JP7619421B2 - Laminate and resin film - Google Patents

Description

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

In general, the surfaces of plastics and metals are more susceptible to scratches than glass, and when they are used as products, it is required that the surface gloss and transparency be maintained. Therefore, in plastic or metal molded bodies, a layer that imparts scratch resistance to the surface is sometimes provided. Specifically, a method is known in which the surface is coated with a high-hardness resin layer called a "hard coat," as exemplified in Non-Patent Document 1. Furthermore, the hard coat layer may be used to impart functions other than scratch resistance to the molded body, such as weather resistance, gas barrier properties, and blocking prevention properties.

The hard coat layer described above is generally formed by applying and curing directly to the surface of the plastic or metal that constitutes the molded body, or by attaching a plastic film with a hard coat layer already formed thereon, or by molding it integrally with the plastic or metal that constitutes the molded body. In addition, when direct application is impossible due to the heat resistance, processing temperature, or solvent resistance of the material that constitutes the molded body, or when it is formed together with a function other than scratch resistance, such as an optical function layer or a design layer, there is also a method in which a hard coat layer is formed on a support substrate separate from the material that constitutes the molded body and then transferred to the surface of the molded body.

In addition, for electronic device applications, for example, in order to make products thinner and to increase the freedom of product shape, a method is being considered in which only the hard coat layer is transferred to the surface of the molded product, instead of molding the hard coat film as a whole.

As such, as a method of transferring only the hard coat layer to a molded body, Patent Document 1 proposes a "transfer sheet having at least a release layer, a functional layer, and an adhesive layer on one side of a substrate, characterized in that the transfer sheet uses as the main material a silicone acrylic resin that forms a strong hardened film by forming silicone bridges in the release layer, and uses a polydimethylsiloxane copolymer as the secondary material."

Patent document 2 proposes a transfer film that is "a transfer film formed by sequentially laminating at least a release layer, a hard coat layer, and an adhesive layer on one side of a base film, the release layer being an acrylic urethane resin having a long-chain alkyl group having 10 to 30 carbon atoms."

Patent Document 3 describes a hard coat transfer film in which at least a release layer and a hard coat layer made of an ultraviolet curable resin are laminated in this order on a plastic film, and the hard coat transfer film is characterized in that it satisfies all of the following conditions (A) to (C): (A) the release layer and the hard coat layer are laminated so as to be in contact with each other; (B) the release layer is a layer made of a thermosetting resin and a hydroxyl group-containing acrylate.

(C) The weight ratio of the hydroxyl-containing acrylate to the thermosetting resin is 3 to 10% by weight.

Patent document 4 proposes a transfer foil that includes at least a substrate, a release layer provided on the substrate, and a protective layer releasably provided on the release layer, the release layer comprising an actinic radiation curable resin and a thermosetting resin, and the protective layer comprising an actinic radiation curable resin.

JP 2004-034385 A JP 2014-104705 A JP 2014-180809 A JP 2017-65017 A

Plastic Hard Coating Application Technology CMC Publishing Co., Ltd. 2004

Thus, there are two essential problems to be solved in transferring a hard coat layer to a molded article:
1. The hard coat layer is unlikely to cause defects such as cissing on the release layer and can be formed uniformly within the surface.
2. The hard coat layer is less likely to tear or zip when transferred to a molded body, and can be easily peeled off at the interface with the release layer. In response to these two issues, the present inventors confirmed the technology of Patent Document 1 and found that while the method described in the specification may be effective for a coating composition for an anti-reflection layer, when applied to a coating composition for a hard coat, cissing occurs during coating, making it difficult to obtain a coating film with good quality, and thus the above issues could not be achieved.

The inventors have confirmed the technologies of Patent Documents 2 to 4, and have found that the method described in the specification does indeed provide good transferability to molded articles in systems in which a thick hard coat layer, a primer layer, and an adhesive layer are laminated for a hard coat coating composition. However, when the resin layer becomes thin, it is not possible to peel it off uniformly within the surface, and the above-mentioned problem cannot be achieved.

For these reasons, it is difficult to solve the fundamental problems involved in transferring a hard coat layer that includes a functional layer using conventional technology.

Therefore, in order to solve the above-mentioned problems, the present inventors have conducted extensive research and have completed the following invention.
1. A laminate having a release layer and a resin layer on at least one surface of a supporting substrate, in this order from the supporting substrate side, wherein the surface of the resin layer has a region (region B) having a lower elastic modulus than a region (region A) having a higher elastic modulus when observed with an atomic force microscope, and the laminate satisfies the following conditions:
Condition 1: Elastic modulus E _B of region B is 1,500 MPa or less. Condition 2: Average number of regions B in a 5 μm square is 50 to 300. 2. The laminate according to 1, characterized in that the following conditions are satisfied.
Condition 3: The difference ( _EA - _EB ) between the elastic modulus _EA of the region A and the elastic modulus _EB of the region B is 100 MPa or more.
Condition 4: The major axis radius of the region B is 25 nm or more and 250 nm or less. 3. The laminate described in 1. or 2., characterized in that the region A contains a resin component represented by Chemical Formula 1 within a range of 5 nm from the surface of the resin layer, and the region B contains a resin component represented by Chemical Formula 2 and/or a resin component represented by Chemical Formula 3.

R ¹ is hydrogen or a methyl group, and R ² , R ³ and R ⁴ are any one of the following (i) to (vi).
(i) a substituted or unsubstituted alkylene group, (ii) a substituted or unsubstituted arylene group, (iii) a substituted alkylene group having an ether group, ester group or amide group therein, (iv) an unsubstituted alkylene group having an ether group, ester group or amide group therein, (v) a substituted arylene group having an ether group, ester group or amide group therein, (vi) an unsubstituted arylene group having an ether group, ester group or amide group therein 4. When observed with an atomic force microscope, a region (referred to as region B) having a lower elastic modulus than a region (referred to as region A) having a higher elastic modulus is present on the surface,
A resin film characterized by satisfying the following conditions.
Condition 1: Elastic modulus E _B of region B is 1,500 MPa or less. Condition 2: Average number of regions B in a 5 μm square is 50 to 300. 5. The resin film according to 4., characterized in that the following conditions are satisfied:
Condition 3: The difference ( _EA - _EB ) between the elastic modulus _EA of the region A and the elastic modulus _EB of the region B is 100 MPa or more.
Condition 4: The major axis radius of the region B is 25 nm or more and 250 nm or less. 6. The resin film according to 4. or 5., characterized in that, within a range of 5 nm from the surface of the resin film, the region A contains a resin component represented by Chemical Formula 1, and the region B contains a resin component represented by Chemical Formula 2 and/or a resin component represented by Chemical Formula 3.

R ¹ is hydrogen or a methyl group, and R ² , R ³ and R ⁴ are any one of the following (i) to (vi).
(i) a substituted or unsubstituted alkylene group; (ii) a substituted or unsubstituted arylene group; (iii) a substituted alkylene group having an ether group, an ester group or an amide group therein; (iv) an unsubstituted alkylene group having an ether group, an ester group or an amide group therein; (v) a substituted arylene group having an ether group, an ester group or an amide group therein; (vi) an unsubstituted arylene group having an ether group, an ester group or an amide group therein.

According to the present invention, it is possible to obtain a laminate from a resin film that is unlikely to impair the functions of the hard coat layer, such as scratch resistance and weather resistance, and is unlikely to impair the appearance quality, such as unevenness and transparency, and that can be transferred uniformly within the plane.

According to the present invention, even if the resin layer formed on the release layer is a thin film, defects such as repelling are unlikely to occur in the resin layer, and further, when it is transferred to a molded body, tearing or zipping is unlikely to occur, and it can be easily peeled off.

FIG. 2 is a cross-sectional view illustrating an example of the configuration of a laminate of the present invention. FIG. 2 is a cross-sectional view illustrating an example of the configuration of a laminate of the present invention. FIG. 2 is a cross-sectional view illustrating an example of the configuration of a laminate of the present invention. FIG. 2 is a cross-sectional view illustrating an example of the configuration of a laminate of the present invention. 1 is a conceptual diagram showing an example of a shape formed by two types of regions A and B. FIG. 1 is a conceptual diagram showing an example of a shape formed by two types of regions A and B. FIG.

The inventors have discovered that the above-mentioned problems can be solved by making the surface of the resin layer satisfy certain conditions. The details are described below.

First, as shown in FIG. 1, the laminate 1 of the present invention has a release layer 4 and a resin layer 5 on at least one surface of a support substrate 3, in this order from the support substrate side. The release layers may be on both surfaces of the support substrate 8 as shown in FIG. 2. Also, as in the laminate 12 of FIG. 3, a protective film 17 having an adhesive layer 18 may be attached to the surface of the resin layer 16 opposite to the surface in contact with the release layer 15, or as in the laminate 20 of FIG. 4, a functional layer 25 may be laminated on the surface of the resin layer 24 opposite to the surface in contact with the release layer 23.

The laminate of the present invention is characterized in that, when observed with an atomic force microscope, the surface of the resin layer has an area (region B) with a lower elastic modulus than an area (region A) with a higher elastic modulus, and further, the elastic modulus of region B is designed to be equal to or less than a certain value, and the average number of regions B present within a 5 μm square field of view is designed to be within a certain range.

Here, we will explain the elastic modulus measurement using an atomic force microscope and the regions A and B estimated from the measurement. This measurement method is a compression test using a probe on an extremely small portion, and measures the degree of deformation due to the pressing force. Therefore, a cantilever with a known spring constant can be used to measure the spatial distribution of the elastic modulus on the surface of the resin layer. Details such as the specific measurement and analysis procedures will be described in the Examples section, but for example, using the atomic force microscope shown below, the probe at the tip of the cantilever is brought into contact with the surface of the resin layer, and the force curve is measured with a pressing force of 55 nN to measure the amount of deflection of the cantilever.

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

At this time, the spatial resolution in the in-plane direction depends on the scanning range and number of scanning lines of the atomic force microscope, but under realistic measurement conditions, the lower limit is approximately 10 nm. In other words, for minute regions less than 10 nm in size, the elastic modulus is detected as average information, but as a result of verifying the correlation with the physical properties that the present invention aims to achieve, it has been confirmed that the physical properties are not affected.

In the spatial distribution of the elastic modulus measured as described above, the surface of the resin layer of the present invention is characterized by having regions A and B having different elastic moduli. In this case, the region with the higher elastic modulus is called region A, and the region with the lower elastic modulus is called region B.

Here, the ideal phase structure will be explained using the diagram. The shapes formed by two different types of regions are roughly divided into a so-called "sea-island structure (Figure 5)" in which one domain is enclosed in the other domain, and a "lamella structure (Figure 6)" that does not have a closed region within the measurement field of view. It is preferable that the elastic modulus distribution on the surface of the resin layer of the present invention is a sea-island structure, and the island side is a region B31 with a low elastic modulus. In a state in which region B forms a continuous phase structure, the size of region B is too large, so that the physical properties of region A32 and region B appear separately during peeling, and the peeling force becomes unstable. The specific analysis procedure for region A and region B, and the judgment criteria when two regions do not exist will be described later in the Examples section. Note that when three or more regions with different elastic moduli are formed by combining the preferred resin layer coating composition described later, the region with the highest elastic modulus is designated as A and the other regions are designated as B, and the average elastic modulus and total number of these regions satisfy the above-mentioned conditions, and it is possible to obtain the same effect.

The reason why the problem of the present invention, that is, the quality of the resin layer is less likely to be degraded and the peeling force can be reduced by providing the above-mentioned structure on the surface of the resin layer, is as follows. The peeling force when peeling between the resin layer and the release layer is thought to be composed of 1) an increase in surface free energy corresponding to the increased surface area due to the peeling between the resin layer and the release layer, and 2) the energy required to deform the peeling interface during peeling.

In contrast, the method described in Patent Document 1 focuses on the release layer (peeling layer) and uses a polydimethylsiloxane copolymer on the peeling layer side to reduce the increase in surface energy caused by peeling (1), and soften the layer to reduce the energy required for deformation of the peeling interface (2), thereby reducing the peeling force. On the other hand, when applied to a hard coat coating composition, cissing occurs during application as described above because the surface free energy is reduced in (1), and the problem of the present invention cannot be solved.

On the other hand, the present invention focuses on the resin layer, rather than on the release layer approach, which may reduce the quality of the resin layer during its formation, and has found that it is possible to reduce the peel force from the viewpoint of 2) above. Furthermore, the present invention has been used as a method for reducing the deformation energy of the peel interface without impairing the function of the resin layer (for example, bulk physical properties such as scratch resistance in the case of a hard coat layer), which is the purpose of the laminate of the present invention. In the present invention, regions A and B are provided on the surface of the resin layer, and the function of the resin layer is ensured in region A, while region B is provided, thereby achieving a reduction in the energy required for deformation of the peel interface.

In this invention, regions A and B are defined as those observed on the surface of the resin layer of the laminate, but it is presumed that a similar structure is also formed between the resin layer and the release layer, and that this function is expressed.

It is necessary that the elastic modulus EB of region B is 1,500 MPa or less (condition 1), and is preferably 1,000 MPa or less. If _EB exceeds 1,500 _MPa , the effect of reducing the peel force described above may not be obtained.

In addition, there is a range that must be satisfied for the average number of regions B present per unit area. Specifically, as in the above-mentioned condition 2, it is necessary that the average number of regions B within a 5 μm square field of view is 50 or more and 300 or less (condition 2). If the number of regions B present within a 5 μm square field of view is less than 50, the effect of reducing the peel force, which is the subject of the present invention, may be insufficient. On the other hand, if the number of regions B present within a 5 μm square field of view exceeds 300, the function required as a resin layer may be reduced. The method for measuring the elastic modulus E _B and the method for analyzing the number of regions B present within a 5 μm square field of view will be described later in the Examples section.

[Embodiments of the present invention]
Hereinafter, the embodiment of the present invention will be described in detail.

[Laminate, Resin Layer, and Resin Film]
The laminate of the present invention has a release layer and a resin layer on at least one surface of the support substrate in this order from the support substrate side. The resin layer in the present invention refers to a layer formed on the support substrate and capable of being peeled off and transferred from the support substrate. A layer formed on the support substrate but not peelable from the support substrate, for example, a release layer to be described later, is not included in the resin layer. The criteria for judging whether or not the layer can be peeled off are evaluated by the cross-cut method described in JIS K5600-5-6:1999, and those classified as Class 4 or higher are deemed peelable, and those classified as Class 0 to 3 are deemed unpeeled. The laminate is made up of all layers including the resin layer, release layer, and support substrate. When only one layer is formed on the release layer, the layer is a resin layer, and when two or more layers are formed on the release layer, the two or more layers excluding the release layer are considered to be one resin layer. In addition, the resin layer peeled off from the support substrate and the release layer may be described as a "resin film" to clarify that the support substrate and the release layer are not included.

The term "layer" as used herein refers to a portion of the laminate that can be distinguished from adjacent portions in the thickness direction by having a boundary surface from the surface side toward the thickness direction, and that has a finite thickness. More specifically, it refers to a portion that can be distinguished by the presence or absence of a discontinuous boundary surface when the cross section of the laminate is observed with an electron microscope (transmission type, scanning type) or optical microscope. Therefore, even if the composition changes in the thickness direction of the resin layer, if there is no boundary surface between them, it is treated as one layer.

The laminate of the present invention may be in a planar state or in a three-dimensional shape as long as it has a resin layer exhibiting the above-mentioned 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 may have other functions such as gloss, fingerprint resistance, moldability, design, scratch resistance, stain resistance, solvent resistance, anti-reflection, anti-static, electrical conductivity, heat reflection, near-infrared absorption, electromagnetic wave shielding, and easy adhesion.

In addition, one or more layers may be formed on the resin layer, for example, a functional layer having the above-mentioned functions, an adhesive layer, an electronic circuit layer, a printing layer, an optical adjustment layer, or other functional layers.

The resin film of the present invention can be obtained, for example, by peeling off the support substrate including the release layer from the laminate described above.

[Difference between Elastic Modulus _EA of Region A and Elastic Modulus _EB of Region B of Resin Layer]
The conditions of the elastic modulus distribution that the resin layer and resin film of the present invention should satisfy have been described above, but there are other conditions that are preferable for achieving the objectives. Specifically, there is a preferable range of difference between the elastic modulus _EA of region A and the elastic modulus _EB of region B, and it is preferable that _{EA -EB} is 100 MPa or more. The existence of an elastic modulus difference between the two regions is a more preferable parameter for ensuring the function of the resin layer and resin film by region A and reducing the energy required for deformation of the peeling interface by region _B. If the elastic modulus difference ( _EA -EB) is less than 100 MPa, the effect of reducing the peeling force described above may be insufficient. There is no particular problem if the difference between the elastic modulus _EA and the elastic modulus _EB is large, but for a material that can be actually used, the limit is about 20,000 MPa. The specific measurement and analysis method of the elastic modulus of each region will be described later in the Examples section.

[Major axis radius of region B of resin layer and resin film]
Furthermore, there is a preferred form for the shape of the region B having a relatively low elastic modulus formed on the surface of the laminate and resin film of the present invention. Specifically, it is preferable that the major axis radius of the region B is 25 nm or more and 250 nm or less. Here, the major axis radius means the radius of the major axis side of the ellipse obtained by elliptical approximation of the shape formed by the region B on the surface of the resin layer and the resin film. In order for the region B to contribute to macroscopic physical properties such as peeling force and handling property, it is necessary to have a certain size or more, and the correlation can be evaluated by using the major axis of the elliptical approximation. If the major axis radius exceeds 250 nm, the function required for the resin layer and the resin film described above may be reduced, and if it is less than 25 nm, the effect of reducing the peeling force described above may not be obtained. The specific measurement and analysis method of the major axis radius of the region B will be described later in the Examples section.

[Surface Composition of Resin Layer and Resin Film]
Furthermore, preferred components exist in the surface composition of the resin layer and the resin film, more specifically, in each of the regions A and B. Specifically, within a depth range of 5 nm from the surface of the resin layer and the resin film, it is preferred that region A contains a resin component represented by Chemical Formula 1, and region B contains a resin component represented by Chemical Formula 2 and/or Chemical Formula 3. In this case, region B may contain the resin component represented by Chemical Formula 1, but it is particularly preferred that region A does not contain or contains relatively little of the resin component represented by Chemical Formula 2 and/or Chemical Formula 3.

R ¹ is hydrogen or a methyl group, and R ² , R ³ and R ⁴ are any one of the following (i) to (vi).
(i) a substituted or unsubstituted alkylene group; (ii) a substituted or unsubstituted arylene group; (iii) a substituted alkylene group having an ether group, an ester group or an amide group therein; (iv) an unsubstituted alkylene group having an ether group, an ester group or an amide group therein; (v) a substituted arylene group having an ether group, an ester group or an amide group therein; and (vi) an unsubstituted arylene group having an ether group, an ester group or an amide group therein.

Here, the surface composition of the resin layer and the resin film is a more preferable parameter for ensuring the functionality of the resin layer and the resin film by the aforementioned region A, while reducing the energy required for deformation of the peeling interface by region B. In order for the material constituting region B to effectively affect the peeling force, it is preferable for it to be present in the vicinity of the surface of the resin layer and the resin film, and specifically, it is preferable for it to be present within a range of 5 nm from the surface in the depth direction.

The methods for evaluating and analyzing the resin components containing each of the above chemical formulas will be described later in the Examples section, but for example, analysis can be performed by using a time-of-flight secondary ion mass spectrometry (TOF-SIMS) in combination with ion sputtering. Sputtering is performed from the surface to a depth of 5 nm using ion sputtering, while TOF-SIMS measurements are performed, and analysis is performed based on the integrated values.

The resin component represented by chemical formula 1 can be detected using negative ions with a mass number of 85 (chemical formula 4) or negative ions with a mass number of 71 (chemical formula 5). In other words, if either negative ions with a mass number of 85 (chemical formula 4) or negative ions with a mass number of 71 (chemical formula 5) are detected, it means that the resin component represented by chemical formula 1 is present.

On the other hand, the resin component represented by chemical formula 2 can be detected using a positive ion with a mass number of 69 (chemical formula 6) and a positive ion with a mass number of 169 (chemical formula 7), and the presence of chemical formula 2 can be determined by detecting these positive ions simultaneously.

Furthermore, the resin component represented by Chemical Formula 3 can be detected using positive ions ( _C2H5O ⁺ ) with a mass number of 45 or positive ions ( _C3H7O ⁺ ) with a mass number of 59. In other words, if either the positive ions ( _C2H5O ⁺ ) with a mass number of 45 or the positive _ions with a mass number of 59 are detected _{, it} means that the resin component represented by Chemical Formula 3 is present.

In addition, when determining whether each of the above components is contained in each region, TOF-SIMS mapping is performed. Ions characteristic of each compound are mapped, and verification is performed by comparing them with the shape of the region obtained from the elastic modulus distribution. The relative content can also be estimated from the strength of the signal intensity during mapping. The specific measurement procedure will be described later.

[Support substrate]
The resin constituting the supporting substrate used in the laminate of the present invention may be either a thermoplastic resin or a thermosetting resin, and may be a homogeneous resin, a copolymer, or a blend of two or more kinds. The resin constituting the supporting substrate is preferably one having good moldability, and from that point of view, a thermoplastic resin is more preferable.

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, polyarylate resins, polyacetal resins, polyphenylene sulfide resins, fluororesins such as tetrafluoroethylene resin, trifluoroethylene resin, trifluorochloroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer, and vinylidene fluoride resin, acrylic resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, and polylactic acid resins. Examples of thermosetting resins include phenolic resins, epoxy resins, urea resins, melamine resins, unsaturated polyester resins, polyurethane resins, polyimide resins, and silicone resins. The thermoplastic resin is preferably a resin with sufficient stretchability and conformability. From the standpoint of strength and heat resistance, it is more preferable that the thermoplastic resin is a polyester resin, a polycarbonate resin, an acrylic resin, or a methacrylic resin.

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

On the other hand, for the purpose of inspecting the optical properties during the laminate manufacturing process, the transparent support is preferably a transparent material with low birefringence, and from the viewpoint of low birefringence, cellulose ester and cyclic olefin are preferred. Commercially available norbornene-based polymers that can be used include Arton (manufactured by JSR Corporation), Zeonex, Zeonor (all manufactured by Zeon Corporation), and TOPAS (manufactured by Polyplastics Corporation).

The support substrate may also contain various additives, such as antioxidants, antistatic agents, crystal nucleating agents, inorganic particles, organic particles, viscosity reducing agents, heat stabilizers, lubricants, infrared absorbing agents, ultraviolet absorbing agents, and doping agents for adjusting the refractive index. The support substrate may have either a single layer structure or a multilayer structure.

It is also possible to carry out various surface treatments before forming the resin layer. Examples of surface treatments 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, the surface of the support substrate can be provided in advance with multiple functional layers such as an easy-adhesion layer, an antistatic layer, an undercoat layer, and an ultraviolet absorbing layer.

The supporting substrate is not particularly limited as long as it is possible to transfer the resin layer, but it is preferable to use a supporting substrate having a release layer on the surface that contacts the resin layer. Details of the release layer will be described later.

[Release layer and method of producing release layer]
The above-mentioned supporting substrate preferably has a release layer satisfying the above-mentioned conditions on at least one surface in contact with the resin layer. The supporting substrate side of the release layer may be composed of a plurality of layers from the viewpoint of imparting adhesion, antistatic property, solvent resistance, etc.

The thickness of the release layer is not particularly limited, but in terms of the in-plane uniformity, quality, and peeling force of the release layer, it is preferably 10 to 500 nm, and more preferably 20 to 200 nm.

The material for the release layer is not particularly limited, but it is preferably formed from a resin composition for the release layer described below, and is preferably formed on the surface of the support substrate by coating, drying, and curing using the method for producing the release layer described below.

The material of the resin composition for the release layer is not particularly limited as long as the surface in contact with the resin layer has the standard deviation and average value of the specific elastic modulus distribution described above, but alkyd-based resins, polyolefin-based resins, resins containing long-chain alkyl groups, fluorine-based resins, silicone-based resins, mixed or copolymerized organic and silicone resins, etc. are preferred.

The method of producing the release layer is not particularly limited as long as the surface in contact with the resin layer has the standard deviation and average value of the specific elastic modulus distribution described above. However, it is preferable to form a coating layer by applying the release layer coating composition by dip coating, roller coating, wire bar coating, gravure coating, or die coating (U.S. Pat. No. 2,681,294), with gravure coating or die coating being preferred.

Next, the coating layer applied onto the support substrate or the like is dried. In addition to completely removing the solvent from the resulting coating layer, it is preferable to heat the coating film during the drying process in order to promote curing of the coating film.

Drying methods include heat transfer drying (contact with a hot object), convection heat transfer (hot air), radiation heat transfer (infrared rays), and others (microwaves, induction heating). Of these, in the manufacturing method of the present invention, a method using convection heat transfer or radiation heat transfer is preferred because it is necessary to precisely uniform the drying speed even in the width direction.

Furthermore, a further curing operation (curing step) may be performed by irradiating heat or energy rays. In the curing step, when curing is performed by heat, the temperature is preferably from room temperature to 200°C, and from the viewpoint of the activation energy of the curing reaction, more preferably from 100°C to 200°C, and even more preferably from 130°C to 200°C.

In addition, when curing with energy rays, electron beams (EB rays) and/or ultraviolet rays (UV rays) are preferred from the viewpoint of versatility. In addition, examples of the type of ultraviolet lamp used when irradiating ultraviolet rays include discharge lamp type, flash type, laser type, and electrodeless lamp type. In the case of ultraviolet curing using a high pressure mercury lamp of the discharge lamp type, ultraviolet irradiation is preferably performed under conditions where the illuminance of ultraviolet rays is preferably 100 to 3,000 (mW/cm ² ), more preferably 200 to 2,000 (mW/cm ² ), and even more preferably 300 to 1,500 (mW/cm ² ), and ultraviolet irradiation is preferably performed under conditions where the integrated light amount of ultraviolet rays is preferably 100 to 3,000 (mJ/cm ² ), more preferably 200 to 2,000 (mJ/cm ² ), and even more preferably 300 to 1,500 (mJ/cm ² ). Here, UV illuminance is the radiation intensity received per unit area, and varies depending on the lamp output, emission spectrum efficiency, diameter of the light-emitting bulb, design of the reflector, and the distance between the irradiated object and the light source. However, illuminance does not vary depending on the transport speed. Also, the integrated UV light amount is the radiation energy received per unit area, and is the total amount of photons that reach the surface. The integrated light amount is inversely proportional to the radiation speed passing under the light source, and 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 substrate by drying and curing the coating layer formed on the support substrate.

[Method of manufacturing laminate]
The method for producing the laminate of the present invention is preferably a method for producing a laminate in which a preferred resin layer coating composition described later is applied onto the release layer of the preferred support substrate described above, and then dried and cured to form a resin layer. The coating method is not particularly limited, and can be appropriately selected from dip coating, roller coating, wire bar coating, gravure coating, die coating (U.S. Pat. No. 2,681,294), etc.

Here, it is important that the surface characteristics of the resin layer satisfy the above-mentioned conditions, and the manufacturing method may be capable of forming a resin layer whose resin composition differs in the thickness direction. When forming a resin layer whose resin composition differs in the thickness direction, the manufacturing method of the laminate is preferably a method of forming a resin layer by sequentially or simultaneously applying at least two or more types of coating compositions for the resin layer, followed by drying and curing, and a manufacturing method of the laminate in which at least two or more types of coating compositions for the resin layer are simultaneously applied is more preferable.

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

Methods of heating in the drying process include heat transfer drying (contact with a hot object), convection heat transfer (hot air), radiation heat transfer (infrared rays), and others (microwaves, induction heating). Of these, methods using convection heat transfer or radiation heat transfer are preferred, as it is necessary to precisely ensure uniform drying speed across the width.

Following the drying step, a further curing operation (curing step) may be carried out by irradiating with heat or active energy rays.

As the active energy ray, from the viewpoint of versatility, an electron beam (EB ray) and/or an ultraviolet ray (UV ray) are preferable. When curing with ultraviolet ray, it is preferable that the oxygen concentration is as low as possible because oxygen inhibition can be prevented, and it is more preferable to cure under a nitrogen atmosphere (nitrogen purging). When the oxygen concentration is high, the curing of the outermost surface is inhibited, the curing of the surface is weakened, and the toughness may be reduced. In addition, the type of ultraviolet lamp used for irradiating ultraviolet ray includes, for example, a discharge lamp type, a flash type, a laser type, an electrodeless lamp type, etc. When using a high pressure mercury lamp of a discharge lamp type, it is preferable to irradiate ultraviolet ray under conditions where the illuminance of the ultraviolet ray is preferably 100 to 3,000 mW/cm ² , more preferably 200 to 2,000 mW/cm ² , and even more preferably 300 to 1,500 mW/cm ² . The ultraviolet irradiation is preferably performed under conditions where the cumulative amount of ultraviolet light is 100 to 3,000 mJ/cm ² , more preferably 200 to 2,000 mJ/cm ² , and even more preferably 300 to 1,500 mJ/cm ² . Here, the illuminance of ultraviolet light is the irradiation intensity received per unit area, and varies depending on the lamp output, emission spectrum efficiency, diameter of the light-emitting bulb, design of the reflector, and the distance between the light source and the irradiated object. However, the illuminance does not vary depending on the conveying speed. Moreover, the cumulative amount of ultraviolet light is the irradiation energy received per unit area, and is the total amount of photons that reach the surface. The cumulative amount of light is inversely proportional to the irradiation speed passing under the light source, and 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 can be produced by applying a coating composition for the resin layer onto the release layer of the above-mentioned supporting substrate, and drying and bonding the composition as necessary. It can be obtained through a curing process.

Here, the term "resin layer coating composition" refers to a liquid consisting of a solvent and a solute, which can be applied to the aforementioned support substrate, volatilized and removed in the process of drying the solvent, and further cured as necessary to form a resin layer. Here, the "type" of resin layer coating composition refers to a liquid in which the type of solute that constitutes the resin layer coating composition is different, even if only partially. The solute consists of resin or a material that can form it in the coating process (hereinafter referred to as a resin precursor), particles, and various additives such as polymerization initiators, curing agents, catalysts, leveling agents, ultraviolet absorbers, and antioxidants.

[Resin precursor]
The resin precursor can be used by itself or by dissolving in a solvent to prepare a coating composition for the resin layer. In particular, it is preferable to use a resin precursor as a material for forming region A. The resin precursor refers to a material that can harden a coating film by volatilization of a solvent, and its own polymerization and crosslinking reaction. That is, the resin layer of the laminate of the present invention and the resin film obtained by peeling off the release film from the laminate contain a cured product obtained by crosslinking the resin precursor.

In the method for producing the laminate of the present invention described above, a material that can be polymerized by the action of active energy rays, either by itself or in combination with a photopolymerization initiator that can be cleaved by active energy rays, to harden the coating film is preferred.

Specifically, when ultraviolet light is used as the active energy ray and a photopolymerization initiator is used in combination, preferred resin precursors are polyfunctional (meth)acrylate monomers, (meth)acrylate oligomers, alkoxysilanes having (meth)acrylic groups, alkoxysilane hydrolysates having (meth)acrylic groups, alkoxysilane oligomers having (meth)acrylic groups, acrylic polymers having (meth)acrylic groups, urethane polymers having (meth)acrylic groups, epoxy polymers having (meth)acrylic groups, and silicone polymers having (meth)acrylic groups.

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

Commercially available polyfunctional acrylic compositions include Mitsubishi Rayon Co., Ltd. (product name "Diabeam" (registered trademark) series, etc.), Nagase & Co., Ltd. (product name "Denacol" (registered trademark) series, etc.), Shin-Nakamura Chemical Co., Ltd. (product name "NK Ester" series, etc.), DIC Corporation (product name "UNIDIC" (registered trademark), etc.), Toagosei Co., Ltd. (product name "Aronix" (registered trademark) series, etc.), NOF Corporation (product name "Blenmar" (registered trademark) series, etc.), Nippon Kayaku Co., Ltd. (product name "KAYARAD" (registered trademark) series, etc.), Kyoeisha Chemical Co., Ltd. (product name "Light Ester" series, etc.), and these products can be used.

The acrylic polymer having a (meth)acrylic group is preferably synthesized by a polymerization reaction of a multifunctional acrylate monomer (e.g., polyol acrylate, polyester acrylate, urethane acrylate, epoxy acrylate). Examples of urethane polymers include melamine polyurethane. The silicone polymer is preferably a co-hydrolyzate of a silane compound (e.g., tetraalkoxysilane, alkyltrialkoxysilane) and a silane coupling agent having a reactive group (e.g., epoxy, methacryl). In addition, the various polymers that do not contain unsaturated groups and 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.

The resin layer and resin film of the laminate of the present invention preferably contain a cured product obtained by curing two types of resin precursors, and more preferably, the combination of the resin precursors is within a specific range.
Specifically, of the two types of resin precursors, it is preferable that the resin precursor having a smaller functional group equivalent (referred to as resin precursor A) and the resin precursor having a larger functional group equivalent (referred to as resin precursor B) satisfy the following conditions.

The functional group equivalent (QA) of resin precursor A and the functional group equivalent (QB) of resin precursor B satisfy the following formula.

0.01< QA/QB <0.05
100 (g/eq) < QA < 400 (g/eq)
The term "functional group equivalent" as used herein refers to the value obtained by dividing the weight-average molecular weight of the resin precursor by the number of functional groups, which are capable of causing a crosslinking reaction.

When the two types of resin precursors meet the above-mentioned conditions, the crack resistance of the resin layer and resin film is improved.

Furthermore, it is preferable that resin precursor A and resin precursor B contain segments of chemical formula 8 and chemical formula 9. By containing segments of chemical formula 8 and 9, it is possible to bring about an interaction between the respective segments, thereby imparting toughness.

Here, R6 is hydrogen or a methyl group, and R5 is any one of the following (i) to (vi).
(i) a substituted or unsubstituted alkylene group; (ii) a substituted or unsubstituted arylene group; (iii) a substituted alkylene group having an ether group, an ester group or an amide group therein; (iv) an unsubstituted alkylene group having an ether group, an ester group or an amide group therein; (v) a substituted arylene group having an ether group, an ester group or an amide group therein; (vi) an unsubstituted arylene group having an ether group, an ester group or an amide group therein.

[Leveling agent]
A preferred resin layer coating composition used to form the resin layer of the present invention preferably contains a leveling agent. It is particularly preferred to configure region B with a leveling agent, which allows the peeling force to be designed within a suitable range while maintaining the function of the resin layer. Examples of leveling agents include acrylic copolymers, silicone-based, and fluorine-based leveling agents. Among these, particularly preferred leveling agents are those containing a hexafluoropropylene group or a polyether group. If the leveling agent contains the above functional group, the coating quality and peeling force can be suitably designed.

[Particle 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 to 20. The number of types of inorganic particles is more preferably 1 to 10, and particularly preferably 1 to 4. Here, "inorganic particles" also includes those that have been surface-treated. This surface treatment refers to the introduction of a compound onto the particle surface by chemical bonding (including covalent bonding, hydrogen bonding, ionic bonding, van der Waals bonding, hydrophobic bonding, etc.) or adsorption (including physical adsorption and chemical adsorption).

Here, the type of inorganic particles is determined by the type of element that constitutes the inorganic particles, and in the case of performing some surface treatment, it is determined by the type of element that constitutes the particles before the surface treatment. For example, titanium oxide (TiO2) and nitrogen-doped titanium oxide (TiO2 _{-xNx )} , in which part of the oxygen of titanium oxide is replaced with nitrogen, which is an anion, are different types of inorganic particles because the elements that constitute the inorganic particles are different. Also, if there are multiple particles (ZnO) consisting of the same element, for example, Zn and O only, even if there are multiple particles with different number average particle diameters or different composition ratios of Zn and O, these are the same type of particles. Also, even if there are multiple Zn particles with different oxidation numbers, as long as the elements that constitute the particles are the same (as long as all elements other than Zn are the same in this example), these are the same type of particles.

Here, the particles present in the resin layer coating composition used in the present invention are referred to as "particle material", and the particles present in the resin layer formed by applying the resin layer coating composition to a coating, drying, curing treatment, deposition, or other treatment are referred to as "particle components".

The inorganic particles are not particularly limited, but are preferably oxides, nitrides, borides, chlorides, carbonates, or sulfates of metals or metalloids. They may be composite oxides containing two types of metals or metalloids, or may have a different element introduced between the lattice, a different element substituted for the lattice points, or lattice defects introduced.

It is further preferred that the inorganic particles are oxide particles formed by oxidizing at least one metal or semi-metal selected from the group consisting of Si, Al, Ca, Zn, Ga, Mg, Zr, Ti, In, Sb, Sn, Ba and Ce.

Specifically, it is at least one metal oxide or semi-metal oxide selected from the group consisting of 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 (SnO 2 )} , antimony oxide (Sb ₂ O ₃ ), and indium tin oxide (In ₂ O ₃ ).

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

Here, "solvent" refers to a substance that is liquid at room temperature and pressure and can be almost completely evaporated during the drying process after application.

The type of solvent is determined by the molecular structure that makes up the solvent. In other words, solvents that have the same elemental composition and the same type and number of functional groups but different bonding relationships (structural isomers), and solvents that are not structural isomers but do not overlap exactly in any conformation in three-dimensional space (stereoisomers) are treated as different types of solvents. For example, 2-propanol and n-propanol are treated as different solvents.

[Other components in the coating composition for resin layer]
In addition, the coating composition for the resin layer preferably contains a polymerization initiator, a curing agent, and a catalyst. The polymerization initiator and the catalyst are used to promote the curing of the resin layer. As the polymerization initiator, one that can initiate or promote the polymerization, condensation, or crosslinking reaction of the components contained in the coating composition for the resin layer by anionic, cationic, or radical polymerization reaction or the like is preferable.

Various polymerization initiators, curing agents, and catalysts can be used. The polymerization initiators, curing agents, and catalysts may be used alone, or multiple polymerization initiators, curing agents, and catalysts may be used simultaneously. Furthermore, acidic catalysts and thermal polymerization initiators may be used in combination. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, and acetic acid. Examples of thermal polymerization initiators include peroxides and azo compounds. Examples of photopolymerization initiators include alkylphenone compounds, sulfur-containing compounds, acylphosphine oxide compounds, and amine compounds. Examples of crosslinking catalysts that promote the reaction of forming urethane bonds include dibutyltin dilaurate and dibutyltin diethylhexoate.

The resin layer coating composition may also contain 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.

As the photopolymerization initiator, an alkylphenone compound is preferred from the viewpoint of curability. Specific examples of alkylphenone compounds include 1-hydroxy-cyclohexyl-phenyl-ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-phenyl)-1-butane, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-(4-phenyl)-1-butane, 2-benzyl-2-dimethylamino-1-(4-mo Examples of such compounds include 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butane, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butane, 1-cyclohexyl-phenyl ketone, 2-methyl-1-phenylpropan-1-one, 1-[4-(2-ethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2-phenyl-2-oxoacetate)oxybisethylene, and polymerized versions of these materials.

As long as the effect of the present invention is not impaired, an ultraviolet absorber, a lubricant, an antistatic agent, etc. may be added to the resin layer coating composition used to form the resin layer. This allows the resin layer to contain an ultraviolet absorber, a lubricant, an antistatic agent, etc. Specific examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, oxalic acid anilide-based, triazine-based, and hindered amine-based ultraviolet absorbers. Examples of antistatic agents include metal salts such as lithium salts, sodium salts, potassium salts, rubidium salts, cesium salts, magnesium salts, and calcium salts.

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

[Application]
The laminate of the present invention can be suitably used for protecting the surface of a molded product made of, for example, plastics or metal, taking advantage of its scratch resistance, conformability to surface shape, etc. Furthermore, a resin film obtained by peeling off the support substrate and the release layer from the laminate of the present invention can be suitably used, for example, as a protective film for a molded product.

[Resin film]
As mentioned above, a resin layer that does not have a supporting substrate and a release layer is referred to as a resin film. The resin film of the present invention is characterized in that, when observed with an atomic force microscope, there is a region on the surface having a lower elastic modulus (referred to as region B) than a region having a higher elastic modulus (referred to as region A), and that it satisfies the following conditions 1 and 2.
Condition 1: Elastic modulus E _B of region B is 1,500 MPa or less. Condition 2: The average number of regions B in a 5 μm square is 50 to 300. Details of region A, region B, condition 1, and condition 2 are as described above in the section on the resin layer of the laminate of the present invention.

In addition, the resin film of the present invention preferably satisfies the following conditions 3 and 4.
Condition 3: The difference ( _EA - _EB ) between the elastic modulus _EA of the region A and the elastic modulus _EB of the region B is 100 MPa or more.
Condition 4: The major axis radius of the region B is 25 nm or more and 250 nm or less. Details of conditions 3 and 4 are as described above in the section on the resin layer of the laminate of the present invention.

Furthermore, in the resin film of the present invention, it is preferable that, within a range of 5 nm from the surface, the region A contains a resin component represented by chemical formula 1, and the region B contains a resin component represented by chemical formula 2 and/or a resin component represented by chemical formula 3. Details of the resin components of chemical formulas 1, 2, and 3 are as described above in the section on the resin layer of the laminate of the present invention.

The method for producing the resin film of the present invention is not particularly limited. For example, the resin film of the present invention can be produced by producing the laminate of the present invention and then peeling off only the resin layer from the laminate.

As mentioned above, the resin film of the present invention can be suitably used, for example, as a protective film for molded objects.

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

[Release layer coating composition 1]
The following materials were mixed and diluted with a methyl ethyl ketone/isopropyl alcohol mixed solvent (mass mixing ratio 50/50) to obtain a coating composition 1 for a release layer having a solids concentration of 5 mass %.
Side-chain carbinol-modified reactive silicone oil (X-22-4015 Shin-Etsu Chemical Co., Ltd., solid content concentration 100% by mass): 5 parts by mass Both-end polyether-modified reactive silicone oil (X-22-4952 Shin-Etsu Chemical Co., Ltd., solid content concentration 100% by mass): 5 parts by mass Acrylic-modified alkyd resin (Haliftar KV-905 Harima Chemical Co., Ltd., solid content concentration 53% by mass): 100 parts by mass Isobutyl alcohol-modified melamine resin
(Melan 2650L, Hitachi Chemical Co., Ltd., solid content concentration 60% by mass): 20 parts by mass; paratoluenesulfonic acid: 5 parts by mass.

[Release layer coating composition 2]
The following materials were mixed and diluted with a toluene/heptane mixed solvent (mass mixing ratio 50/50) to obtain coating composition 3 for release layer having a solid content concentration of 2 mass %.
Toluene solution of methylvinylpolysiloxane and methylhydrogenated polysiloxane (LTC752 Coating, manufactured by Dow Corning Toray Co., Ltd., solids concentration 30% by mass): 85 parts by mass; Stripping additive (BY24-4980, manufactured by Dow Corning Toray Co., Ltd., solids concentration 30% by mass): 5 parts by mass; Complex solution of methylvinylpolysiloxane and platinum (PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.): 0.1 parts by mass.

[Release layer coating composition 3]
The following materials were mixed and diluted with a methyl ethyl ketone/isopropyl alcohol mixed solvent (mass mixing ratio 50/50) to obtain coating composition 5 for release layer having a solids concentration of 5 mass %.
A mixed solution of long-chain alkyl group-containing aminoalkyd resin in toluene/xylene/isobutanol/methanol (Tesfine ^R 305, manufactured by Hitachi Chemical Co., Ltd., solids concentration 50% by mass).

[Release layer coating composition 4]
The following materials were mixed and diluted with a methyl ethyl ketone/isopropyl alcohol mixed solvent (mass mixing ratio 50/50) to obtain coating composition 5 for release layer having a solids concentration of 5 mass %.
・One-end carbinol modified reactive silicone oil (X-22-170DX Shin-Etsu Chemical Co., Ltd., solid content concentration 100% by mass): 1 part by mass ・Both-end polyether modified reactive silicone oil (X-22-4952 Shin-Etsu Chemical Co., Ltd., solid content concentration 100% by mass): 5 parts by mass ・Acrylic modified alkyd resin (Haliftar KV-905 Harima Chemical Co., Ltd., solid content concentration 53% by mass): 100 parts by mass ・Isobutyl alcohol modified melamine resin (Melan 2650L Hitachi Chemical Co., Ltd., solid content concentration 60% by mass): 20 parts by mass ・Paratoluenesulfonic acid: 5 parts by mass.

[Preparation of coating composition for resin layer]
[Coating composition 1 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 1 having a solids concentration of 20% by mass.
Resin precursor A: butyl acetate/ethyl acetate solution of polymer acrylate resin, 160 parts by mass ("Unidic" V-6850, DIC Corporation, solid content concentration 50% by mass)
Resin precursor B: 20 parts by mass of urethane acrylate oligomer ("Shiko" UV3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 100% by mass); 1 part by mass of leveling agent ("Ftergent" 212M, manufactured by Neos Co., Ltd., solid content concentration 100% by mass); 3.0 parts by mass of α-hydroxyacetophenone type photopolymerization initiator ("Irgacure" (registered trademark) 184, manufactured by BASF Japan Ltd.).

[Coating composition 2 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 2 having a solids concentration of 20% by mass.
Resin precursor A: butyl acetate/ethyl acetate solution of polymer acrylate resin, 190 parts by mass ("Unidic" V-6850, DIC Corporation, solid content concentration 50% by mass)
Resin precursor B: 5 parts by mass of urethane acrylate oligomer ("Shiko" UV3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 100% by mass) Leveling agent ("Ftergent" 602A, manufactured by Neos Co., Ltd., solid content concentration 50 1 part by mass (mass%) α-hydroxyacetophenone type photopolymerization initiator 3.0 parts by mass ("Irgacure" (registered trademark) 184 manufactured by BASF Japan Ltd.).

[Coating composition 3 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 3 having a solids concentration of 20% by mass.
Resin precursor A: butyl acetate/ethyl acetate solution of polymer acrylate resin, 160 parts by mass ("Unidic" V-6850, DIC Corporation, solid content concentration 50% by mass)
Resin precursor B: 20 parts by mass of urethane acrylate oligomer ("Shiko" UV3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 100% by mass) Leveling agent ("BYK" (registered trademark) -UV3535, manufactured by BYK Japan (solid content concentration 100 mass%) 1 part by mass; α-hydroxyacetophenone type photopolymerization initiator 3.0 parts by mass ("Irgacure" (registered trademark) 184, manufactured by BASF Japan Ltd.).

[Coating composition 4 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 4 having a solids concentration of 20% by mass.
Resin precursor A: butyl acetate/ethyl acetate solution of polymer acrylate resin, 160 parts by mass ("Unidic" V-6850, DIC Corporation, solid content concentration 50% by mass)
Resin precursor B: 20 parts by mass of urethane acrylate oligomer ("Shiko" UV3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 100% by mass) Leveling agent ("Ftergent" 212M, manufactured by Neos Corporation, solid content concentration 100% by mass) ) 3 parts by mass; α-hydroxyacetophenone type photopolymerization initiator 3.0 parts by mass ("Irgacure" (registered trademark) 184, manufactured by BASF Japan Ltd.).

[Coating composition 5 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 5 having a solids concentration of 20% by mass.
Resin precursor A: butyl acetate/ethyl acetate solution of polymer acrylate resin, 160 parts by mass ("Unidic" V-6850, DIC Corporation, solid content concentration 50% by mass)
Resin precursor B: 20 parts by mass of urethane acrylate oligomer ("Shiko" UV3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 100% by mass) Leveling agent ("Ftergent" 212M, manufactured by Neos Co., Ltd., solid content concentration 100 0.3 parts by mass (mass%) α-hydroxyacetophenone type photopolymerization initiator 3.0 parts by mass ("Irgacure" (registered trademark) 184 manufactured by BASF Japan Ltd.).

[Coating composition 6 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 6 having a solids concentration of 20% by mass.
Resin precursor A: butyl acetate/ethyl acetate solution of polymer acrylate resin, 190 parts by mass ("Unidic" V-6850, DIC Corporation, solid content concentration 50% by mass)
Resin precursor B: 5 parts by mass of urethane acrylate oligomer ("Shiko" UV3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 100% by mass) Leveling agent (LINC-3A, manufactured by Kyoeisha Chemical Co., Ltd., solid content concentration 100% by mass) 1 part by weight of α-hydroxyacetophenone type photopolymerization initiator 3.0 parts by weight ("Irgacure" (registered trademark) 184, manufactured by BASF Japan Ltd.).

[Coating composition 7 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 7 having a solids concentration of 20% by mass.
Polymer acrylate resin butyl acetate/ethyl acetate solution 200 parts by mass ("Unidic" V-6850, DIC Corporation, solids concentration 50% by mass)
Leveling agent ("BYK" (registered trademark) -UV3535, manufactured by BYK Japan Co., Ltd., solid content concentration 100% by mass) 1 part by mass α-hydroxyacetophenone type photopolymerization initiator 3.0 parts by mass ("Irgacure" ( (Registered Trademark) 184 (manufactured by BASF Japan Ltd.)

[Coating composition 8 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 3 having a solids concentration of 20% by mass.
Resin precursor A: butyl acetate/ethyl acetate solution of polymer acrylate resin, 160 parts by mass ("Unidic" V-6850, DIC Corporation, solid content concentration 50% by mass)
Resin precursor B: 20 parts by mass of urethane acrylate oligomer ("Shiko" UV3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 100% by mass) Leveling agent ("BYK" (registered trademark) -UV3535, manufactured by BYK Japan (solid concentration 100 mass%) 3 parts by mass of α-hydroxyacetophenone type photopolymerization initiator ("Irgacure" (registered trademark) 184 manufactured by BASF Japan Ltd.).

[Coating composition 9 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 9 having a solids concentration of 20% by mass.
Resin precursor A: butyl acetate/ethyl acetate solution of polymer acrylate resin, 160 parts by mass ("Unidic" V-6850, DIC Corporation, solid content concentration 50% by mass)
Resin precursor B: 20 parts by mass of urethane acrylate oligomer ("Shiko" UV3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 100% by mass) Leveling agent ("BYK" (registered trademark) -UV3535, manufactured by BYK Japan (solid concentration 100 mass%) 0.5 mass parts; α-hydroxyacetophenone type photopolymerization initiator 3.0 mass parts ("Irgacure" (registered trademark) 184, manufactured by BASF Japan Ltd.).

[Coating composition 10 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 10 having a solids concentration of 20% by mass.
Polyfunctional acrylate monomer 100 parts by mass ("KAYARAD" (registered trademark) PET30, manufactured by Nippon Kayaku Co., Ltd., solid content concentration 100% by mass)
- 3.0 parts by mass of α-hydroxyacetophenone type photopolymerization initiator ("Irgacure" (registered trademark) 184 manufactured by BASF Japan Ltd.).

[Coating composition 11 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 11 having a solids concentration of 20% by mass.
Resin precursor A: butyl acetate/ethyl acetate solution of polymer acrylate resin, 160 parts by mass ("Unidic" V-6850, DIC Corporation, solid content concentration 50% by mass)
("Unidic" V-6850, DIC Corporation, solid content concentration 50% by weight)
Resin precursor B: 20 parts by mass of urethane acrylate oligomer ("Shiko" UV3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 100% by mass) Leveling agent ("Ftergent" 212M, manufactured by Neos Co., Ltd., solid content concentration 100 0.1 parts by mass (mass%) α-hydroxyacetophenone type photopolymerization initiator 3.0 parts by mass ("Irgacure" (registered trademark) 184 manufactured by BASF Japan Ltd.).

[Coating composition 12 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 12 having a solids concentration of 20% by mass.
Resin precursor A: butyl acetate/ethyl acetate solution of polymer acrylate resin, 160 parts by mass ("Unidic" V-6850, DIC Corporation, solid content concentration 50% by mass)
("Unidic" V-6850, DIC Corporation, solid content concentration 50% by weight)
Resin precursor B: 20 parts by mass of urethane acrylate oligomer ("Shiko" UV3200B, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content concentration 100% by mass) Leveling agent ("Ftergent" 212M, manufactured by Neos Co., Ltd., solid content concentration 100 5 parts by mass (mass%) α-hydroxyacetophenone type photopolymerization initiator 3.0 parts by mass ("Irgacure" (registered trademark) 184 manufactured by BASF Japan Ltd.).

[Coating composition 13 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 13 having a solids concentration of 20% by mass.
Polyfunctional acrylate monomer 100 parts by mass ("KAYARAD" (registered trademark) PET30, manufactured by Nippon Kayaku Co., Ltd., solid content concentration 100% by mass)
Leveling agent (LINC-5A, manufactured by Kyoeisha Chemical Co., Ltd., solid content concentration 100% by mass) 1 part by mass α-hydroxyacetophenone type photopolymerization initiator 3.0 parts by mass ("Irgacure" (registered trademark) 184, manufactured by BASF Japan Ltd.) Made in Japan.

[Coating composition 14 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 14 having a solids concentration of 20% by mass.
Resin precursor A: urethane acrylate oligomer A1 80 parts by weight Resin precursor B: urethane acrylate oligomer B1 20 parts by weight Leveling agent ("Ftergent" 212M, manufactured by Neos Co., Ltd., solid content concentration 100% by weight) 1 part by weight - 3.0 parts by mass of α-hydroxyacetophenone type photopolymerization initiator ("Irgacure" (registered trademark) 184, manufactured by BASF Japan Ltd.).

The synthesis method for urethane acrylate oligomer A1 is as follows. 108 parts by mass of bisphenol A diepoxy resin (YD-8125, manufactured by Nippon Steel Chemical Co., Ltd.), 45 parts by mass of acrylic acid as a (meth)acrylic acid derivative, 0.2 parts by mass of hydroquinone monomethyl ether as a polymerization inhibitor, and 0.8 parts by mass of dimethylaminoethyl methacrylate as a catalyst were added, and the mixture was heated to 95°C with stirring, and the reaction was continued for 14 hours while maintaining the temperature at 95°C. The first stage reaction was terminated when the acid value reached 1 mgKOH/g or less, and an epoxy acrylate having two hydroxyl groups was obtained.

Next, after lowering the temperature to 60°C, ethyl acetate was added as a diluting solvent, and 0.03 parts by mass of di-n-butyltin dilaurate was added as a catalyst. With stirring, 83 parts by mass of dicyclohexylmethane diisocyanate was added dropwise over 2 hours, followed by 94 parts by mass of pentaerythritol triacrylate, which was then added dropwise over 1 hour. After the addition, the reaction was continued for 5 hours, yielding urethane acrylate oligomer A1 with five functionalities and a weight average molecular weight of 1200.

The synthesis method for urethane acrylate oligomer B1 is as follows. 70 parts by mass of polytetramethylene glycol (PTMG1000, manufactured by Mitsubishi Chemical Corporation), 33 parts by mass of polyoxyethylene bisphenol A ether (Newpol BPE-40, manufactured by Sanyo Chemical Industries, Ltd.), and ethyl acetate were added and heated to an internal temperature of 60°C. 0.03 parts by mass of di-n-butyltin dilaurate was added as a synthesis catalyst, and 31 parts by mass of isophorone diisocyanate was added dropwise over 1 hour with stirring. After completion of the dropwise addition, the reaction was continued for 2 hours.

Next, 2.4 parts by mass of 2-hydroxyethyl acrylate was added dropwise over a period of 1 hour. After the addition, the reaction was continued for 5 hours to obtain bifunctional urethane acrylate oligomer B1 with a weight average molecular weight of 14,000.

[Coating composition 15 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 15 having a solids concentration of 20% by mass.
Resin precursor A: urethane acrylate oligomer A1 60 parts by weight Resin precursor B: urethane acrylate oligomer B1 40 parts by weight Leveling agent ("Ftergent" 212M, manufactured by Neos Co., Ltd., solid content concentration 100% by weight) 1 part by weight - 3.0 parts by mass of α-hydroxyacetophenone type photopolymerization initiator ("Irgacure" (registered trademark) 184, manufactured by BASF Japan Ltd.).

[Coating composition 16 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 16 having a solids concentration of 20% by mass.
Resin precursor A: urethane acrylate oligomer A1 80 parts by weight Resin precursor B: urethane acrylate oligomer B2 20 parts by weight Leveling agent ("Ftergent" 212M, manufactured by Neos Co., Ltd., solid content concentration 100% by weight) 1 part by weight - 3.0 parts by mass of α-hydroxyacetophenone type photopolymerization initiator ("Irgacure" (registered trademark) 184, manufactured by BASF Japan Ltd.).

The synthesis method of resin precursor B2 is as follows. 70 parts by mass of polytetramethylene glycol (PTMG1000, manufactured by Mitsubishi Chemical Corporation), 33 parts by mass of polyoxyethylene bisphenol A ether (Newpol BPE-40, manufactured by Sanyo Chemical Industries, Ltd.), and ethyl acetate were added and heated to an internal temperature of 60°C. 0.03 parts by mass of di-n-butyltin dilaurate was added as a synthesis catalyst, and 31 parts by mass of isophorone diisocyanate was added dropwise over 1 hour with stirring. After completion of the dropwise addition, the reaction was continued for 2 hours.

Next, 1.2 parts by mass of 2-hydroxyethyl acrylate and 3.0 parts by mass of pentaerythritol triacrylate were added dropwise over 1 hour. After the addition, the reaction was continued for 5 hours to obtain a tetrafunctional urethane acrylate oligomer B2 solution with a weight average molecular weight of 15,000 as resin precursor B.

[Coating composition 17 for resin layer]
The following materials were mixed and diluted with methyl ethyl ketone to obtain a resin layer coating composition 17 having a solids concentration of 20% by mass.
Resin precursor A: 80 parts by mass of urethane acrylate oligomer (EBCRYL3701, Daicel Allnex Corporation)
Resin precursor B: Urethane acrylate oligomer B1 20 parts by mass Leveling agent ("Ftergent" 212M, manufactured by Neos Co., Ltd., solid content concentration 100% by mass) 1 part by mass α-hydroxyacetophenone type photopolymerization initiator 3.0 parts by mass ("Irgacure" (registered trademark) 184 manufactured by BASF Japan Ltd.).

[Preparation of Support Substrates 1 to 4 with Release Layer]
Using the above-mentioned coating composition for the release layer and the supporting substrate, a release layer was formed by the following method, and a supporting substrate with a release layer was prepared. The combination of the coating composition for the release layer, the method for forming the release layer, and the thickness of the release layer used is as shown in Table 1.

[Method 1 for forming release layer]
Using a coating device having a small diameter gravure coater, the release layer coating composition was applied to a polyester film having a thickness of 50 μm (manufactured by Toray Industries, Inc., under the trade name "Lumilar" (registered trademark) R75X) by adjusting the gravure line frequency, peripheral speed, and solid content concentration so as to obtain a release layer thickness as shown in Table 1. The coating composition was then dried and cured by holding the film at a hot air temperature of 140° C. for 30 seconds, thereby obtaining a support substrate 1 with a release layer.

[Method 2 for forming release layer]
Using a coating device having a small diameter gravure coater, release layer coating compositions 2, 3 and 4 were applied to a polyester film having a thickness of 50 μm (manufactured by Toray Industries, Inc., under the trade name "Lumilar" (registered trademark) R75X) by adjusting the gravure line number, peripheral speed and solid content concentration so as to obtain the release layer thickness shown in Table 1, and then the coating composition was dried and cured by holding the coating composition at a hot air temperature of 120° C. for 30 seconds to obtain support substrates with release layers 2 to 4.

[Method 3 for forming release layer]
Using a coating device having a small diameter gravure coater, the release layer coating composition was applied to a 40 μm thick triacetyl cellulose film (TD40UL manufactured by Fujifilm Corporation) by adjusting the gravure line count, peripheral speed, and solid content concentration so as to obtain the release layer thickness shown in Table 1, and then the film was dried and cured by holding the film at a hot air temperature of 140° C. for 30 seconds to obtain a support substrate 5 with a release layer.

[Creation of Laminate]
A resin layer was formed using the above-mentioned coating composition for the resin layer and the support substrate with a release layer to prepare a laminate. The combination of the coating composition for the resin layer, the method for forming the resin layer, and the thickness of the resin layer is as shown in Table 1.

[Method of forming resin layer]
Using a continuous coating device having a single-layer slot die coater, the above-mentioned resin layer coating composition was applied to the support substrate with the release layer by adjusting the discharge flow rate from the slot so that the resin layer thickness would be as shown in Table 1, and then the coating was dried by holding it at a hot air temperature of 80°C for 30 seconds.Then, the coating was cured by irradiating it with a high-pressure mercury lamp under conditions of an oxygen partial pressure of 0.1 volume% or less, an irradiation output of 400 W/ ^cm2 , and an irradiation intensity of 120 mJ/ ^cm2 , thereby forming a resin layer.

Laminates for Examples 1 to 17 and Comparative Examples 1 to 4 were prepared using the above method. The method for preparing the laminates and the thickness of the resin layer corresponding to each Example and Comparative Example are shown in Table 1.

[Formation of resin film 1]
The support substrate with the release layer was peeled off from the laminate produced in Example 1, to obtain a resin film 1.

[Formation of resin film 2]
The support substrate with the release layer was peeled off from the laminate produced in Example 2, to obtain a resin film 2.

[Formation of resin film 3]
The support substrate with the release layer was peeled off from the laminate produced in Example 3 to obtain a resin film 3.

[Formation of resin film 4]
The support substrate with the release layer was peeled off from the laminate produced in Example 4, to obtain a resin film 4.

[Formation of resin film 5]
The support substrate with the release layer was peeled off from the laminate produced in Example 5 to obtain a resin film 5.

[Formation of resin film 6]
The support substrate with the release layer was peeled off from the laminate produced in Example 6 to obtain a resin film 6.

[Formation of resin film 7]
The support substrate with the release layer was peeled off from the laminate produced in Example 7 to obtain Resin Film 7.

[Formation of resin film 8]
The support substrate with the release layer was peeled off from the laminate produced in Example 8 to obtain a resin film 8.

[Formation of resin film 9]
The support substrate with the release layer was peeled off from the laminate produced in Example 9, to obtain Resin Film 9.

[Formation of resin film 10]
The support substrate with the release layer was peeled off from the laminate produced in Example 10 to obtain a resin film 10.

[Formation of resin film 11]
The support substrate with the release layer was peeled off from the laminate produced in Example 11 to obtain a resin film 11.

[Formation of resin film 12]
The support substrate with the release layer was peeled off from the laminate produced in Example 12 to obtain a resin film 12.

[Formation of resin film 13]
The support substrate with the release layer was peeled off from the laminate produced in Example 13 to obtain a resin film 13.

[Formation of resin film 14]
The support substrate with the release layer was peeled off from the laminate produced in Example 14 to obtain a resin film 14.

[Formation of resin film 15]
The support substrate with the release layer was peeled off from the laminate produced in Example 15 to obtain a resin film 15.

[Formation of resin film 16]
The support substrate with the release layer was peeled off from the laminate produced in Example 16 to obtain a resin film 16.

[Formation of resin film 17]
The support substrate with the release layer was peeled off from the laminate produced in Example 17 to obtain a resin film 17.

By the above-mentioned method, the resin films of Examples 18 to 2634 were prepared. The method of forming the resin film and the thickness of the resin film corresponding to each Example are shown in Table 2.

[Evaluation of physical properties of laminate and resin film]
The laminates produced in Examples 1 to 17 and Comparative Examples 1 to 4 and the resin films produced in Examples 18 to 34 were subjected to the following physical property evaluations, and the results obtained are summarized in Tables 3 and 4. Unless otherwise specified, measurements were performed three times for one sample in each Example and Comparative Example at different locations, and the average value was used. Furthermore, the presence or absence of the resin components represented by Chemical Formulas 1 to 3 calculated based on the physical property evaluation results is listed in Tables 3 and 4.

[Elastic Modulus Distribution of Resin Layer and Resin Film Surface]
The elastic modulus distribution of the resin layer and the resin film surface was measured using an AFM (Dimension Icon manufactured by Bulker Corporation) in PeakForceQNM mode. Analysis was performed based on the JKR contact theory using the attached analysis software "NanoScopeAnalysis V1.40" from the obtained force curve to obtain the elastic modulus distribution.

Specifically, the cantilever's warpage sensitivity, spring constant, and tip curvature were determined according to the PeakForceQNM mode manual, and then measurements were performed under the following conditions, and the data from the DMT Modulus channel obtained was used as the elastic modulus of the B surface. Although the spring constant and tip curvature vary depending on the individual cantilever, a cantilever that satisfies the conditions of a spring constant of 0.3 (N/m) or more and 0.5 (N/m) or less and a tip curvature radius of 15 (nm) or less was adopted and used for the measurement, as a range that does not affect the measurement. The measurement conditions are shown below.
Measurement equipment: Atomic force microscope (AFM) manufactured by Burker Corporation
Measurement mode: PeakForceQNM (force curve method)
Cantilever: Bruker AXS SCANASYST-AIR
(Material: Si, spring constant K: 0.4 (N/m), tip curvature radius R: 2 (nm))
Measurement atmosphere: 23°C, in air Measurement range: 5 (μm) Square resolution: 512 x 512
Cantilever movement speed: 10 (μm/s)
Maximum pressing load: 10 (nN).

[Elastic modulus E _A of region A, elastic modulus E _B of region B, and their difference (E _A -E _B )]
The data of the DMT Modulus channel obtained was then analyzed using the analysis software "NanoScopeAnalysis V1.40". First, the Number Histogram Bins (number of classes) was set to 3,000 points in Depth mode, and the frequency histogram of the elastic modulus (horizontal axis - elastic modulus (MPa), vertical axis - frequency (%)) was calculated. Next, the number of peaks was determined for the frequency histogram of the elastic modulus obtained by the following method. Here, the peak means a maximum value of frequency, and when the frequency histogram of the elastic modulus has only one maximum value, the maximum value is the peak, and when the volume-based frequency distribution has two or more maximum values, the maximum value with a frequency difference of 2% or more from the minimum value existing between the target maximum values is treated as the peak. The number of peaks was determined for the frequency histogram of the elastic modulus obtained based on this criterion.

Next, the elastic moduli corresponding to the peaks determined above were read from the frequency histogram of elastic moduli, the maximum one was designated as the elastic modulus _EA of region A, and the product of the elastic modulus x and the frequency F(x) was calculated at each point of the remaining peaks, and the sum ΣxF(x) was divided by the sum ΣF(x) of the frequencies to obtain a frequency-weighted average value, which was adopted as the elastic modulus _EB of region B. Note that when there is only one applicable peak, it is determined that region B does not exist, and the physical properties of region B are deemed not applicable.

[Average number of regions B]
The number of regions B was calculated using the elastic modulus distribution obtained above. First, the obtained image was smoothed under the condition of Plane Fit (XY, 3rd) in the analysis software "NanoScopeAnalysis V1.40", and then the contrast was adjusted using Image Color Scale Adjust (Autoscale). Next, the image was converted to grayscale using image processing software EasyAccess Ver6.7.1.23, the white balance was adjusted so that the brightest and darkest parts were within an 8-bit tone curve, and the contrast was adjusted so that the boundaries of the regions were clearly distinguishable. Next, the pixels were binarized at the aforementioned boundary using image analysis software ImageJ 1.45s (developed by the National Institutes of Health (NIH)), and each region was analyzed by Particle Analyze (Include holes: Yes, Size: 0-Infinity). The total number of data displayed in the Results window was taken as the number of regions B contained in the range of 5 μm × 5 μm. Similar measurements and analyses were repeated at five locations, and the average value was taken as the average number of regions B.

[Major axis radius of region B]
Next, the major axis radius was analyzed by Particle Analyze (Include holes: Yes, Size: 0-Infinity) using image analysis software ImageJ 1.45s (developed by the National Institutes of Health (NIH)). Specifically, Fit Ellipse (ellipse approximation) was selected from Set Measurements, and the average value of Major displayed in the Results window was adopted as the major axis radius.

[Surface Composition of Resin Layer and Resin Film]
Using a time-of-flight secondary ion mass spectrometer TOF-SIMS V manufactured by ION TOF and measurement software SURFACE LAB 6 manufactured by the same company, the mass distribution of positive ions and negative ions was measured by secondary ion mass spectrometry in a range of 5 nm from the outermost surface of the resin layer and the resin film under the following conditions.
Measurement conditions Primary ion species: _Bi3 ⁺⁺
Primary ion current: 1.000 pA
Acceleration voltage: 25 kV
Measurement range: 100 μm x 100 μm
Resolution: 128 x 128
Number of scans: 36.

First, a mass distribution analysis was performed on the obtained data. It was determined that when the mass distribution contains negative ions with a mass number of 85 or negative ions with a mass number of 71, the resin component represented by chemical formula 1 is present; when it simultaneously contains positive ions with a mass number of 69 (chemical formula 4) and positive ions with a mass number of 169 (chemical formula 5), the resin component represented by chemical formula 2 is present; and when it contains positive ions with a mass number of 45 or positive ions with a mass number of 59, the resin component represented by chemical formula 3 is present.

At this time, an Ar gas cluster sputter gun was used for cutting in the depth direction. To determine the sputtering rate, the thickness of the resin layer and resin film of the laminate were measured in advance. The sample, whose resin layer thickness was known, was then cut down to the supporting substrate side, and the cutting rate per unit time was calculated. From this, the time required to cut 5 nm was calculated, and the integrated result of this time was used as the analysis result for the range of 5 nm from the outermost surface of the resin layer and resin film.

Next, an analysis of the spatial distribution was performed. A spatial distribution image of the outermost surface was reconstructed from the data measured above. At this time, when negative ions with mass numbers of 85 or 71, positive ions with mass numbers of 150 (chemical formula 4), positive ions with mass numbers of 393 (chemical formula 5), positive ions with mass numbers of 45, and positive ions with mass numbers of 59 were detected, the analysis conditions were adjusted to the polarity and mass of the ions of interest, and analysis was performed.

Specifically, first, the software built into the secondary ion mass spectrometer was used to extract two-dimensional position information on the outermost surface of the resin layer, as well as information on the secondary ion intensity of each fragment ion at the corresponding position.

The standard deviation of the secondary ion intensity can be calculated based on the extracted secondary ion intensity value. The obtained spatial distribution was analyzed in the same manner as the elastic modulus distribution, the average number was calculated, and if the difference with the elastic modulus distribution was less than ±5%, it was determined that they constituted the same domain.

[Evaluation of properties of laminate and resin layer]
The laminate and the resin layer were subjected to the following characteristic evaluations, and the results are shown in Table 5. Unless otherwise specified, the measurements were performed three times for one sample in each Example and Comparative Example at different locations, and the average values were calculated and rounded off to the first decimal place.

[Evaluation of Scratch Resistance of Resin Layer Surface]
For the laminates produced in Examples 1 to 17 and Comparative Examples 1 to 4, the surface of the resin layer was rubbed 10 times back and forth with a load of 250 kg/ ^cm2 using a flat abrasion tester (PA-300A manufactured by Daiei Scientific Instruments Co., Ltd.) using #0000 steel wool, and the presence or absence of scratches was visually observed and judged according to the following criteria, with 4 points or more being considered a pass.
10 points: 0 bottles; 7 points: 1 or more, but less than 5 bottles; 4 points: 5 or more, but less than 10 bottles; 1 point: 10 or more bottles.
[Evaluation of peelability of resin layer]
For the laminates produced in Examples 1 to 17 and Comparative Examples 1 to 4, one side of an adhesive film (PANAC Corporation, Panaclean PD-S1, 25 μm product) from which the separator had been removed was attached to the surface of the resin layer of the laminate while taking care not to trap air bubbles, and then the separator was peeled off from the adhesive film, and a PET film (188 μm, Toray Industries, Inc., "Lumirror" (registered trademark) T60) was attached.

The supporting substrate and the resin layer were previously peeled slightly from an end, and the peeled resin layer was peeled in a 180° direction and judged according to the following criteria, with an average score of 4 or more being considered a pass.
10 points: The film can be peeled off uniformly within the surface even at a peeling speed of 10,000 mm/min.
7 points: The film could not be peeled off uniformly within the surface at a peel speed of 10,000 mm/min, but could be peeled off uniformly within the surface at a peel speed of 1,000 mm/min.
4 points: The film could not be peeled off uniformly within the surface at a peeling speed of 1,000 mm/min, but could be peeled off uniformly within the surface at a peeling speed of 300 mm/min.
1 point: The film could not be peeled off uniformly within the surface at 300 mm/min.

[Evaluation of resin layer quality]
For the laminates produced in Examples 1 to 17 and Comparative Examples 1 to 4, 100 ^m2 was visually inspected with a light source reflected on the surface of the resin layer, and the number of deformations (cissing, foreign matter) with a diameter of 1 mm or more was observed was judged according to the following criteria, with an average score of 4 points or more being considered a pass.
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 conformability of resin layer]
For the laminates produced in Examples 1 to 17 and Comparative Examples 1 to 4, one side of an adhesive film (Panac Corporation, Panaclean PD-S1, 25 μm product) from which the separator had been peeled off was attached to the surface of the resin layer of the laminate while taking care not to introduce air bubbles, and then cut into a rectangle 90 mm wide x 90 mm long in a manner that would not cause cracks at the edges. The separator on the other side was peeled off and attached to a cylinder with a diameter of 30 mm. The state of the resin layer at this time was observed and judged according to the following criteria, with an average score of 4 or more being considered a pass.
10 points: The resin layer can be applied evenly without cracking or lifting; 7 points: Fine cracks are observed at the edges of the resin layer, but the rest of the resin layer can be applied evenly; 4 points: Fine cracks are observed at the edges and center of the resin layer, but the rest of the resin layer can be applied evenly; 1 point: Cracks or lifting occurs in the center of the resin layer, making it impossible to apply evenly.

[Crack resistance of resin layer]
For the laminates produced in Examples 1 to 17 and Comparative Examples 1 to 4, one side of an adhesive film (Panac Corporation, Panaclean PD-S1, 25 μm product) from which the separator had been removed was attached to the surface of the resin layer of the laminate while taking care not to trap air bubbles, and holes were punched with a 6 mm diameter hole punch for documents. Then, the separator on the other side of the adhesive layer was peeled off, and the laminate was attached to glass.

After leaving the sample in an environment of 23° C. and 50% humidity for 48 hours, the area around the hole was observed and judged according to the following criteria, with an average score of 4 points or more being considered a pass.
10 points: no cracks or chips are found around the hole in the resin layer; 7 points: chips are found around the hole in the resin layer, but no cracks; 4 points: cracks less than 0.5 mm from the edge of the hole are found around the hole in the resin layer; 1 point: cracks 0.5 mm or more from the edge of the hole are found around the hole in the resin layer

[Evaluation of Resin Layer Lifting]
The laminates produced in Examples 1 to 17 and Comparative Examples 1 to 4 were cut with a cutter knife into 100 x 200 mm squares, and the cut ends were observed when wrapped around a cylinder with a diameter of 30 mm. The results were judged according to the following criteria, with an average score of 4 or more being considered a pass.
10 points: No lifting occurs at either the end when cut with a cutter knife or the end when wrapped around a cylinder.
7 points: The ends do not float when cut with a cutter knife, but there is a slight float at the ends when wrapped around a cylinder.
4 points: The end portion is slightly raised when cut with a cutter knife, and is slightly raised when wrapped around a cylinder.
1 point: When cut with a cutter knife, the end portion floats, and when wrapped around a cylinder, the entire end portion floats.

Reference Signs List 1, 6, 12, 20, 26, 33: Laminate 2, 7, 13, 21, 27, 34: Release film 3, 8, 14, 19, 22, 28, 35: Support substrate 4, 9, 10, 15, 23, 29, 36: Release layer 5, 11, 16, 24, 30, 37: Resin layer 17: Protective film 18: Adhesive layer 25: Functional layer 31: Region B (island side) of sea-island structure
32: Island area A (sea side)
38: Region B of lamellar structure
39: Region A of lamellar structure

The resin film and laminate of the present invention have excellent scratch resistance, transportability as a thin film, and conformability to surface shapes. Taking advantage of the advantages of transferring layers with functions such as weather resistance, gas barrier properties, and blocking prevention, the resin film and laminate of the present invention can be suitably used for moldings such as plastics and metals.

To give some examples, it can be suitably used for the surface materials, internal materials, constituent materials, and manufacturing process materials of plastic molded products such as glasses/sunglasses, cosmetic cases, and food containers, aquariums, showcases for exhibitions, smartphone housings, touch panels, color filters, flat panel displays, flexible displays, flexible devices, wearable devices, sensors, circuit materials, electrical and electronic applications, home appliances such as keyboards, television and air conditioner remote controls, mirrors, window glass, buildings, dashboards, car navigation touch panels, vehicle parts such as rearview mirrors and windows, and various printed materials, medical films, sanitary material films, medical films, agricultural films, building material films, etc.

Claims (4)

A method for producing a laminate having a release layer and a resin layer in this order from the supporting substrate side on at least one surface of the supporting substrate, comprising:
The method for producing the laminate includes applying a coating composition for a resin layer onto a release layer of a supporting substrate , and then drying and curing the coating composition to form a resin layer,
The coating composition for the resin layer contains two types of resin precursors, and a resin component represented by Chemical Formula 2 and/or a resin component represented by Chemical Formula 3,
In the coating composition for resin layer, when the total content of the resin precursors is 100 parts by mass, the content of the resin component represented by Chemical Formula 2 and/or the resin component represented by Chemical Formula 3 is 0.3 to 3.0 parts by mass,
When observed by an atomic force microscope, a region (referred to as region B) having a lower elastic modulus than a region (referred to as region A) having a higher elastic modulus is present on the surface of the resin layer, and within a range of 5 nm from the surface of the resin layer, the region A contains a resin component represented by Chemical Formula 1,
The method for producing a laminate, wherein the laminate satisfies the following conditions:
Condition 1: Elastic modulus E _B of region B is 1,500 MPa or less. Condition 2: The average number of regions B in a 5 μm square is 50 to 300.

R ¹ is hydrogen or a methyl group, and R ² , R ³ and R ⁴ are any one of the following (i) to (vi).
(i) a substituted or unsubstituted alkylene group; (ii) a substituted or unsubstituted arylene group; (iii) a substituted alkylene group having an ether group, an ester group or an amide group therein; (iv) an unsubstituted alkylene group having an ether group, an ester group or an amide group therein; (v) a substituted arylene group having an ether group, an ester group or an amide group therein; (vi) an unsubstituted arylene group having an ether group, an ester group or an amide group therein. The method for producing a laminate according to claim 1, wherein the two types of resin precursors are either a multifunctional (meth)acrylate monomer, a (meth)acrylate oligomer, an alkoxysilane having a (meth)acrylic group, an alkoxysilane hydrolyzate having a (meth)acrylic group, an alkoxysilane oligomer having a (meth)acrylic group, an acrylic polymer having a (meth)acrylic group, a urethane polymer having a (meth)acrylic group, an epoxy polymer having a (meth)acrylic group, or a silicone polymer having a (meth)acrylic group. The method for producing a laminate according to claim 1 or 2, which is used in applications in which the resin layer is attached to an adherend and the supporting substrate is peeled off from the resin layer. The method for producing a laminate according to any one of claims 1 to 3, characterized in that the following conditions are satisfied:
Condition 3: The difference ( _EA - _EB ) between the elastic modulus _EA of the region A and the elastic modulus _EB of the region B is 100 MPa or more.
Condition 4: the major axis radius of the region B is 25 nm or more and 250 nm or less

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