0000, using a plane abrasion tester (PA-300A manufactured by Daiei Kagaku Seisakusho Co., Ltd.), a load of 250 kg / At cm ² , the surface of the resin layer was rubbed back and forth 10 times, visually observed for the presence or absence of scratches, and judged according to the following criteria, with a score of 4 or more being passed.
10 points: 0 7 points: 1 or more, less than 5 4 points: 5 or more, less than 10 1 point: 10 or more.

[Evaluation of peelability of resin layer]
The surface of one side of the pressure-sensitive adhesive film (Panaclean Corporation Panaclean PD-S1 25 μm product) is peeled off to the surface of the resin layer of the laminate so that no air bubbles enter, and then the pressure-sensitive adhesive film separator is peeled off. The film was affixed to a PET film (188 μm Toray Industries, Inc. “Lumilar” (registered trademark) T60).

The support base material and the resin layer were peeled off a little from the end portion in advance, the peeled resin layer was peeled in the direction of 180 degrees, and the determination was made according to the following criteria, and four or more points were accepted.
10 points: Even at a peeling speed of 10,000 mm / min, it can be peeled uniformly in the surface.
Seven points: At a peeling speed of 10,000 mm / min, it cannot be peeled uniformly in the plane, and at 1,000 mm / min, it can be peeled uniformly in the plane.
4 points: The film cannot be peeled uniformly in the plane at a peeling speed of 1,000 mm / min, and can be peeled uniformly in the plane at 300 mm / min.
1 point: Cannot be peeled off uniformly at 300 mm / min.

[Evaluation of resin layer quality]
About the laminated bodies produced in Examples 1 to 10 and Comparative Examples 1 to 5, 50 m ² was visually inspected in a state where the light source was reflected on the surface of the resin layer, among which deformation having a diameter of 1 mm or more (repel, foreign matter) ) Was observed according to the following criteria, and 4 or more points were accepted.
10 points: 1 or less 7 points: 2 or more and 5 or less 4 points: 6 or more and 10 or less 1 point: 11 or more.

[Evaluation of shape followability of resin layer]
The surface of one side of the pressure-sensitive adhesive film (Panak Corporation Panaclean PD-S1 25 μm product) was peeled off to the surface of the resin layer of the laminate so that no air bubbles enter, and then 90 mm wide x 90 mm long rectangular Then, cut out in a way that does not crack at the end, peel off the separator on the other side, attach it to a cylinder with a diameter of 30 mm, observe the state of the resin layer at this time, and make a determination according to the following criteria An average score of 4 or more was accepted.
10 points: The resin layer does not crack or float and can be applied uniformly 7 points: Fine cracks can be seen at the end of the resin layer, but other points can be applied uniformly 4 points : Fine cracks can be seen at the edge and center of the resin layer, but other than that, it can be applied uniformly. 1 point: Cracks and floats enter the center of the resin layer and cannot be applied uniformly. .

[Evaluation of float of resin layer]
When the laminates produced in Examples 1 to 10 and Comparative Examples 1 to 5 were cut into 100 × 200 mm squares with a cutter knife and wound around a cylinder with a diameter of 30 mm, the ends of the cut portions were observed, and the following criteria were used: Judgment was made and 4 or more points were accepted.
10 points: No floating occurs at either the end when cut with a cutter knife or the end when wound on a cylinder.
7 points: No lifting occurs at the end when cut with a cutter knife, and slight lifting occurs at the end when wound around a cylinder.
4 points: Slight lifting occurs at the end when cut with a cutter knife, and slight lifting occurs at the end when wound on a cylinder.
1 point: Floating occurs at the end when cut with a cutter knife, and floating occurs at the entire end when wound around a cylinder.

1, 8, 15: Elastic modulus 2, 9, 16: High elastic modulus side 3, 10, 17: Low elastic modulus side 4, 11, 18: Position in thickness direction of resin layer 5, 12, 19: Surface side 6 , 13, 20: Support base material side 7, 14, 21: Elastic modulus at each position in the thickness direction 22, 28, 35: Laminate 23, 29, 36: Support base material 24, 30, 37: Resin layer 25, 31, 38: Release layer 26, 33: Low elastic modulus layer 27, 32, 34: High elastic modulus layer 41: Low elastic modulus part 39, 43: High elastic modulus part 40, 42: Composition gradient part 44: Multilayer slide Die 45, 54: Most upstream slot 46, 55: Second slot from upstream 47: Third slot 48 from upstream 48: Most downstream slot 49: Slide surface 50, 56: Die lip 51, 57, 61: Upstream side 52, 58, 62 in the conveying direction of the supporting base material: Conveying direction of the downstream side 53 of Jimotozai: multilayer slot die 59, 60: Single-layer slot die

  The laminate of the present invention is excellent in scratch resistance, transportability in a thin film, followability to surface shape, and takes advantage of the advantage of transferring a layer having functions such as weather resistance, gas barrier properties, and antiblocking properties. It can be suitably used for molded bodies such as plastics and metals.

  For example, glasses / sunglasses, cosmetic boxes, plastic molded products such as food containers, water tanks, showcases for exhibitions, smartphone housings, touch panels, color filters, flat panel displays, flexible displays, flexible devices, wearables Devices, sensors, circuit materials, electrical / electronic applications, keyboards, home appliances such as remote controls for TVs and air conditioners, mirrors, window glass, buildings, dashboards, car navigation / touch panels, vehicle parts such as room mirrors and windows, and various The printed material, medical film, sanitary material film, medical film, agricultural film, building material film, and the like can be suitably used for each surface material, internal material, constituent material, and manufacturing process material.

Claims (4)

A laminate having a resin layer on at least one surface of a support substrate, wherein the laminate satisfies the following conditions 1 and 2.
Condition 1: The indentation modulus of the surface of the resin layer measured by a microhardness meter is 1 GPa or more. Condition 2: The 180 ° peeling force between the resin layer and the supporting substrate is F (N / m), and the Young's modulus of the resin layer after peeling is When E (Pa), breaking elongation is L (-), and resin layer thickness is T (m), all of the following formulas 1 to 3 are satisfied Formula 1 E · L · T / F ≧ 15
Formula 2 5 × 10 ⁻⁷ ≦ T ≦ 1.8 × 10 ⁻⁵
Formula 3 F ≧ 1 The laminated body according to claim 1, wherein the following condition 3 is satisfied in an elastic modulus distribution in a thickness direction in a cross section perpendicular to the support base of the resin layer.
Condition 3: In the elastic modulus distribution in the thickness direction, the total thickness of the region below the elastic modulus of 0.5 GPa is 20% or more and 80% or less of the total thickness of the resin layer. With respect to the surface (surface B) on which the resin layer is in contact with the surface of the support substrate, the standard deviation of the elastic modulus distribution in the range of 3 μm square measured by an atomic force microscope is 30 MPa or more. The laminate according to claim 1 or 2. The resin film formed by peeling a support base material from the laminated body in any one of Claims 1-3.