Transfer film, its manufacturing method and transfer method

Abstract

This invention provides a transfer laminate with a structural color layer, and more particularly, a transfer laminate with a structural color layer on a substrate film, exhibiting excellent peelability of the substrate film after transfer to an adherend. The transfer laminate comprises a substrate film having a curing resin layer (A), a curing resin layer (B), and a resin layer (C) sequentially on one side thereof. The curing resin layer (A) is a structural color layer with structural color development formed from a cured layer of a curing resin composition (a) containing microparticles (X). The resin layer (C) is a sealing layer.

Description

Technical Field

[0001] This invention relates to a transfer laminate with a structural color layer, a method for manufacturing the same, and a transfer method. More specifically, it relates to a transfer laminate that exhibits excellent peelability after being transferred to a substrate, a method for manufacturing the same, and a transfer method using the transfer laminate. Background Technology

[0002] In recent years, structural colors have been applied in various fields such as industrial materials, electronic component materials, and battery packaging materials. For example, laminated films with a structural color layer (a layer with structural color rendering) on ​​the substrate film have been used in optical material packaging materials, automotive interiors, etc. (e.g., Patent Documents 1-3).

[0003] In addition, the use of laminated films with structural color layers as transfer films (decorative films) that impart design features to substrates by being adhered to them was also studied.

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent No. 5003268

[0007] Patent Document 2: International Publication No. 2008 / 120529

[0008] Patent Document 3: Japanese Patent Application Publication No. 2014-189719 Summary of the Invention

[0009] The problem that the invention aims to solve

[0010] In order to use a laminated film with a structural color layer as a transfer film for transfer onto a substrate, it is necessary to be able to easily peel the substrate film off from the structural color layer after the transfer film is applied to the substrate.

[0011] Furthermore, when the transfer film is bonded to the substrate via a sealing layer, the adhesion between the sealing layer and the structural color layer becomes a problem in improving the peelability of the transfer film.

[0012] However, the current situation is that previous research on using laminated films with structural color layers as transfer films, and the peelability of transfer films in this case, has not been sufficiently conducted.

[0013] The problem of this invention is to provide a transfer laminate with a structural color layer and a method for manufacturing the same. In particular, the problem of this invention is to provide a transfer laminate with a structural color layer on a substrate film and excellent peelability of the substrate film after transfer to an adherend, and a method for manufacturing the same.

[0014] Another problem with the present invention is to provide a transfer method using the transfer laminate film.

[0015] Solution for solving the problem

[0016] The inventors conducted in-depth research and found that by further providing a resin layer (C) to the laminated film obtained by stacking a cured resin layer (A) and a cured resin layer (B) on a substrate film, and by controlling the surface roughness of the substrate film and the water droplet contact angle difference between the surfaces of the cured resin layer (B) and the resin layer (C), the above-mentioned problems can be solved, thereby completing the following invention.

[0017] That is, the present invention provides the following [1] to [7].

[0018] [1] A transfer laminate film, wherein the transfer laminate film is a transfer laminate film having a curing resin layer (A), a curing resin layer (B) and a resin layer (C) sequentially on one side of a substrate film, wherein the curing resin layer (A) is a structural color layer having structural color development properties formed by a cured layer of a curing resin composition (a) containing microparticles (X), and the resin layer (C) is a sealing layer.

[0019] [2] According to the transfer film described in [1], the arithmetic mean height (Sa) of the surface of the cured resin layer (A) side of the substrate film is 50 nm to 600 nm.

[0020] [3] According to the transfer film described in [1], the water droplet contact angle difference between the surface of the cured resin layer (B) and the surface of the resin layer (C) is 0 to 35°.

[0021] [4] According to the transfer laminated film described in [2], wherein the storage modulus of the cured resin layer (B) at 25°C is 1.0 × 10⁻⁶. 3 Pa ~ 2.0 × 10 8 Pa.

[0022] [5] The transfer laminate according to [3] or [4], wherein a release layer is provided between the substrate film and the cured resin layer (A).

[0023] [6] A transfer laminate according to any one of [1] to [5], wherein the ratio of the total thickness of the cured resin layer (A) and the cured resin layer (B) to the thickness of the resin layer (C) is in the range of 10:1 to 10:5.

[0024] [7] A method for manufacturing a transfer laminate film, the method for manufacturing a transfer laminate film according to any one of [1] to [6], comprising: a heat treatment step of heating the curing resin composition (a) coated on the substrate film to form the curing resin layer (A); a heat treatment step of heating the curing resin composition (b) for forming the curing resin layer (B) coated on the curing resin layer (A) at a temperature of 130°C or below to form the curing resin layer (B); or an irradiation step of irradiating the curing resin composition (b) for forming the curing resin layer (B) coated on the curing resin layer (A) with active energy rays to form the curing resin layer (B); and a step of coating the curing resin composition (c) for forming the resin layer (C) on the curing resin layer (B) and drying it to form the resin layer (C).

[0025] [8] A transfer method wherein, after the resin layer (C) of the transfer laminate according to any one of [1] to [6] is pressed against and pressed against the substrate, the substrate film is peeled off and the cured resin layer (A) and the cured resin layer (B) are transferred to the substrate via the resin layer (C).

[0026] Invention Effects

[0027] According to the present invention, a transfer laminate having a structural color layer is provided, particularly a transfer laminate having a structural color layer on a substrate film and exhibiting excellent peelability of the substrate film after transfer to an adherend, a method for manufacturing the same, and a transfer method using the transfer laminate using the present invention are provided.

[0028] The transfer laminate of the present invention is useful in various fields such as industrial materials, electronic component materials, and battery packaging materials as a transfer laminate for imparting structural colors to various components and products. Attached Figure Description

[0029] Figure 1 This is a schematic diagram showing the state of structural color development in a cured resin layer (A) through the regular arrangement of particles (X). Detailed Implementation

[0030] Hereinafter, an example of an embodiment of the present invention will be described. However, the present invention is not limited to the embodiment described below.

[0031] [Laminated film for transfer printing]

[0032] The transfer laminate of the present invention (hereinafter, sometimes referred to as "the transfer laminate") is a transfer laminate in which a curing resin layer (A), a curing resin layer (B) and a resin layer (C) are sequentially provided on one side of a substrate film, wherein the curing resin layer (A) is a structural color layer with structural color development formed by a cured layer of a curing resin composition (a) containing microparticles (X), and the resin layer (C) is a sealing layer.

[0033] Hereinafter, the present invention will be described based on an embodiment of a transfer laminate in which a curing resin layer (A), a curing resin layer (B), and a resin layer (C) serving as a sealing layer are sequentially provided on a substrate film.

[0034] Hereinafter, the peelability of the substrate film when the transfer laminate film of the present invention is peeled off after being applied to the substrate will be referred to as "peelability".

[0035] <Substrate Film>

[0036] The substrate film constituting this transfer laminate (hereinafter, sometimes referred to as "the substrate film") only needs to be in film form, and its material is not particularly limited. For example, it can be made of paper, resin, metal, etc. Among these, resin is preferred from the viewpoint of mechanical strength and flexibility.

[0037] Examples of resin-based substrate films include those formed from polymers such as polyethylene, polypropylene, cyclic olefin polymers (COP), polyester, polystyrene, acrylonitrile-butadiene-styrene resin (ABS resin), acrylic resin, polycarbonate, polyurethane, triacetyl cellulose (TAC), polyvinyl chloride, polyethersulfone, polyamide, polyimide, and polyamide-imide.

[0038] In addition, as long as it can be film-formed, it can also be a substance made by mixing these materials (blended polymer) or a substance made by combining the constituent units (copolymer).

[0039] The preferred substrate varies depending on the intended application. For example, when heat resistance, flatness, strength, and other physical properties are required, polyester films are particularly preferred among the films exemplified above.

[0040] The aforementioned polyester film can be a single layer or a multilayer film (i.e., a laminated film) with two or more layers having different properties.

[0041] Furthermore, the polyester film can be a non-stretched film (sheet) or a stretched film. Preferably, it is a stretched film stretched along a uniaxial or biaxial direction. From the viewpoint of balancing mechanical properties and planarity, a biaxially stretched film is more preferred. Therefore, a biaxially stretched polyester film is even more preferred.

[0042] The aforementioned polyester film is a film made of polyester resin as the main component.

[0043] The polyester resin, which is the main component of polyester film, can be either homopolymer polyester or copolymer polyester.

[0044] It should be noted that the main component resin refers to the resin with the largest mass proportion in the resin constituting the polyester film. It is acceptable as long as it accounts for more than 50% by mass, or more than 75% by mass, or more than 90% by mass, or more than 100% by mass of the resin constituting the polyester film.

[0045] As the aforementioned homopolymer polyester, a homopolymer polyester obtained by polycondensation of an aromatic dicarboxylic acid and an aliphatic diol is preferred. Examples of aromatic dicarboxylic acids include terephthalic acid and 2,6-naphthalenedicarboxylic acid, with terephthalic acid being preferred. Examples of aliphatic diols include ethylene glycol, diethylene glycol, 1,4-butanediol, and 1,4-cyclohexanediethanol, with ethylene glycol being preferred.

[0046] Representative homopolymer polyesters include polyethylene terephthalate (PET) and polybutylene terephthalate (PBT).

[0047] The dicarboxylic acid component of the aforementioned copolyester may include one or more of isophthalic acid, phthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, adipic acid, sebacic acid, etc., and the diol component may include one or more of ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,4-cyclohexanediol, neopentyl glycol, etc. Preferably, the dicarboxylic acid component of the copolyester includes terephthalic acid, the diol component includes ethylene glycol, and the third component is any other than those listed above.

[0048] Furthermore, when formability, strength, etc. are required, copolyester films, ABS resin films, acrylic resin films, polyurethane films, and polyvinyl chloride films are particularly preferred among the films exemplified above.

[0049] Examples of acrylic resin films include "ACRYPLEN (registered trademark)" (manufactured by Mitsubishi Chemical Co., Ltd.) and "TECHNOLLOY (registered trademark)" (manufactured by Sumitomo Chemical Co., Ltd.).

[0050] Examples of ABS resin films include ABS film (manufactured by OKAMOTO Co., Ltd.) and ABS sheet (manufactured by Sekisui Molding Industries, Ltd.).

[0051] Examples of polyurethane membranes include those manufactured by SHEEDOM Corporation and NIHON UNIPOLYMER Corporation.

[0052] In the base film of this transfer laminate, particles may be incorporated for the primary purpose of imparting peelability and slip properties, thereby preventing damage during each process. When particles are incorporated, the type of particles is not particularly limited, as long as they impart slip properties. Specific examples include inorganic particles such as silica, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, alumina, and titanium dioxide, and organic particles such as acrylic resin, styrene resin, urea resin, phenolic resin, epoxy resin, and benzoguanamine resin. Furthermore, in the case of polyester films, precipitated particles formed by precipitating and micro-dispersing a portion of a metal compound such as a catalyst may be used in the polyester manufacturing process.

[0053] On the other hand, there are no particular restrictions on the shape of the particles used; any shape, such as spherical, blocky, rod-shaped, or flat, can be used. Furthermore, there are no particular restrictions on their hardness, specific gravity, or color. Two or more of these particles can be used in combination as needed.

[0054] Furthermore, the average particle size of the particles used is preferably 0.1 to 7 μm, more preferably 0.5 to 6 μm, and particularly preferably 1 to 5 μm. By using an average particle size within the above range, a suitable surface roughness can be imparted to the film, ensuring good peelability and sliding properties with the cured resin layer (A).

[0055] It should be noted that the average particle size is calculated by averaging the diameters of more than 10 particles measured using a scanning electron microscope (SEM). In the case of non-spherical particles, the average of the longest and shortest diameters is taken as the diameter of each particle. The same applies to the average particle size of microparticle (X) and particles in the slippery layer, which will be discussed later.

[0056] When particles are incorporated, it is preferable to provide a surface layer and an intermediate layer, with the surface layer containing particles. In this case, it is more preferable to provide a multi-layer structure having a surface layer containing particles, an intermediate layer, and another surface layer containing particles in sequence.

[0057] Furthermore, the particle content in the substrate film is preferably 0.01% to 5% by mass, more preferably 0.1% to 4% by mass. By setting the particle content within the above range, it is easy to impart a suitable surface roughness to the substrate film, and to easily impart peelability and sliding properties to the cured resin layer (A).

[0058] There are no particular restrictions on the color of the polyester film that constitutes the substrate film. It can be a colorless transparent polyester film or a colored polyester film such as black, white, or brown.

[0059] The thickness of the substrate film is preferably 9 μm to 350 μm, more preferably 12 μm to 250 μm, and particularly preferably 25 μm to 125 μm. If the substrate film is within the above range, the transfer laminate film has excellent operability as a substrate film, peel strength, and thin-film properties.

[0060] When the substrate film has a laminated structure having two or more layers, a three-layer structure consisting of a base layer A, a surface layer B, and a surface layer C, or a B / A / B structure consisting of a base layer A and a surface layer B, is preferred. When the substrate film has a laminated structure having two or more layers, the main component resin constituting each layer is preferably polyester, as described above.

[0061] <Preferred Solution for This Substrate Film>

[0062] As an example of a preferred embodiment of the substrate film in this transfer laminate, a substrate film having an arithmetic mean height (Sa) of 50 nm to 600 nm on the surface of the cured resin layer (A) side is provided. As long as the arithmetic mean height (Sa) of the surface of the substrate film on the cured resin layer (A) side is within the specified range, the substrate film can be peeled off from the substrate side with good peelability after the transfer laminate of the present invention has been applied to the substrate.

[0063] Considering the relationship with the adhesion to the cured resin layer (A), it is generally preferred that the substrate film has a small surface roughness. However, in this invention, it was unexpectedly found that a surface roughness in a specific range that is larger than usual is preferable in order to improve peelability.

[0064] If the arithmetic mean height (Sa) of the surface of the substrate film on the cured resin layer (A) side is less than 50 nm, there is a tendency for the adhesion between the substrate film and the cured resin layer (A) to become stronger and the peelability to decrease when making a laminated film for transfer. In addition, if the arithmetic mean height (Sa) of the surface of the film on the cured resin layer (A) side is greater than 600 nm, there is a tendency for the arrangement of particles in the cured resin layer (A) to be disturbed and the color rendering of structural colors to decrease.

[0065] From this perspective, the arithmetic mean height (Sa) of the surface of the cured resin layer (A) side of the substrate film is more preferably 60 nm to 500 nm, and even more preferably 70 nm to 450 nm.

[0066] It should be noted that the arithmetic mean height (Sa) of the substrate film is measured by the method described in the embodiments described later.

[0067] To produce a substrate film with such an arithmetic mean height (Sa), for example, it is considered to set the particle content in the aforementioned substrate film to at least 0.5% by mass, for example, 0.5% to 5% by mass. In particular, it is preferable to contain 0.5% to 5% by mass, more preferably 1% to 4.5% by mass, especially preferably 1.5% to 4.0% by mass of particles with an average particle size of 1 μm to 7 μm, more preferably 2 μm to 6 μm, and especially preferably 3 μm to 5 μm.

[0068] Furthermore, there are no particular limitations on the type of particles, as long as they impart slipperiness. Specific examples include inorganic particles such as silicon dioxide, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium phosphate, magnesium phosphate, kaolin, alumina, and titanium dioxide, as well as organic particles such as acrylic resin, styrene resin, urea resin, phenolic resin, epoxy resin, and benzoguanamine resin. For example, commercially available products include Fuji Silicon Chemical Co., Ltd.'s SYLYSIA550.

[0069] Furthermore, in order to produce a substrate film with such an arithmetic mean height (Sa), when the polyester film has a multilayer structure of two or more layers, the average particle size of the particles used in the polyester layer on the side where the curing resin layer (A) is provided is preferably 1 μm to 7 μm, more preferably 2 μm to 6 μm, and particularly preferably in the range of 3 μm to 5 μm. In addition, the particle content in this polyester layer is preferably 0.5% to 5% by mass, more preferably 1.0% to 4.5% by mass, and particularly preferably 1.5% to 4.0% by mass. If the average particle size and particle content are within the above ranges, a film with the surface roughness characteristic of the present invention can be obtained, exhibiting excellent release properties between the substrate film and the curing resin layer (A), as well as excellent sliding properties.

[0070] It should be noted that the polyester layer on the side opposite to the side where the cured resin layer (A) is provided may or may not contain particles, but from the viewpoint of slip resistance, it is preferable to contain particles.

[0071] <Cure Resin Layer (A)>

[0072] The curing resin layer (A) of this transfer laminate (hereinafter, sometimes referred to as "this curing resin layer (A)") is formed by curing the curing resin composition (a) (hereinafter, sometimes referred to as "this curing resin composition (a)") and is provided only on one side of this substrate film.

[0073] This cured resin layer (A) is a structural color layer with structural color development properties.

[0074] The cured resin composition (a) contains components that become polymers by polymerization, specifically, it may contain any polymeric compound selected from photopolymerizable compounds and thermal polymerizable compounds.

[0075] The present cured resin composition (a) requires the presence of particulate matter (X).

[0076] In this invention, it is speculated that the structure obtained by forming particles (X) with a certain degree of regularity can exhibit structural color.

[0077] From the viewpoint of improving durability, the cured resin layer (A) preferably further contains a crosslinking agent (Y), and the microparticles (X) are preferably microparticles having reactive functional groups.

[0078] The crosslinking agent (Y) forms a crosslinked structure through reaction with the reactive functional groups of the microparticles (X), thereby imparting strength to the coating film, that is, durability to the cured resin layer (A), and adhesion to the substrate film. Furthermore, in this case, by adjusting the amount of crosslinking agent (Y), the reflectivity of the laminated film surface can be prepared.

[0079] <Particle (X)>

[0080] The microparticle (X) is composed of a general polymer, which may be a non-crosslinked polymer or a crosslinked polymer, and preferably has reactive functional groups described later.

[0081] As general polymers, examples include polyamides, polyimides, low-density polyethylene, high-density polyethylene, poly(meth)acrylates, polystyrene and its derivatives, polyvinyl chloride, phenolic resins, and polycarbonates.

[0082] Among these, poly(meth)acrylates and polystyrene are preferred from the perspectives of easy availability of raw materials and ease of producing particles with uniform particle size. Among these, polystyrene is preferred from the perspective of obtaining polymers with high refractive index.

[0083] Polymers with high refractive index are preferred because the refractive index difference between the inside and outside of the particles increases, resulting in improved structural color rendering.

[0084] Regarding methods for manufacturing microparticles (X), for example, there are methods such as obtaining polymers of appropriate size through bulk polymerization, suspension polymerization, emulsion polymerization, solution polymerization, etc., pulverizing them to produce microparticles, and then uniformizing the particle size through operations such as sieving. In addition, there are methods that directly obtain microparticles (X) with uniform particle size through soap-free emulsion polymerization. Among these, considering superior productivity, methods based on soap-free emulsion polymerization are preferred.

[0085] In this invention, the particle (X) may be used in a single form or in a mixture of two or more forms.

[0086] [Poly(meth)acrylates]

[0087] In this invention, poly(meth)acrylates refer to polymers whose main component is (meth)acrylate units. Here, "main component" means that, relative to the polymer as a whole, the content of (meth)acrylate units is 50% by mass or more, and further 60% by mass or more. "(meth)acrylate" refers to one or both of "acrylic acid" and "methacrylic acid".

[0088] Examples of methacrylates that can be used as raw materials to form methacrylate units include methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate.

[0089] Poly(meth)acrylates can be random copolymers or block copolymers, but are generally random copolymers.

[0090] In addition to the aforementioned methacrylates, poly(meth)acrylates can also be copolymerized with any monomers.

[0091] As any monomer, examples include styrene-based monomers such as styrene and methylstyrene; metal salts such as sodium salts of styrene sulfonic acid; acidic monomers such as acrylic acid and methacrylic acid; and acrylamide-based monomers such as acrylamide and N-propylacrylamide.

[0092] Among these, metal salts such as sodium salt of styrene sulfonic acid are preferred from the perspective of better particle size control.

[0093] Furthermore, when introducing cross-linking structures into poly(meth)acrylates, it is sufficient to copolymerize known multifunctional monomers.

[0094] [Polystyrene]

[0095] In this invention, polystyrene refers to polymers whose main component is styrene units. Here, "main component" means that the content of styrene units relative to the polymer as a whole is 50% by mass or more, and further 60% by mass or more.

[0096] Polystyrene can be either random copolymers or block copolymers, but it is generally a random copolymer.

[0097] Polystyrene can be copolymerized with any monomer other than styrene.

[0098] As any monomer, examples include styrene other than styrene such as methylstyrene and chlorostyrene; metal salts such as sodium salts of styrene sulfonic acid; acidic monomers such as acrylic acid and methacrylic acid; (meth)acrylates such as methyl methacrylate and ethyl methacrylate; and acrylamides such as acrylamide and N-propylacrylamide.

[0099] Among these, metal salts such as sodium salt of styrene sulfonic acid are preferred from the perspective of better particle size control.

[0100] Furthermore, when introducing cross-linking structures into polystyrene, it is sufficient to copolymerize known multifunctional monomers.

[0101] Polystyrene products preferably contain 80.0% to 99.75% by mass of styrene units. If the content of styrene units is within this range, the refractive index of the particles increases, and the structural color rendering is improved, therefore this is preferred. The content of styrene units is more preferably 90.0% by mass or more. Furthermore, it is more preferably 99.4% by mass or less.

[0102] [Number-average particle size]

[0103] From the viewpoint of achieving good structural color development, the number-average particle size of the particles (X) is preferably 50 nm to 450 nm, particularly preferably 100 nm to 400 nm, and especially preferably 150 nm to 300 nm.

[0104] In particular, from the viewpoint of achieving good structural color in the visible light region, the number-average particle size is preferably 151 nm to 359 nm, more preferably 170 nm to 330 nm, and especially preferably 180 nm to 300 nm.

[0105] Furthermore, in order to exhibit structural color in the ultraviolet region, it is preferable to use microparticles with a small number-average particle size, for example, 80 nm to 150 nm, and in order to exhibit structural color in the infrared region, it is preferable to use microparticles with a large number-average particle size, for example, 360 nm to 800 nm.

[0106] It should be noted that the number-average particle size of the particles (X) is a value determined by the method described in the embodiments described later.

[0107] [Glass transition temperature (Tg)]

[0108] The glass transition temperature (Tg) of the microparticles (X) is preferably 81°C or higher, more preferably 90°C or higher, even more preferably 95°C or higher, particularly preferably 100°C or higher, and especially preferably 105°C or higher. If the Tg of the microparticles (X) is 81°C or higher, they exhibit excellent heat resistance and maintain their structure even under high-temperature operating conditions, thus making it preferable.

[0109] Here, the glass transition temperature (Tg) of the particle (X) is a value determined by the method described in the following embodiments.

[0110] [Reactive functional groups]

[0111] The microparticles (X) of the present invention preferably have reactive functional groups. Examples of reactive functional groups include hydroxyl, carboxyl, glycidyl, oxetyl, ketone, aldehyde, silyl, allyl, vinyl ether, amino, and phosphate groups. They may be present individually or in combination with more than one.

[0112] Among these, from the viewpoint of color development, hydroxyl, glycidyl, oxetyl, ketone, aldehyde, silyl, allyl, vinyl ether, amino, and phosphate groups are preferred, hydroxyl, glycidyl, oxetyl, ketone, and aldehyde groups are more preferred, and glycidyl, ketone, and aldehyde groups are even more preferred.

[0113] When the particle (X) has two or more reactive functional groups, at least one is preferably a ketone group, and more preferably a combination of a ketone group and a carboxyl group.

[0114] Furthermore, when the particle (X) has two reactive functional groups, and at least one is a ketone group, the content ratio of the ketone group (molar ratio of ketone group to the other reactive functional group) is preferably 0.01 or more, more preferably 0.1 or more, and on the other hand, preferably 100 or less, more preferably 10 or less. In particular, when the other reactive functional group is a carboxyl group, the content ratio of the ketone group is preferably 0.01 or more, more preferably 1.0 or more, and on the other hand, preferably 10 or less, more preferably 5.0 or less.

[0115] There are no particular limitations on the method of introducing reactive functional groups into microparticles (X). For example, the following method can be listed: copolymerizing a polymerizable monomer with reactive functional groups with monomers with free radical polymerizability such as (meth)acrylates, styrene, or other arbitrary monomers that constitute the polymeric unit of the polymer microparticle.

[0116] The following are examples of polymerizable monomers that have hydroxyl groups as reactive functional groups, but are not limited to these examples.

[0117] Hydroxyl-containing (meth)acrylic monomers such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate; polyalkylene glycol (meth)acrylic monomers such as polyethylene glycol mono(meth)acrylate and polypropylene glycol mono(meth)acrylate; hydroxyalkyl vinyl ether monomers such as hydroxyethyl vinyl ether and hydroxybutyl vinyl ether; allyl monomers containing hydroxyl groups such as allyl alcohol and 2-hydroxyethyl allyl ether.

[0118] These monomers can be used alone or in combination of two or more.

[0119] The following are examples of polymerizable monomers that have a carboxyl group as a reactive functional group, but are not limited to these examples.

[0120] Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, and fumaric acid; monoalkyl (carbon 1-8) esters of itaconic acid such as monobutyl itaconic acid; monoalkyl (carbon 1-8) esters of maleic acid such as monobutyl maleate; vinyl-containing aromatic carboxylic acids such as vinyl benzoic acid; and various carboxyl-containing monomers and their salts.

[0121] These monomers can be used alone or in combination of two or more. Furthermore, they can be neutralized to produce balancing ions such as Na.

[0122] The following are examples of polymerizable monomers that have glycidyl or oxobutyl groups as reactive functional groups, but are not limited to these examples.

[0123] Glycidyl methacrylate, β-methyl glycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, methyl 3,4-epoxycyclohexyl methacrylate, 4-hydroxybutyl methacrylate glycidyl ether, p-glycidyl styrene, (3-ethyloxetane-3-yl)methyl methacrylate, etc.

[0124] These monomers can be used alone or in combination of two or more.

[0125] The following are examples of polymerizable monomers that have ketone or aldehyde groups as reactive functional groups, but are not limited to these examples.

[0126] Diacetone acrylamide, diacetone methacrylamide, acrolein, N-vinylformamide, vinyl methyl ketone, vinyl ethyl ketone, acetoacetoxyethyl acrylate, acetoacetoxypropyl acrylate, acetoacetoxybutyl acrylate, acetoacetoxyethyl methacrylate, acetoacetoxypropyl methacrylate, acetoacetoxybutyl methacrylate, etc.

[0127] These monomers can be used alone or in combination of two or more.

[0128] The following are examples of polymerizable monomers that have silyl groups as reactive functional groups, but are not limited to these examples.

[0129] Vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, p-styrylmethoxysilane, 3-methacryloxypropyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, etc.

[0130] These monomers can be used alone or in combination of two or more.

[0131] The following are examples of polymerizable monomers that have allyl, vinyl ether, amino, and phosphate groups as reactive functional groups, but are not limited to these examples.

[0132] Allyl methacrylate, 2-(2-ethyleneoxyethoxy)ethyl methacrylate, 2-(meth)acryloyloxyethyl acid phosphate, bis[2-(meth)acryloyloxyethyl] phosphate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-aminoethyl methacrylate, etc.

[0133] These monomers can be used alone or in combination of two or more.

[0134] [Method for manufacturing particulate matter (X)]

[0135] The microparticles (X) are preferably obtained by soap-free emulsion polymerization. Soap-free emulsion polymerization is a well-known polymerization method, as described below, for example.

[0136] Ion-exchanged water is added to the reaction vessel. While heating and stirring, polymerization aids are added as needed to ensure thorough dispersion of the aids in the ion-exchanged water. Next, polymerization initiators are added while continuing stirring. Then, monomers are added dropwise while continuing stirring to initiate the polymerization reaction. As polymerization proceeds, particles are formed.

[0137] It should be noted that when obtaining microparticles (X) via soap-free emulsion polymerization, it is preferable not to use surfactants even below the critical micelle concentration. By not using surfactants, microparticles with higher monodispersity can be obtained.

[0138] The concentration of solid components during polymerization, i.e. the concentration of particles (X) relative to the whole system during polymerization, is preferably 20 to 40 by mass.

[0139] If the concentration of solid components during polymerization is above the lower limit, the productivity of particles (X) increases. Furthermore, if it is below the upper limit, no polymerization debris or deposits adhering to the inner walls of the polymerization apparatus will be generated.

[0140] When using a polymerization initiator, the polymerization temperature is generally set to 60–90°C. After the reaction is complete, the microparticles (X) are removed in the form of an emulsion.

[0141] The pH of the emulsion is preferably 3.0 to 11.0. If the pH of the emulsion is outside this range, the productivity is insufficient from the viewpoint of metal corrosion. Furthermore, when a ketone group is selected as the reactive functional group of the microparticle (X) and an acylhydrazine compound is selected as the crosslinking agent (Y), the pH is preferably 3.0 to 11.0, more preferably 3.0 to 8.0, and even more preferably 6.0 to 8.0. If the pH is less than 3.0, the productivity is insufficient from the viewpoint of metal corrosion. If the pH exceeds 11.0, the reactivity of the ketone group with the acylhydrazine compound decreases, and a structure exhibiting sufficient physical durability cannot be obtained.

[0142] Therefore, if the pH of the emulsion deviates from the preferred range described above, it is preferable to add an appropriate amount of alkali or acid to adjust the pH.

[0143] Typically, the pH of the emulsion obtained during the manufacture of the aforementioned microparticles (X) is around 2.0 to 7.0. Therefore, an alkali is usually added to adjust the pH. Ammonia or similar substances are preferred as the alkali used for pH adjustment, considering that it can be easily removed from the structure through heating or similar methods.

[0144] Examples of polymerization initiators used in soap-free emulsion polymerization include water-soluble polymerization initiators such as sodium persulfate, potassium persulfate, and ammonium persulfate; oil-soluble polymerization initiators such as benzoyl peroxide and lauroyl peroxide; and redox polymerization initiators based on combinations of oxidants and reductants.

[0145] <Crosslinking agent (Y)>

[0146] This cured resin composition (a) contains a crosslinking agent (Y), which causes the reactive functional groups of the particles (X) to react with the crosslinking agent and crosslink, thereby enabling chemical bonding between the particles (X). As a result, the cured resin layer (A) formed using this cured resin composition (a) has excellent durability and adhesion to the substrate film, and is therefore preferred.

[0147] As a crosslinking agent (Y), any compound having reactive functional groups that are introduced into the particles (X) can be used. Examples include multifunctional epoxy compounds, isocyanate compounds, hydrazide compounds, oxazoline compounds, amine compounds, carboxylic acid compounds, free radical polymerizable monomers, aziridine compounds, silane compounds, and carbodiimide compounds. They can be used alone or in combination of two or more.

[0148] As multifunctional epoxides, the following compounds can be listed, but are not limited to the example compounds listed below.

[0149] Various epoxy prepolymers and multifunctional epoxy resins, including ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, resorcinol diglycidyl ether, propylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, glycidyl ether type, glycidyl ester type, glycidyl amine type, aliphatic type, alicyclic type, phenolic varnish type, aminophenol type, hydantoin type, isocyanurate type, biphenol type, naphthalene type, etc.

[0150] They can be used individually or in combination of two or more.

[0151] The following compounds are examples of multifunctional isocyanates, but are not limited to these examples. It should be noted that isocyanate compounds also include end-capped isocyanates.

[0152] Hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, decamethylene diisocyanate, lysine diisocyanate, trioxane ethylidene diisocyanate, and other aliphatic diisocyanates; benzodimethylene-1,4-diisocyanate, benzodimethylene-1,3-diisocyanate, tetramethylbenzodimethylene diisocyanate, and other aromatic aliphatic diisocyanates; isophorone diisocyanate, Norbornene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated xylene diisocyanate, methylene dicyclohexyl diisocyanate (also known as hydrogenated diphenylmethane diisocyanate), hydrogenated tetramethylbenzene dimethyl diisocyanate and other alicyclic diisocyanates, as well as trimers, urea formates, biurets, dimers, dimer-trimers, carbodiimides, urea ketene imides, adducts obtained by reacting said isocyanates with polyols with two or more functions.

[0153] They can be used individually or in combination of two or more.

[0154] The following compounds are examples of multifunctional hydrazide compounds, but are not limited to the following example compounds.

[0155] Aliphatic diacylhydrazides include oxalate diacylhydrazides, malonate diacylhydrazides, succinate diacylhydrazides, glutarate diacylhydrazides, adipic acid diacylhydrazides, and sebacylhydrazides. In addition, there are diacylhydrazides of unsaturated dicarboxylic acids, such as polyhydrazides of carbonate, aliphatic, alicyclic, and aromatic diaminoureas, aromatic dicarboxylic acid diacylhydrazides, polyacylhydrazides of polyacrylic acid, diacylhydrazides of aromatic hydrocarbons, hydrazine-pyridine derivatives, and maleic acid diacylhydrazides.

[0156] They can be used individually or in combination of two or more.

[0157] Examples of multifunctional oxazoline compounds include the polymer "EPOCROS (Nippon Shokubai Co., Ltd.)" which contains an oxazoline group. Multifunctional oxazoline compounds can be used alone or in combination of two or more.

[0158] As multifunctional amine compounds, the following compounds can be listed, but are not limited to the following example compounds.

[0159] Ethylenediamine and its adducts, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, hexamethylenediamine and its modifiers, N-aminoethylpiperazine, diaminopropylpiperazine, trimethylhexamethylenediamine, dihexamethylenetriamine, dicyandiamide, diacetylacrylamide, various modified aliphatic polyamines, polyoxypropylenediamine and other aliphatic amines; 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3-amino-1-cyclohexylaminopropane, 4,4'-diaminodicyclohexylmethane, isophoronediamine, 1,3-bis(aminomethyl) Cyclohexane, N-dimethylcyclohexylamine, bis(aminomethyl)norbornene and other alicyclic amines and their modified derivatives; 4,4'-diaminodiphenylmethane (methylene diphenylamine), 4,4'-diaminodiphenyl ether, diaminodiphenyl sulfone, m-phenylenediamine, 2,4'-toluenediamine, m-toluenediamine, o-toluenediamine, m-phenylenediamine, phenylenediamine and other aromatic amines and their modified derivatives; other special amine modified derivatives; amide amines, amino polyamide resins and other polyamide amines; dimethylaminomethylphenol, 2,4,6-tris(dimethylaminomethyl)phenol, tris(dimethylaminomethyl)phenol tri-2-ethylhexanoate and other tertiary amines; etc.

[0160] They can be used individually or in combination of two or more.

[0161] The following compounds are examples of multifunctional carboxylic acid compounds, but are not limited to these examples. It should be noted that carboxylic acid compounds also include their anhydrides.

[0162] Malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, sebacic acid, fumaric acid, maleic acid, terephthalic acid, isophthalic acid, etc.

[0163] They can be used individually or in combination of two or more.

[0164] The following compounds are examples of multifunctional free radical polymerizable monomers, but are not limited to the listed examples.

[0165] N-[tris(3-(meth)acrylamide propoxymethyl)methyl]acrylamide, N,N-bis(2-(meth)acrylamide ethyl) (meth)acrylamide, N,N'-[oxybis(2,1-ethylenedioxy-3,1-propadiyl)]bis(meth)acrylamide, N,N'-1,2-ethylenedioxybis{N-[2-((meth)acryloylamino)ethyl](meth)acrylamide}bisacrylamide, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, 1,2,4-cyclohexane tetra(meth)acrylate, pentaglycerol triacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol triacrylate, tripentaerythritol hexaacrylate, etc.

[0166] They can be used individually or in combination of two or more.

[0167] Examples of multifunctional aziridine compounds include the polymer "CHEMITITE (Nippon Shokubai Co., Ltd."), which contains an aziridine group. Multifunctional aziridine compounds can be used alone or in combination of two or more.

[0168] As multifunctional silane compounds, the following compounds can be listed, but are not limited to the following example compounds.

[0169] Methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, dimethoxydiphenylsilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltriethoxysilane, 1,6-bis(trimethoxysilyl)hexane, 3,3,3-trifluoropropyltrimethoxysilane, hexamethyldisilazane, etc.

[0170] They can be used individually or in combination of two or more.

[0171] As a multifunctional carbodiimide compound, for example, the polymer "CARBODILITE (Nisshinbo Chemical Co., Ltd.)" containing a carbodiimide group can be used alone or in combination of two or more.

[0172] [Preferred combination of reactive functional groups of microparticles (X) and crosslinking agent (Y)]

[0173] In this invention, the following combination is preferred as a combination of the reactive functional groups of the microparticle (X) and the crosslinking agent (Y).

[0174] When the reactive functional groups of the particles (X) are ketone or aldehyde groups, the crosslinking agent (Y) of the combination is preferably an acylhydrazine compound.

[0175] When the reactive functional groups of the particles (X) are glycidyl or oxetyl, the crosslinking agent (Y) of the combination is preferably an amine compound, a carboxylic acid compound, or an acylhydrazine compound.

[0176] When the reactive functional group of the particle (X) is a hydroxyl group, the crosslinking agent (Y) of the combination is preferably an isocyanate compound.

[0177] When the reactive functional group of the particle (X) is a carboxyl group, the crosslinking agent (Y) of the combination is preferably an epoxy compound, an oxazoline compound, an aziridine compound, or a carbodiimide compound.

[0178] When the reactive functional group of the particle (X) is silyl, the crosslinking agent (Y) of the combination is preferably a silane compound.

[0179] When the reactive functional groups of the particles (X) are allyl or vinyl ether, the crosslinking agent (Y) of the combination is preferably a free radical polymerizable monomer.

[0180] Water-soluble resins

[0181] From the viewpoint of forming a uniform coating film, the cured resin layer (A) and the cured resin composition (a) preferably further comprise a water-soluble resin.

[0182] Water-soluble resins are substances that are dissolved in water or at least dispersed in water within a polymer compound.

[0183] As a water-soluble resin, it is preferable to have ionic groups such as sulfonyl groups and carboxyl groups in the molecule, as well as water-soluble substituents such as hydroxyl groups, and to be soluble in water.

[0184] Water-soluble resins can be classified into nonionic and ionic types.

[0185] Examples of nonionic water-soluble resins include water-soluble polyacrylamide, water-soluble acrylic resins, nonionic polyvinyl alcohol resins, polyvinylpyrrolidone, polyethylene oxide, polyvinyl acetate; and natural polymers such as starch, gelatin, and casein.

[0186] Examples of ionic water-soluble resins include water-soluble polyester resins, polyacrylic acid, ionic polyvinyl alcohol resins, and carboxymethyl cellulose.

[0187] Among these, nonionic and / or ionic polyvinyl alcohol (PVA) resins are preferred due to the high hydrolysis resistance of the polymer backbone. Furthermore, among water-soluble resins, ionic water-soluble resins are preferred from the viewpoint of solubility in water.

[0188] In this invention, only one type of water-soluble resin may be used, or two or more types may be used in combination.

[0189] [Ionic water-soluble resins]

[0190] Ionic water-soluble resins refer to water-soluble resins with anionic or cationic components, specifically as described above.

[0191] Among ionic water-soluble resins, ionic polyvinyl alcohol-based resins are preferred due to their excellent solvent resistance.

[0192] [Ionic polyvinyl alcohol resins]

[0193] Ionic polyvinyl alcohol resins refer to polyvinyl alcohol resins that contain ionic groups such as sulfonyl groups or their salts, carboxyl groups or their salts, and quaternary ammonium salts in their molecular chains.

[0194] As ionic polyvinyl alcohol resins, examples include polyvinyl alcohol resins containing sodium salts of sulfonyl groups in the molecular chain and polyvinyl alcohol resins containing sodium salts of carboxyl groups in the molecular chain.

[0195] Among these, polyvinyl alcohol resins containing sodium salts with sulfonyl groups are preferred, based on the reason that salts are easily dissociated.

[0196] Commercially available products that are ionic polyvinyl alcohol resins include, for example, GOHSENX (a specially modified polyvinyl alcohol resin manufactured by Mitsubishi Chemical Corporation).

[0197] <Water-soluble>

[0198] It is preferable to prepare the coating solution by diluting the cured resin composition (a) with an aqueous solvent.

[0199] It is preferable to form the cured resin layer (A) by coating the substrate film as a liquid coating liquid, drying and curing it.

[0200] The components constituting this cured resin composition (a) are soluble or dispersed in an aqueous solvent. In this invention, the cured resin composition (a) preferably does not contain organic solvents.

[0201] "Substantially does not contain organic solvents" means that, apart from water, small amounts of organic solvents that are unavoidably not completely removed during the manufacturing process of the particles (X) may be mixed in without prejudice to the spirit of the invention. Specifically, the amount is 5% by mass or less relative to the total mass of water, preferably 3% by mass or less, and particularly preferably 2% by mass or less. Specific examples of organic solvents include, for example, alcohol-based solvents such as methanol, ethanol, propanol, isopropanol, and butanol.

[0202] There is no particular limitation on the amount of water solvent used, and it is appropriately determined taking into account the coatability of the prepared cured resin composition (a), the viscosity and surface tension of the liquid, the compatibility of the solid components, etc. The cured resin composition (a) is preferably prepared using water solvent as a coating liquid with a preferred solid component concentration of 5% to 80% by mass, more preferably 10% to 70% by mass, and particularly preferably 15% to 60% by mass.

[0203] In particular, taking into account the coating appearance of the cured resin composition (a) and the appearance of the formed cured resin layer (A), the solid content concentration of the cured resin composition (a) is preferably 24% by mass or more, for example, 24% by mass to 40% by mass, and particularly preferably 24% by mass to 30% by mass.

[0204] It should be noted that the "solid component" in this cured resin composition (a) refers to the component other than the solvent, which is a volatile component. It includes not only solid components but also semi-solid and viscous liquid components.

[0205] <Other Ingredients>

[0206] Various additives may be appropriately incorporated into the cured resin composition (a) as needed, without prejudice to the spirit of the invention. Examples of additives include, for instance, antioxidants, antistatic agents, leveling agents, dispersants, thixotropic agents (thickeners), and defoamers. Only one of these additives may be incorporated, or two or more may be incorporated.

[0207] <Content of each component>

[0208] From the viewpoint of effectively obtaining the improved coating strength effect brought about by the crosslinking agent (Y) and achieving good structural color development, the content of the crosslinking agent (Y) in the cured resin layer (A) and the cured resin composition (a) is preferably in the range of 0.01 parts by mass to 50 parts by mass relative to 100 parts by mass of the particles (X), more preferably in the range of 0.05 parts by mass to 40 parts by mass, even more preferably in the range of 0.1 parts by mass to 30 parts by mass, and particularly preferably in the range of 1 part by mass to 20 parts by mass.

[0209] Furthermore, from the same point of view, the content of the crosslinking agent (Y) is preferably in the following amounts: the reaction equivalent of the crosslinking agent (Y) relative to the reactive functional groups of the particles (X) is 0.1 equivalent to 10 equivalents, particularly 0.5 equivalents to 1.5 equivalents.

[0210] When the cured resin layer (A) and the cured resin composition (a) contain water-soluble resin, from the viewpoint of structural color development, the content of water-soluble resin is preferably in the range of 0.001 parts by mass to 0.4 parts by mass relative to 100 parts by mass of the particles (X) in the cured resin layer (A) and the cured resin composition (a), more preferably in the range of 0.005 parts by mass to 0.4 parts by mass, and even more preferably in the range of 0.05 parts by mass to 0.4 parts by mass.

[0211] It should be noted that, from the viewpoint of structural color development, the content of particulate matter (X) in the solid components of the cured resin layer (A) and the cured resin composition (a) is preferably 50% by mass or more, more preferably 60% to 99.9% by mass, particularly preferably 70% to 99.5% by mass, and especially preferably in the range of 80% to 99% by mass.

[0212] <Preparation method of this cured resin composition (a)>

[0213] This cured resin composition (a), particularly the cured resin composition (a) containing an aqueous solvent, can be prepared by mixing the aqueous solvent with other components such as microparticles (X), a crosslinking agent (Y), and a water-soluble resin as needed.

[0214] For example, it can be prepared by mixing an emulsion containing microparticles (X) manufactured using the aforementioned method, a crosslinking agent (Y), other components such as a water-soluble resin used as needed, and an aqueous solvent for adjusting the concentration of solid components.

[0215] <Thickness of cured resin layer (A)>

[0216] The thickness of the cured resin layer (A) is typically 1 μm to 10 μm, preferably 2 μm to 9 μm, more preferably 3 μm to 8 μm, and particularly preferably 5 μm to 7 μm. By setting the thickness of the cured resin layer (A) within the aforementioned range, the desired structural color is easily developed.

[0217] Here, the thickness of the cured resin layer (A) is the thickness after the cured resin composition (a) is applied and cured in the method for forming the cured resin layer (A) described later.

[0218] <Method for forming the cured resin layer (A)>

[0219] As described above, the cured resin layer (A) can be obtained by coating the cured resin composition (a) onto the surface of a substrate film, drying it to form a coating layer, and then curing the coating layer.

[0220] As a method for coating the cured resin composition (a), conventionally known coating methods such as air knife coating, blade coating, rod coating, barcoating, doctor blade coating, extrusion coating, dip coating, reverse roller coating, transfer roller coating, gravure coating, kissing roller coating, cast coating, spraying, curtain coating, calendering coating, and extrusion coating can be used.

[0221] There are no particular limitations on drying conditions; it can be carried out at room temperature or by heating. When heating is used, higher heating temperatures tend to increase the coating strength, but on the other hand, they tend to decrease the reflectivity.

[0222] Considering the heat resistance of the particles (X), if the temperature exceeds 120°C, the particles (X) tend to begin to melt easily. Therefore, the heating temperature is preferably 25°C to 120°C, more preferably 25°C to 110°C, and particularly preferably in the range of 90°C to 110°C.

[0223] Furthermore, the drying time is not particularly limited as long as the aqueous solvent can be fully evaporated, for example, 10 seconds to 30 minutes, preferably 15 seconds to 10 minutes.

[0224] That is, the transfer film is preferably manufactured according to the manufacturing method of the present invention of the laminated film having a heat treatment step, which is a process of heating the cured resin composition (a) coated on the substrate film at 25°C to 120°C for 10 seconds to 30 minutes, preferably 10 seconds to 10 minutes, and particularly preferably 15 seconds to 5 minutes to form the cured resin layer (A).

[0225] The curing method of this curing resin composition (a) can be appropriately selected according to the curing mechanism of this curing resin composition (a). If this curing resin composition (a) is a thermosetting resin composition, it can be cured simply by heating. In addition, if it is a photocurable resin composition, it can be cured simply by irradiating it with active energy rays.

[0226] Among the active energy rays that can be used to cure the present curing resin composition (a) are ultraviolet light, electron beams, X-rays, infrared rays, and visible light. Of these active energy rays, ultraviolet light and electron beams are preferred from the viewpoint of curability and prevention of resin degradation.

[0227] From the viewpoints of molding time and productivity, as well as preventing thermal shrinkage and thermal degradation of the components caused by heating, the curing method of this curing resin composition (a) is preferably performed by energy beam irradiation. The energy beam irradiation can be performed from either side, from the substrate film side, or from the opposite side of the substrate film.

[0228] When forming this cured resin layer (A), if the cured resin composition (a) is cured by ultraviolet irradiation, various ultraviolet irradiation devices can be used as the light source, such as xenon lamps, high-pressure mercury lamps, metal halide lamps, LED-UV lamps, etc. The ultraviolet irradiation dose (unit: mJ / cm²) is specified. 2 It is usually 50 mJ / cm 2 ~3000mJ / cm 2 From the viewpoints of curability of the present curing resin composition (a) and flexibility of the cured product (cured film), 100 mJ / cm is preferred. 2 ~1000mJ / cm 2 From the viewpoint of the planarity of the cured resin layer (A), a value of 100 mJ / cm is more preferable. 2 ~500mJ / cm 2 The scope should be appropriately determined.

[0229] Furthermore, when forming this cured resin layer (A), various electron beam irradiation devices can be used when curing the cured resin composition (a) by electron beam irradiation. The electron beam irradiation dose (Mrad) is typically 0.5Mrad to 20Mrad, and from the viewpoints of curability of the cured resin composition (a), flexibility of the cured product, and prevention of damage to the substrate, it is preferable to appropriately determine it in the range of 1Mrad to 15Mrad.

[0230] <Cure Resin Layer (B)>

[0231] The curing resin layer (B) (hereinafter sometimes referred to as "the curing resin layer (B)") of this transfer laminate is typically formed by curing a curing resin composition (b) (hereinafter sometimes referred to as "the curing resin composition (b)"), and is laminated on the curing resin layer (A), that is, the side of the curing resin layer (A) opposite to the substrate film. Therefore, this transfer laminate is a laminate formed by sequentially laminating at least the substrate film, the curing resin layer (A), the curing resin layer (B), and the resin layer (C) described later.

[0232] This cured resin layer (B) protects the cured resin layer (A) and maintains the color development of the structure.

[0233] <This cured resin composition (b)>

[0234] From the viewpoint of reducing thermal damage to the particles (X) contained in the cured resin layer (A), the cured resin composition (b) is preferably selected to be of the type that can be cured at a temperature below 120°C, or can be cured at a cumulative light intensity of 250 mJ / cm. 2 The following are the types of curing based on irradiation dose.

[0235] As compounds contained in this curing resin composition (b), conventionally known materials can be used as long as the curing resin composition (b) meets any of the aforementioned conditions. For example, silicone resins and urethane resins as thermosetting resins, acrylic resins, silicone-based compounds such as organosilicon-containing (meth)acrylates as UV-curing resins, or fluorinated (meth)acrylate compounds, fluorinated epoxy acrylates, and other urethane (meth)acrylates can be used. Only one of these silicone resins, silicone compounds, fluorinated compounds, and acrylic resins can be used, or two or more can be used in combination.

[0236] If the curable resin is used, the surface of the cured resin layer (B) may also be incidentally given antifouling properties (water repellency, oil repellency).

[0237] Manufactured by organic silica resin, example, possible example, Isshin Etsu Chemical Industry Co., Ltd. one-component RTV resin (example, KE-3423, KE-347, KE-3475, KE-3495, KE-4895, KE-4896, KE-1830, KE-1884, KE-3 479, KE-348, KE-4897, KE-4898, KE-1820, KE-1825, KE-1831, KE-1833, KE-1885, KE-1056, KE-1151, KE-1842, KE-1886, KE-3424 G, KE-3494, KE-3490, KE-40RTV, KE-4890, KE-3497, KE-3498, KE-3493, KE-3466, KE-3467, KE-1862, KE-1867, KE-3491, KE-3492, KE-3417, KE-3418, KE-3427, KE-3428, KE-41, KE-42, KE-44, KE-45, KE-441, KE-445, KE-45S, etc.), two-component RTV rubber manufactured by Shin-Etsu Chemical Co., Ltd. (for example, KE-1 800T-A / B, KE-66, KE-1031-A / B, KE-200, KE-118, KE-103, KE-108, KE-119, KE-109E-A / B, KE-1051J-A / B, KE-1012-A / B, KE-106, KE-1282-A / B, KE-1283-A / B, KE-1800-A / B / C, KE-1801-A / B / C, KE-1802-A / B / C, KE-1281-A / B, KE-1204-A / B, KE-1204-AL / BL, KE -1280-A / B, KE-513-A / B, KE-521-A / B, KE-1285-A / B, KE-1861-A / B, KE-12, KE-14, KE-17, KE-113, KE-24, KE-26, KE-1414, KE-14 15, KE-1416, KE-1417, KE-1300T, KE-1310ST, KE-1314-2, KE-1316, KE-1600, KE-1603-A / B, KE-1606, KE-1222-A / B, KE-1241, etc.) etc.

[0238] In addition, one example of the compound contained in the solidified resin composite (b) is an organic silicon low-density material.

[0239] As organosilicon oligomers, examples include organosilicon oligomers obtained by (co)hydrolysis / condensation of at least one of the alkoxysilanes and their partially hydrolyzed condensates shown in formula (1) below.

[0240] (R) 1 ) m (R) 2 ) n Si(OR) 3 ) 4-m-n ...(1)

[0241] In the above equation (1), R 1 and R 2 The monovalent hydrocarbon groups, which independently represent hydrogen atoms or are either substituted or unsubstituted, can be bonded together. The number of carbon atoms in the monovalent hydrocarbon group is preferably 1 to 12, more preferably 1 to 8. Specific examples include alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, and n-octyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl; halogen-substituted hydrocarbon groups such as chloromethyl, γ-chloropropyl, and 3,3,3-trifluoropropyl; and isocyanate groups formed by the bonding of isocyanate groups of (meth)acryloyloxy, epoxy, mercapto, amino, and isocyanate groups, such as γ-methacryloyloxypropyl, γ-epoxypropoxypropyl, 3,4-epoxycyclohexylethyl, γ-mercaptopropyl, γ-aminopropyl, and γ-isocyanate propyl.

[0242] Among these, especially in applications requiring scratch resistance and weather resistance, alkyl groups are preferred, and in applications requiring toughness and dyeability, epoxy, (meth)acryloyloxy, and isocyanurate substituted hydrocarbon groups are preferred.

[0243] R 3 Alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl, and isopropyl, are examples. Among these, considering their high reactivity in hydrolysis and condensation, and the resulting alcohol R... 3 If OH has a high vapor pressure and is easy to remove by distillation, then methyl or ethyl OH is preferred.

[0244] m and n are mutually independent integers of 0 or 1, and m+n satisfies 0, 1, or 2. Here, in equation (1), when m=0 and n=0, the raw material for the organosilicon oligomer is Si(OR) 3 )4 represents a tetraalkoxysilane or a partially hydrolyzed condensate thereof. Specific examples of tetraalkoxysilanes or their partially hydrolyzed condensates include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrabutoxysilane, tetramethoxysilane, or their partially hydrolyzed condensates.

[0245] It should be noted that the partially hydrolyzed condensate of alkoxysilanes refers to the compound obtained by adding water to at least one of the above-mentioned alkoxysilanes, stirring and heating in the presence of a catalyst, to partially hydrolyze and condense the condensate.

[0246] Organosilicon oligomers are also available as commercially available products. Examples include "MS51" and "MS56" (manufactured by Mitsubishi Chemical Co., Ltd.); "SILICATE 35", "SILICATE 45", and "FR-3" (manufactured by Tama Chemical Industry Co., Ltd.); "ESI40" and "ESI48" (manufactured by COLCOAT Co., Ltd.); "KC-89S", "KR-515", "KR-500", "X-40-9225", "X-40-9246", "X-40-9250", "KR-401N", "X-40-9227", "KR-510", "KR-9218", "KR-213", "KR-400", "X-40-2327", "KR-401", and "X-40-2761" (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0247] Furthermore, these organosilicon oligomers can be used in conjunction with curing catalysts to promote curing. As the curing catalyst, any suitable curing catalyst can be used. For example, titanium-based catalysts, such as "D-25" and "D-20" (manufactured by Shin-Etsu Chemical Co., Ltd.), are commercially available; aluminum-based catalysts, such as "DX-9740" (manufactured by Shin-Etsu Chemical Co., Ltd.), are commercially available; and phosphoric acid-based catalysts, such as "X-40-2309" (manufactured by Shin-Etsu Chemical Co., Ltd.), are commercially available.

[0248] As an acrylic resin, urethane (meth)acrylate is preferred.

[0249] In this invention, the term "(meth)acrylate" refers to one or both of "acrylate" and "methacrylate". The same applies to "(meth)acrylic acid" and "(meth)acryloyl".

[0250] (Carbamate (meth)acrylate)

[0251] Carbamate (meth)acrylates are produced by reacting isocyanate compounds with hydroxyl-containing (meth)acrylate compounds, or by reacting isocyanate compounds, polyol compounds, and hydroxyl-containing (meth)acrylate compounds. Carbamate (meth)acrylates can be used alone or in combination with two or more.

[0252] Examples of isocyanate compounds include aromatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates, among which diisocyanate compounds are preferred. Furthermore, isocyanate compounds with an isocyanurate skeleton, obtained by isocyanuric acid esterification of diisocyanate compounds, can also be used as isocyanate compounds.

[0253] Examples of the aforementioned aromatic polyisocyanates include toluene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, phenylenediamine diisocyanate, tetramethylphenylenediamine diisocyanate, phenyl diisocyanate, and naphthalene diisocyanate.

[0254] Examples of the aforementioned aliphatic polyisocyanates include hexamethylene diisocyanate, pentamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate.

[0255] Examples of the aforementioned alicyclic polyisocyanates include, for example, hydrogenated diphenylmethane diisocyanate, hydrogenated diphenylmethylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and 1,4-bis(isocyanatomethyl)cyclohexane.

[0256] Among these, aliphatic diisocyanates and alicyclic diisocyanates are preferred from the viewpoint of excellent resistance to yellowing. Furthermore, isocyanate compounds having an isocyanurate skeleton are also preferred. Similarly, isocyanate compounds having an isocyanurate skeleton obtained by isocyanuric acid esterification of aliphatic or alicyclic diisocyanates are also preferred. Among these, isocyanate compounds having an isocyanurate skeleton are more preferred.

[0257] Isocyanate compounds can be used alone or in combination with two or more.

[0258] Examples of hydroxyl-containing (meth)acrylate compounds include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and other hydroxyalkyl (meth)acrylates; 2-hydroxyethylacryloyl phosphate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, dipropylene glycol (meth)acrylate, fatty acid-modified glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, and 2-hydroxy-3-hydroxy(meth)acrylate. Monofunctional hydroxyl-containing (meth)acrylates containing one olefinic unsaturated group, such as methacryloyloxypropyl ester; difunctional hydroxyl-containing (meth)acrylates containing two olefinic unsaturated groups, such as diglyceride di(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate; and trifunctional or higher hydroxyl-containing (meth)acrylates containing three or more olefinic unsaturated groups, such as pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, and ethylene oxide-modified dipentaerythritol penta(meth)acrylate. These can be used individually or in combination of two or more.

[0259] Among these, considering excellent reactivity and versatility, as well as excellent scratch resistance of the cured coating, polyfunctional (meth)acrylate compounds containing two or more olefin unsaturated groups are preferred, with pentaerythritol tri(meth)acrylate being particularly preferred.

[0260] The above-mentioned polyol compounds are any compounds having two or more hydroxyl groups (except for the above-mentioned hydroxyl-containing (meth)acrylate compounds).

[0261] Examples of the aforementioned polyol compounds include, for example, aliphatic polyols, alicyclic polyols, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polybutadiene polyols, polyisoprene polyols, (meth)acrylic acid polyols, and polysiloxane polyols.

[0262] Examples of aliphatic polyols include, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, dimethylolpropane, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-tetramethylenediol, 1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, 1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol, pentaerythritol diacrylate, 1,9-nonanediol, 2-methyl-1,8-octanediol, etc., which contain two hydroxyl groups; sugar alcohols such as xylitol and sorbitol; and aliphatic alcohols containing three or more hydroxyl groups such as glycerol, trimethylolpropane, and trimethylolethane.

[0263] Examples of the aforementioned alicyclic polyols include cyclohexanediols such as 1,4-cyclohexanediol and cyclohexyldiethanol, hydrogenated bisphenols such as hydrogenated bisphenol A, and tricyclodecanediethanol.

[0264] Examples of polyether polyols include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polybutane glycol, polypentamethylene glycol, polyhexamethylene glycol, and other polyether polyols containing alkylene structures, as well as random or block copolymers of these polyalkylene glycols.

[0265] Examples of the aforementioned polyester polyols include, for example, condensation polymers of polyols and polycarboxylic acids, ring-opening polymers of cyclic esters (lactones), and reactants formed from the three components of polyols, polycarboxylic acids, and cyclic esters.

[0266] Examples of the aforementioned polyols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,4-tetramethylene glycol, 1,3-tetramethylene glycol, 2-methyl-1,3-trimethylene glycol, 1,5-pentamethylene glycol, neopentyl glycol, 1,6-hexamethylene glycol, 3-methyl-1,5-pentamethylene glycol, 2,4-diethyl-1,5-pentamethylene glycol, glycerol, trimethylolpropane, trimethylolethane, cyclohexanediols (such as 1,4-cyclohexanediol), bisphenols (such as bisphenol A), and sugar alcohols (such as xylitol and sorbitol).

[0267] Examples of the aforementioned polycarboxylic acids include, for instance, aliphatic dicarboxylic acids such as malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid, octanoic acid, azelaic acid, sebacic acid, and dodecanoic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, terephthalic acid, and trimellitic acid.

[0268] Examples of the aforementioned cyclic esters include propiolactone, β-methyl-δ-valerolactone, and ε-caprolactone.

[0269] Examples of polycarbonate-based polyols include, for example, reactants of polyols with carbonyl chlorides and ring-opening polymers of cyclic carbonates (alkylene carbonates, etc.).

[0270] The polyols used in the above-mentioned polycarbonate-based polyols include those exemplified in the description of the above-mentioned polyester-based polyols.

[0271] Examples of the aforementioned alkylene carbonates include, for example, ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, and hexamethylene carbonate.

[0272] It should be noted that polycarbonate-based polyols are compounds that have carbonate bonds in the molecule and hydroxyl groups at the end, and can also have ester bonds in addition to carbonate bonds.

[0273] Examples of polyolefin polyols include those with homopolymers or copolymers of ethylene, propylene, butene, etc., as a saturated hydrocarbon backbone and hydroxyl groups at the ends of their molecules.

[0274] Examples of polybutadiene-based polyols include those with butadiene copolymers as the hydrocarbon backbone and hydroxyl groups at the molecular ends.

[0275] Polybutadiene-based polyols can be hydrogenated polybutadiene polyols in which all or part of the olefinic unsaturated groups contained in their structure are hydrogenated.

[0276] Examples of polyisoprene-based polyols include those with isoprene copolymers as the hydrocarbon backbone and hydroxyl groups at the molecular ends.

[0277] Polyisoprene polyols can be hydrogenated polyisoprene polyols in which all or part of the olefinic unsaturated groups contained in their structure are hydrogenated.

[0278] Examples of the aforementioned (meth)acrylate polyols include those having at least two hydroxyl groups within the molecule of a polymer or copolymer of (meth)acrylates. Examples of such (meth)acrylates include, for instance, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, dodecyl methacrylate, octadecyl methacrylate, and other alkyl methacrylates. Furthermore, copolymers of (meth)acrylates with hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, and other hydroxyalkyl methacrylates may also be used.

[0279] Examples of polysiloxane-based polyols include dimethyl polysiloxane polyol and methylphenyl polysiloxane polyol.

[0280] The above-mentioned polyol compounds can be used in one or in combination of two or more.

[0281] In the addition reaction of the above isocyanate compounds with hydroxyl-containing (meth)acrylate compounds, or the addition reaction of isocyanate compounds, hydroxyl-containing (meth)acrylate compounds, and polyols, the reaction is terminated at the time point when the residual isocyanate group content in the reaction system becomes less than 0.5% by mass, to obtain urethane (meth)acrylate.

[0282] When the urethane (meth)acrylate contains a substance obtained by reacting an isocyanate compound, a polyol compound, and a hydroxyl-containing (meth)acrylate compound, it is preferably manufactured by reacting an isocyanate-containing reaction product obtained by reacting an isocyanate compound with a polyol compound, or by reacting a mixture of the reaction product and the isocyanate compound with a hydroxyl-containing (meth)acrylate compound.

[0283] The urethane (meth)acrylate obtained by such a reaction can be a mixture of substances formed by reacting isocyanate compounds and hydroxyl-containing (meth)acrylate compounds with substances formed by reacting isocyanate compounds, polyol compounds and hydroxyl-containing (meth)acrylate compounds.

[0284] In the reaction of isocyanate compounds with hydroxyl-containing (meth)acrylate compounds, a catalyst is preferred for promoting the reaction. Examples of such catalysts include: organometallic compounds such as dibutyltin dilaurate, dibutyltin diacetate, trimethyltin hydroxide, tetra-n-butyltin, zinc diacetylacetonate, zirconium tri(acetylacetonate)ethylacetoacetate, and zirconium tetraacetylacetonate; metal salts such as tin octenate, zinc hexanoate, zinc octenate, zinc stearate, zirconium 2-ethylhexanoate, cobalt naphthenate, stannous chloride, stannous chloride, and potassium acetate; and triethylamine, triethylenediamine, benzyldiethylamine, 1,4-diazabicyclo[2.2.2]octane, and 1,8-diazabicyclo[5.4.0]eleven. Amine catalysts such as carbene, N,N,N',N'-tetramethyl-1,3-butanediamine, N-methylmorpholine, and N-ethylmorpholine; bismuth nitrate, bismuth bromide, bismuth iodide, and bismuth sulfide; in addition, organic bismuth compounds such as dibutylbismuth dilaurate and dioctylbismuth dilaurate; bismuth salts of 2-ethylhexanoate, bismuth cycloalkanoates, bismuth isodecanate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bismuth dineodecanate, bismuth disalicylate, and bismuth digallate, etc., are used. Among them, dibutyltin dilaurate and 1,8-diazabicyclo[5.4.0]undecene are preferred. They can be used alone or in combination of two or more.

[0285] Furthermore, in the reaction of isocyanate compounds with hydroxyl-containing (meth)acrylate compounds, organic solvents that do not have functional groups that react with isocyanate groups can be used, such as esters like ethyl acetate and butyl acetate; ketones like methyl ethyl ketone and methyl isobutyl ketone; and aromatic organic solvents like toluene and xylene. In addition, polymerization inhibitors can also be used appropriately.

[0286] Uraffinate (meth)acrylates are reaction products of hydroxyl-containing (meth)acrylate compounds and isocyanate compounds, or hydroxyl-containing (meth)acrylate compounds, isocyanate compounds, and polyol compounds. They can also be generated by reacting a mixture of hydroxyl-containing and non-hydroxyl-containing (meth)acrylates with isocyanate compounds. Alternatively, they can be generated by reacting a mixture of hydroxyl-containing and non-hydroxyl-containing (meth)acrylates, isocyanate compounds, and polyol compounds. In this case, the non-hydroxyl-containing (meth)acrylates remain as unreacted material, but it is preferable to include them directly in the cured resin composition for use.

[0287] Furthermore, in the reactions of the isocyanate compounds and hydroxyl-containing (meth)acrylate compounds described above, as mentioned above, part or all of the isocyanate compounds may be reaction products of the isocyanate compounds and polyol compounds.

[0288] The (meth)acryloyl equivalent of the urethane (meth)acrylate is, for example, 120 g / eq or more and 250 g / eq or less, preferably 135 g / eq or more and 220 g / eq or less, and more preferably 150 g / eq or more and 200 g / eq or less. If the (meth)acryloyl equivalent of the urethane (meth)acrylate is within the above range, a cured resin layer (B) with a suitable crosslinking density can be formed by adjusting the crosslinking points. By forming the cured resin layer (B) in a laminate or similar composite structure, a suitable hardness can be imparted.

[0289] When the cured resin composition (b) contains urethane (meth)acrylate, the proportion of urethane (meth)acrylate in the cured resin composition (b) relative to the total amount of solid components is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more.

[0290] In this invention, it is preferable to prepare the base polymer by polymerizing the above-mentioned urethane (meth)acrylate alone, or by mixing and polymerizing two or more of them. The base polymer is preferably dissolved or dispersed in a solvent or the like described later, coated onto the cured resin layer (A), and cured to form the cured resin layer (B).

[0291] (solvent)

[0292] The curing resin composition (b) is preferably solvent-free, but it can also be prepared as a coating liquid by dilution with a solvent. The curing resin composition (b) can be prepared as a cured resin layer (B) by applying it as a liquid coating liquid onto the cured resin layer (A) and drying and curing it. The components constituting the curing resin composition (b) can be dissolved in a solvent or dispersed in a solvent.

[0293] Here, water, or organic solvents such as ester solvents, ether solvents, and alcohol solvents are preferred as solvents used.

[0294] Specific examples of organic solvents include ether solvents such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether (PGM), anisole, and phenethyl ether; ester solvents such as ethyl acetate, butyl acetate, isopropyl acetate, and ethylene glycol diacetate; amide solvents such as dimethylformamide, diethylformamide, dimethylacetamide, and N-methylpyrrolidone; cellosol solvents such as methyl cellosol, ethyl cellosol, and butyl cellosol; alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol; and halogen solvents such as dichloromethane and chloroform. These organic solvents can be used alone or in combination with two or more.

[0295] There is no particular limitation on the amount of solvent used, and it is appropriately determined taking into account the coatability of the prepared cured resin composition (b), the viscosity and surface tension of the liquid, and the compatibility of the solid components. The cured resin composition (b) is prepared using the aforementioned solvent as a coating liquid with a solid component concentration preferably of 15 to 80% by mass, more preferably 20 to 70% by mass.

[0296] It should be noted that the "solid component" in this cured resin composition (b) refers to the component other than the solvent, which is a volatile component. It includes not only solid components but also semi-solid and viscous liquid components.

[0297] (Other ingredients)

[0298] Without prejudice to the spirit of the invention, the cured resin composition (b) may contain photopolymerizable compounds such as (meth)acrylates in addition to the above-described contents.

[0299] Furthermore, various additives may be appropriately incorporated into the cured resin composition (b) as needed, without prejudice to the spirit of the invention. As additives, for example, photoinitiators, light stabilizers, antioxidants, antistatic agents, organic pigments, organic particles, inorganic particles, refractive index modifiers, flame retardants, leveling agents, dispersants, thixotropic agents (thickeners), defoamers, etc., may be used in combination.

[0300] (Photoinitiator)

[0301] In the case that the cured resin composition (b) is a photocurable resin composition, it is preferable to contain a photoinitiator to improve curability. The photoinitiator is a photopolymerization initiator, and known photoinitiators can be used. Examples of photopolymerization initiators include photoradical generators and photoacid generators.

[0302] Photoradical generators that can be used in the photopolymerization initiator of this cured resin composition (b) include, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and other benzoin and their alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenylacetophenone [e.g., trade name "Omnirad (registered trademark) 651", manufactured by IGM RESINS], 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone [e.g., trade name "Omnirad (registered trademark) 184", manufactured by IGM RESINS], 2-hydroxy-2-methyl-1-phenylpropane-1-one [e.g., trade name "Omnirad (registered trademark) 1173", manufactured by IGM RESINS], 2-hydroxy-2-methyl-1-phenylpropane-1-one [e.g., trade name "Omnirad (registered trademark) 1173", manufactured by IGM RESINS], and 2-hydroxy-2-methyl-1-phenylpropane-1-one [e.g., trade name "Omnirad (registered trademark) 1173", manufactured by IGM RESINS]. [Manufactured by RESINS], 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanoyl)benzyl)phenyl)-2-methylpropane-1-one [e.g., trade name "Omnirad (registered trademark) 127", manufactured by IGM RESINS], 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one [e.g., trade name "Omnirad (registered trademark) 2959", manufactured by IGM RESINS], 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one [e.g., trade name "Omnirad (registered trademark) 907", manufactured by IGM RESINS] Alkyl phenyl ketones such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone; phosphine oxides such as 2,4,6-trimethylbenzoyl diphenylphosphine oxide [e.g., trade name "Omnirad (registered trademark) TPO", manufactured by IGM RESINS] and bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide [e.g., trade name "Omnirad (registered trademark) 819", manufactured by IGM RESINS]; anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, and 2-pentylanthraquinone; benzophenone and its various derivatives; formic acid derivatives such as methyl benzoylformate and ethyl benzoylformate, etc.

[0303] These photoradical generators can be used alone or in combination of two or more.

[0304] Among these photoradical generators, from the viewpoint of the lightfastness of the cured product, alkyl phenyl ketones, phosphine oxides, and formic acid derivatives are preferred, with 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-1-(4-(4-(2-hydroxy-2-methylpropanoyl)benzyl)phenyl)-2-methylpropane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, and methyl benzoylformate being particularly preferred.

[0305] As a photoacid generator, known photoacid generators can be used. Among them, diaryl iodide salts and triaryl sulfonate salts are preferred from the viewpoints of curing properties and acid generation efficiency. Specific examples of photoacid generators include anionic salts of di(alkyl-substituted)phenyliodonium (specifically, PF6 salt, SbF5 salt, tetra(perfluorophenyl)borate, etc.).

[0306] As a specific example of anionic salts of dialkyl-substituted phenyliodonium, PF6 salts of dialkylphenyliodonium [trade name "Omniad (registered trademark) 250", manufactured by IGM RESINS] are particularly preferred.

[0307] These photoacid-producing agents can be used alone or in combination of two or more.

[0308] From the viewpoint of improving curability, the content of photoinitiator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and particularly preferably 1 part by mass or more, relative to the total 100 parts by mass of compounds having (meth)acryloyl groups in the cured resin composition (b). On the other hand, from the viewpoint of maintaining the stability of the coating liquid when the cured resin composition (b) is prepared into a solution and the viewpoint of the planarity of the cured coating film, it is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and particularly preferably 5 parts by mass or less.

[0309] (Refractive index adjuster)

[0310] From the perspective of further improving the structural color rendering properties, it is also preferable to add a refractive index modifier to the cured resin composition (b). As a method for adjusting the refractive index, for example, one method is to lower the refractive index of the cured resin layer (B) to increase the refractive index difference with the cured resin layer (A). In this case, low-refractive-index microparticles can be used as the refractive index modifier. By including low-refractive-index microparticles in the cured resin composition (b) to adjust the refractive index of the cured resin layer (B), and increasing the refractive index difference with the cured resin layer (A), the structural color rendering properties of the laminated film can be further improved.

[0311] Examples of low refractive index particles mentioned above include hollow silica particles and hollow acrylic particles.

[0312] From the perspective of having a lower refractive index and being able to penetrate the voids of the cured resin layer (A), hollow silica particles with a high hollowness ratio and a small diameter are preferred. It should be noted that the refractive index of the low refractive index particles is usually 1.7 or less, and preferably 1.5 or less.

[0313] The average particle size of the aforementioned microparticles is preferably 10 nm to 100 nm, particularly preferably 20 nm to 90 nm, and even more preferably 40 nm to 80 nm. If the average particle size is too small, the hollowness decreases and the refractive index of the microparticles themselves increases. Furthermore, if the average particle size is too large, it cannot enter the voids of the cured resin layer (A), and the effect of refractive index adjustment cannot be obtained.

[0314] Here, the average particle size refers to the value measured by methods such as laser diffraction / scattering, dynamic light scattering (DLS), centrifugal sedimentation, particle trajectory analysis (PTA), and scanning electron microscopy (SEM). As long as it is a commercially available product, the catalog value can be used.

[0315] The content of the aforementioned microparticles depends on the relationship between the microparticles (X) in the cured resin layer (A) and the diameter of the aforementioned microparticles. For example, relative to 100 parts by mass of microparticles (X) in the cured resin layer (A), it is preferably 1 to 50 parts by mass, particularly preferably 5 to 30 parts by mass, and even more preferably 7 to 20 parts by mass. Whether the content is too low or too high, there is a tendency to make it difficult to obtain the effect of improving the color development of the laminate structure.

[0316] <Thickness of this cured resin layer (B)>

[0317] The thickness of the cured resin layer (B) is preferably such that it fully covers the cured resin layer (A) after coating and curing. That is, if it has a thickness of 1 μm to 10 μm from the surface of the cured resin layer (A), the cured resin layer (A) can be protected, and the structural color development and the peelability of the substrate film when making a transfer laminate can be fully obtained. Therefore, it is preferred, more preferably 2 μm to 8 μm, and particularly preferably 3 μm to 7 μm.

[0318] Here, the thickness of the cured resin layer (B) is the thickness after the cured resin composition (b) is applied and cured in the method for forming the cured resin layer (B) described later.

[0319] <Refractive index of this cured resin layer (B)>

[0320] The refractive index of the cured resin layer (B), as measured by the method described in the embodiments described later, is preferably 1.55 or less, more preferably 1.30 to 1.55, and particularly preferably 1.35 to 1.54. If the refractive index of the cured resin layer (B) is within the above range, good structural color development can be exhibited.

[0321] <Storage modulus of this cured resin layer (B)>

[0322] Especially when considering the difference in water droplet contact angle between the cured resin layer (B) and the resin layer (C) described later to improve peelability, the storage modulus of the cured resin layer (B) at 25°C, measured by the method described in the following embodiments, is preferably 1.0 × 10⁻⁶. 3 Pa ~ 2.0 × 10 8 Pa, preferably 1.0 × 10 Pa. 5 Pa ~ 1.0 × 10 8 Pa.

[0323] If the storage modulus of the cured resin layer (B) is below the aforementioned lower limit, there is a tendency for the peelability between the substrate film and the cured resin layer (A) to deteriorate when the substrate film is peeled off after the laminated film for transfer is transferred to the substrate. On the other hand, if the storage modulus of the cured resin layer (B) is above the aforementioned upper limit, there is a tendency for the cured resin layer (B) to crack and deteriorate in appearance or have poor structural color development when the substrate film is peeled off after the laminated film for transfer is transferred to the substrate.

[0324] The glass transition temperature (Tg) of the cured resin layer (B), as measured by the method described in the embodiments described later, is preferably -130°C or higher, more preferably -100°C to 0°C, and particularly preferably -90°C to -10°C. If the Tg of the cured resin layer (B) is within the above range, a transfer laminate with excellent peelability, structural color development, and appearance can be obtained.

[0325] If the Tg of the cured resin layer (B) is below the aforementioned lower limit, there is a tendency for the peelability between the substrate film and the cured resin layer (A) to deteriorate when the substrate film is peeled off after the laminated film for transfer is transferred to the substrate. On the other hand, if the Tg of the cured resin layer (B) is above the aforementioned upper limit, there is a tendency for the cured resin layer (B) to crack and deteriorate in appearance or have poor structural color development when the substrate film is peeled off after the laminated film for transfer is transferred to the substrate.

[0326] In order to form such a cured resin layer (B), the cured resin composition (b) used in the formation of the cured resin layer (B) preferably contains a polyether-based urethane (meth)acrylate resin with a low storage modulus at room temperature (25°C) and an organosilicon resin, and more preferably does not contain a (meth)acrylate compound with high Tg.

[0327] <Method for forming the cured resin layer (B)>

[0328] The cured resin layer (B) can be formed by coating the cured resin composition (b) onto the surface of the cured resin layer (A) formed on the substrate film to form a coating layer, and then curing the coating layer.

[0329] As a method for coating the cured resin composition (b), conventionally known coating methods such as air knife coating, doctor blade coating, bar coating, wire bar coating, doctor blade coating, extrusion coating, dip coating, reverse roller coating, transfer roller coating, gravure coating, kissing roller coating, cast coating, spray coating, curtain coating, calendering coating, and extrusion coating can be used.

[0330] There are no particular limitations on drying conditions; it can be carried out at room temperature or by heating. When heating is used, higher heating temperatures tend to increase the coating strength, but on the other hand, they tend to decrease the reflectivity.

[0331] Considering the heat resistance of the particles (X) in the cured resin layer (A) that forms the lower layer of the cured resin layer (B), if the temperature exceeds 130°C, the particles (X) tend to begin to melt easily. Therefore, the heating temperature is preferably below 130°C, more preferably 20°C to 130°C, even more preferably 30°C to 120°C, and particularly preferably in the range of 40°C to 110°C.

[0332] Furthermore, the drying time is not particularly limited as long as it is within the range that ensures the coating strength of the cured resin composition (b), for example, 10 seconds to 30 minutes, preferably 15 seconds to 10 minutes.

[0333] That is, the transfer laminate is preferably manufactured according to the manufacturing method of the transfer laminate of the present invention, which includes a heat treatment step, wherein the heat treatment step is a step of heating the cured resin composition (b) coated on the cured resin layer (A) formed on the substrate film at 25°C to 120°C for 10 seconds to 30 minutes, preferably 10 seconds to 10 minutes, and particularly preferably 15 seconds to 5 minutes to form the cured resin layer (B).

[0334] The curing method of this curing resin composition (b) can be appropriately selected according to the curing mechanism of this curing resin composition (b). If this curing resin composition (b) is a thermosetting resin composition, it can be cured simply by heating. In addition, if it is a photocurable resin composition, it can be cured simply by irradiating it with active energy rays.

[0335] Among the active energy rays that can be used to cure the present curing resin composition (b) are ultraviolet rays, electron beams, X-rays, infrared rays, and visible light. From the viewpoint of curability and prevention of resin degradation, ultraviolet rays and electron beams are preferred.

[0336] From the viewpoints of molding time and productivity, as well as preventing thermal shrinkage and thermal degradation of the components caused by heating, the curing method of this curing resin composition (b) is preferably performed by irradiation with active energy rays. Irradiation with active energy rays can be performed from either side, from the side of the substrate film, or from the opposite side of the substrate film, but usually from the coated side of this curing resin composition (b).

[0337] When the cured resin layer (B) is formed, the cured resin composition (b) is cured by ultraviolet irradiation. Various ultraviolet irradiation devices can be used as its light source, such as xenon lamps, high-pressure mercury lamps, metal halide lamps, LED-UV lamps, etc.

[0338] Cumulative light intensity of active energy rays (unit: mJ / cm) 2 The preferred value is 20 mJ / cm. 2 ~250mJ / cm 2 From the viewpoint of curability of the present curing resin composition (b) and flexibility of the cured product (cured film), 40 mJ / cm is more preferable. 2 ~250mJ / cm 2 From the viewpoint of the planarity of the cured resin layer (B), a value of 80 mJ / cm is more preferable. 2 ~250mJ / cm 2 The scope should be appropriately determined.

[0339] That is, the transfer film is preferably manufactured according to the manufacturing method of the transfer film of the present invention, which includes an irradiation treatment step, wherein the irradiation treatment step is performed by irradiating the film with active energy rays at a cumulative light intensity of 250 mJ / cm. 2 The process of forming the cured resin layer (B) by irradiating the cured resin composition (b) coated on the cured resin layer (A) formed on the substrate film under the following conditions.

[0340] Furthermore, when forming this cured resin layer (B), if the cured resin composition (b) is cured by electron beam irradiation, various electron beam irradiation devices can be used. The electron beam irradiation dose (Mrad) is typically 0.5Mrad to 20Mrad, and from the viewpoints of curability of the cured resin composition (b), flexibility of the cured product, and prevention of damage to the substrate, it is preferably appropriately determined in the range of 1.0Mrad to 15Mrad.

[0341] <Cascading Method>

[0342] The laminated film of the present invention can be any structure in which the cured resin layer (B) covers the cured resin layer (A). The cured resin layer (A) and the cured resin layer (B) can be laminated sequentially. For example, a structure in which the cured resin layer (B) contains the cured resin layer (A), or where the cured resin layer (B) partially permeates into the cured resin layer (A), is also included in the present invention. Where such a lamination method is possible, it is not necessarily limited to a scheme of sequentially laminating the cured resin layer (A) and the cured resin layer (B) in stages. Furthermore, the interface between the two layers may not be clearly defined. For example, in one layer, the surface of the cured resin layer (C) is the cured resin layer (B), and the surface of the substrate film is the cured resin layer (A). As long as it is substantially a laminated structure of the cured resin layer (A) and the cured resin layer (B), it is included in the present invention. Considering the heat resistance and strength of the cured resin layer (A) as a structural color layer, it is preferable to have a structure in which the cured resin layer (B) is impregnated in the cured resin layer (A) and covered.

[0343] <Resin Layer (C)>

[0344] The resin layer (C) (hereinafter sometimes referred to as "this resin layer (C)") is a sealing layer, wherein, from the viewpoint that it can be easily and firmly welded by heating, it is preferably a heat-sealing layer.

[0345] When the resin layer (C) is a heat-sealing layer, there is no particular limitation on the heating and welding temperature. From the viewpoint of the roll shape's anti-adhesion properties and the adaptability to subsequent processing, it is preferably 70°C to 250°C, and particularly preferably around 100°C to 220°C.

[0346] There are no particular limitations on the resin constituting this resin layer (C), and examples include polyester resins such as polyethylene terephthalate resins and polybutylene terephthalate resins, polyolefin resins such as polyethylene resins and polypropylene resins, and acrylic resins, which are commonly used in the sealing layer of transfer films. Among these, polyester resins are preferred from the perspective of good adhesion to the cured resin layer (B), especially good adhesion to urethane (meth)acrylate resins suitable for use in the cured resin layer (B).

[0347] Furthermore, from the viewpoint of adhesion to the adhered object and anti-adhesion of the roll shape, the resin used in this resin layer (C) preferably has a Tg of 30 to 120°C, more preferably 40 to 110°C, and particularly preferably 50 to 100°C.

[0348] As the resin composition (c) for forming such a heat-sealing layer, namely the resin layer (C), commercially available products can be used. Examples of commercially available polyester resin compositions for heat-sealing layer formation include Henkel Japan's "HS1138", Mitsubishi Chemical's "TP-235", and Mitsubishi Chemical's "TP-294". Furthermore, examples of polyolefin resin compositions include Mitsubishi Chemical's "SURFLEN P-1000", Mitsui Chemicals' "UNISTOLE R-200X", Mitsui Chemicals' "UNISTOLE R-303XE", and Mitsui Chemicals' "UNISTOLE R-200EM".

[0349] <Thickness of this resin layer (C)>

[0350] From the viewpoint of adhesive strength to the adhered objects, the thickness of this resin layer (C) is preferably 0.5 μm to 5.0 μm, more preferably 1.0 μm to 4.0 μm, and even more preferably 3 μm. Here, the thickness of this resin layer (C) refers to the thickness after the aforementioned resin composition (c) for forming this resin layer (C) is applied and dried.

[0351] <Method for forming this resin layer (C)>

[0352] This resin layer (C) can be formed by coating the surface of the cured resin layer (B) formed on the cured resin layer (A) on the substrate film with a resin composition (c) (hereinafter, sometimes referred to as "this resin composition (c)") diluted with a solvent as needed, and then drying and heat-curing the coating layer.

[0353] As a method for coating the resin composition (c), conventionally known coating methods such as air knife coating, doctor blade coating, bar coating, wire bar coating, doctor blade coating, extrusion coating, dip coating, reverse roller coating, transfer roller coating, gravure coating, kissing roller coating, cast coating, spray coating, curtain coating, calendering coating, and extrusion coating can be used.

[0354] Taking into account the heat resistance of the particles (X) in the cured resin layer (B) below the resin layer (C) and the cured resin layer (A) below it, the drying / heating temperature is preferably 25°C to 200°C, more preferably 25°C to 180°C, and particularly preferably in the range of 40°C to 160°C.

[0355] It should be noted that the resin layer (C) used as the heat-sealing layer can also improve peelability without depending on the surface roughness of the substrate film by using a resin material with a lower glass transition temperature (Tg), using a roller transfer printing machine, or adjusting heat sealing conditions such as pressing temperature / pressing pressure.

[0356] <The ratio of the combined thickness of the cured resin layer (A) and the cured resin layer (B) to the thickness of the resin layer (C)>

[0357] The ratio of the combined thickness of the cured resin layer (A) and the cured resin layer (B) to the thickness of the resin layer (C) ((thickness of cured resin layer (A) + thickness of cured resin layer (B)) / thickness of resin layer (C)) is preferably in the range of 10:1 to 10:5. If this thickness ratio is less than the lower limit mentioned above, there is a tendency for insufficient heat-sealing strength and reduced peelability of the substrate film of the transfer laminate. Furthermore, if this thickness ratio exceeds the upper limit mentioned above, there is a tendency for adhesion to easily occur in the roll shape.

[0358] The thickness ratio is more preferably 10:1.5 to 10:4, and even more preferably 10:2 to 10:3.

[0359] <Difference in water droplet contact angle between this cured resin layer (B) and this resin layer (C)>

[0360] As an example of a preferred embodiment of the transfer film, a transfer film in which the water droplet contact angle difference between the surface of the cured resin layer (B) and the surface of the resin layer (C) is 0 to 35° can be cited.

[0361] If the water droplet contact angle difference between the cured resin layer (B) and the resin layer (C) is 35° or less, the adhesion between the cured resin layer (B) and the resin layer (C) is good. When this transfer film is transferred to the substrate, even if stress is applied when peeling off the substrate film, interfacial delamination between the cured resin layer (B) and the resin layer (C) will be prevented. From this point of view, the water droplet contact angle difference is more preferably 0 to 30°, and even more preferably 0 to 25°.

[0362] The water droplet contact angle of the surface of the cured resin layer (B) refers to the water droplet contact angle of the surface of the cured resin layer (B) on the side of the resin layer (C), and the water droplet contact angle of the surface of the resin layer (C) refers to the water droplet contact angle of the surface of the resin layer (C) on the side of the cured resin layer (B). Both are measured by the methods described in the embodiments described later.

[0363] It should be noted that the preferred range for the water droplet contact angle on the surface of each layer is as follows.

[0364] From the viewpoint of improving the interlayer adhesion, the water droplet contact angle of the surface of the cured resin layer (B) on the side of the resin layer (C) is preferably 50° to 90°, and particularly preferably 55° to 85°.

[0365] To form this cured resin layer (B) with such a water droplet contact angle, for example, a method can be described using a cured resin composition (b) containing urethane (meth)acrylate resin.

[0366] Furthermore, from the viewpoint of improving the interlayer adhesion, the water droplet contact angle of the surface of the cured resin layer (B) of the resin layer (C) is preferably 50° to 90°, and particularly preferably 55° to 85°.

[0367] To form this resin layer (C) with such a water droplet contact angle, for example, a method of using a polyester resin with a low Tg as the resin layer (C) can be cited.

[0368] <Cascading Method>

[0369] The above description describes the sequential lamination of the cured resin layer (A), the cured resin layer (B), and the resin layer (C). However, in the transfer film of the present invention, any configuration in which the cured resin layer (B) covers the cured resin layer (A) is acceptable. For example, a configuration in which the cured resin layer (B) contains the cured resin layer (A) is also included in the present invention. By adopting such a configuration, an apparent double-layer structure is formed, resulting in excellent coating strength, color development, and adhesion to the resin layer (C). While such a lamination method is possible, it is not necessarily limited to a stepwise sequential lamination of the cured resin layer (A) and the cured resin layer (B). Furthermore, the interface between the two layers may not be clearly defined. For example, a layer may have the cured resin layer (B) on its surface side and the cured resin layer (A) on its substrate film side; as long as the configurations are substantially the same, this is included in the present invention.

[0370] Furthermore, the substrate film, the cured resin layer (A), the cured resin layer (B), and the resin layer (C) can be arranged sequentially, and other functional layers can be sandwiched between each layer.

[0371] In addition, the transfer film can also have a release paper laminated on the resin layer (C) that serves as its sealing layer, and the release paper can be peeled off during use to transfer the film to the substrate.

[0372] <Release Layer>

[0373] In order to improve the peelability of the substrate film, the transfer laminate can have a release layer sandwiched between the substrate film and the cured resin layer (A).

[0374] The release layer can be formed by coating a release agent composition and then drying it.

[0375] Release agents that form the release layer are typically made from long-chain alkyl compounds, waxes, fluorinated compounds, or organosilicon compounds.

[0376] More specifically, the following substances can be listed.

[0377] Long-chain alkyl compounds refer to compounds having straight-chain or branched alkyl groups with 6 or more carbon atoms, preferably 8 or more, and more preferably 12 or more. Specific examples are not particularly limited, but include polyethylene compounds containing long-chain alkyl groups, acrylic compounds containing long-chain alkyl groups, polyester compounds containing long-chain alkyl groups, amine compounds containing long-chain alkyl groups, ether compounds containing long-chain alkyl groups, and quaternary ammonium salts containing long-chain alkyl groups. High molecular weight compounds are preferred when considering heat resistance and staining resistance. Furthermore, polyethylene compounds containing long-chain alkyl groups are preferred when considering release properties and ease of handling.

[0378] Wax refers to waxes selected from natural waxes, synthetic waxes, and waxes containing these.

[0379] Natural waxes refer to plant-based waxes, animal-based waxes, mineral-based waxes, and petroleum waxes.

[0380] Plant-based waxes include candelilla wax, carnauba wax, rice bran wax, wood wax, and jojoba oil.

[0381] Examples of animal-derived waxes include beeswax, lanolin, and whale wax.

[0382] As mineral-based waxes, examples include lignite wax, ozokerite, and ceresin.

[0383] As petroleum waxes, examples include paraffin wax, microcrystalline wax, and petroleum jelly.

[0384] Synthetic waxes include synthetic hydrocarbons, modified waxes, hydrogenated waxes, fatty acids, amides, amines, imides, esters, and ketones. Among synthetic hydrocarbons, Fischer-Tropsch wax (also known as Sasol wax) and polyethylene wax are well-known, but also include polymers with low molecular weight (specifically, polymers with a viscosity number average molecular weight of 500 to 20,000). These include polypropylene, ethylene-acrylic acid copolymers, polyethylene glycol, polypropylene glycol, and block or graft compounds of polyethylene glycol and polypropylene glycol. Modified waxes include lignite wax derivatives, paraffin wax derivatives, and microcrystalline wax derivatives. Here, derivatives refer to compounds obtained through any of the following treatments: refining, oxidation, esterification, saponification, or a combination thereof. Hydrogenated waxes include cured castor oil and cured castor oil derivatives. Among these waxes, synthetic hydrocarbon systems are preferred from the viewpoint of performance stability and ease of acquisition, and oxidized polyethylene wax and oxidized polypropylene wax are more preferred.

[0385] Fluorine compounds are compounds containing fluorine atoms. From the perspective of the coating appearance in online coating, organic fluorine compounds are preferred, such as compounds containing perfluoroalkyl groups, polymers of olefin compounds containing fluorine atoms, and aromatic fluorine compounds such as fluorinated benzene. Considering heat resistance and staining properties, polymeric compounds are preferred.

[0386] Such a release agent composition is preferably applied at a coating amount of 0.05 g / m². 2 ~0.20g / m 2 The coating is applied to the substrate film by sequentially forming the cured resin layer (A), the cured resin layer (B), and the resin layer (C) on the substrate film on which the release layer is formed.

[0387] <Slippery Layer>

[0388] This transfer film may have a slip-resistant layer. It is preferable that the slip-resistant layer is located on the side of the substrate film opposite to the side where the cured resin layer (A) and the cured resin layer (B) are located. By providing a slip-resistant layer to this transfer film, its sliding properties are improved, as are its roll-wrap and processability.

[0389] The slip layer is formed, for example, from a slip layer composition comprising an adhesive resin, a crosslinking agent, and particles.

[0390] Examples of adhesive resins include polyester resins, acrylic resins, urethane resins, polyethylene-based resins such as polyvinyl alcohol, polyalkylene glycols, polyalkylimides, methylcellulose, hydroxycellulose, and starches. Among these, from the viewpoint of improving adhesion to the substrate film, polyester resins, acrylic resins, and urethane resins are preferred, and polyester resins and acrylic resins are more preferred. These adhesive resins can be used alone or in combination of two or more.

[0391] The content of the adhesive resin in the slip layer composition is, for example, 20% to 90% by mass, preferably 30% to 80% by mass, based on the solid content.

[0392] Various known crosslinking agents can be used, such as oxazoline compounds, melamine compounds, epoxy compounds, isocyanate compounds, carbodiimide compounds, and silane coupling compounds. It should be noted that the oxazoline compound can be an acrylic polymer having an oxazoline group. Among these, melamine compounds, oxazoline compounds, and epoxy compounds are preferred. These crosslinking agents can be used individually or in combination of two or more.

[0393] The content of the crosslinking agent in the slip layer composition is, for example, 5% to 50% by mass, preferably 10% to 40% by mass, based on the solid content.

[0394] Specific examples of particles used in the slip-resistant layer include silica, alumina, kaolin, calcium carbonate, and organic polymer particles. From the viewpoint of transparency, silica is preferred. From the viewpoint of not impairing the surface smoothness of the substrate film and ensuring good slip resistance, the average particle size is preferably 0.005 μm to 1.0 μm, more preferably 0.01 μm to 0.8 μm, and even more preferably in the range of 0.01 μm to 0.6 μm. The particle content in the slip-resistant layer composition, based on solid content, is, for example, 1% to 20% by mass, preferably 3% to 15% by mass. The slip-resistant layer may use one type of particle alone or in combination of two or more types.

[0395] The slip-resistant layer composition is generally preferably diluted with water, an organic solvent, or a mixture thereof. The slip-resistant layer is preferably formed by applying the diluted slip-resistant layer composition as a coating liquid to the surface of the substrate film and then drying it. Coating is preferably performed using conventionally known methods.

[0396] The thickness of the slip layer is typically in the range of 0.003 μm to 1 μm, preferably 0.005 μm to 0.6 μm, and more preferably 0.01 μm to 0.4 μm. By setting the thickness to 0.003 μm or more, the particles contained in the slip layer can be sufficiently retained, thus imparting slip properties. Furthermore, by setting it to 1 μm or less, it is less likely to cause deterioration in appearance or adhesion.

[0397] <Coating>

[0398] The formation of the release layer and the slip layer on the surface of the substrate film is preferably performed online. Online coating is preferably performed on the substrate film during the substrate film production line. For example, in the case of a biaxially stretched film, after applying a coating liquid for forming at least one of the release layer and the slip layer at the end of the longitudinal stretching stage, it is preferable to allow the coating liquid to dry and cure in subsequent substrate film manufacturing processes.

[0399] Properties of laminated films for transfer printing

[0400] (Structural colorimetry)

[0401] The microparticles (X) used in this invention exhibit structural colorimetry. For example... Figure 1 As shown, structural coloration refers to the expression of structural color when particles of uniform size are arranged regularly.

[0402] Structure-based color rendering refers to an angle-dependent color rendering phenomenon where the color appears to change depending on the viewing angle due to optical physical phenomena such as interference and scattering that occur based on the wavelength of light caused by the regular arrangement of particles in the crystal structure.

[0403] In other words, structural color refers to color development based on light interference and reflection (Bragg diffraction) originating from periodic microstructures (nm level). It has the following advantages: it develops color without using pigments or dyes, and although it is non-metallic, it can achieve a metallic luster.

[0404] Since the color of a structure depends on the nature of light, it is expressed not only in the visible light region, but also in the ultraviolet and infrared regions.

[0405] In this invention, from the viewpoint of utilizing structural color to enhance the decorative properties of the film, it is preferable to exhibit structural color in the visible light region.

[0406] Here, the visible light region represents wavelengths from 360nm to 830nm, the ultraviolet region represents wavelengths from 200nm to 359nm, and the infrared region represents wavelengths from 831nm to 2500nm.

[0407] In this invention, as an evaluation of structural color rendering, as described in the following embodiments, a visual sensory evaluation is performed on the surface of the transfer laminate after the transfer laminate has been transferred to the substrate and the substrate film has been peeled off, namely the surface of the cured resin layer (A), both when viewed from the front and when viewed at an angle of 45 degrees.

[0408] <Application>

[0409] The transfer laminate of the present invention is preferably used for decorative applications such as decorative sheets. In addition, it can also be used for various applications such as industrial materials, optical applications, and packaging materials.

[0410] <Method for manufacturing the laminated film for this transfer printing>

[0411] This transfer laminate can be manufactured through the following steps: a heat treatment step of heating the cured resin composition (a) coated on the substrate film to form the cured resin layer (A); a heat treatment step of heating the cured resin composition (b) for forming the cured resin layer (B) coated on the cured resin layer (A) to form the cured resin layer (B), or an irradiation step of irradiating the cured resin composition (b) for forming the cured resin layer (B) coated on the cured resin layer (A) with active energy rays to form the cured resin layer (B); and a step of coating the cured resin layer (B) with a resin composition (c) for forming the resin layer (C) and drying it to form the resin layer (C).

[0412] The processing conditions for each step are as described in the instructions for each layer.

[0413] In the manufacture of this transfer film, in the heat treatment process of heating the curing resin composition (b) for forming the curing resin layer (B) to form the curing resin layer (B), the heating temperature is preferably 130°C or less.

[0414] <Transfer Method>

[0415] The transfer method of the present invention is to press the resin layer (C) of the transfer laminated film against the substrate and then peel off the substrate film to transfer the cured resin layer (A) and the cured resin layer (B) to the substrate via the resin layer (C).

[0416] When the resin layer (C) is a heat-sealing layer, the heating and pressing conditions during the transfer vary depending on the type of resin composition used in the resin layer (C), but are generally preferably carried out at a heating temperature of 160°C to 240°C and a pressing pressure of 0.1 MPa to 0.2 MPa.

[0417] In the transfer method of the present invention, there are no particular limitations on the material of the substrate to which the transfer film is adhered, and examples include films and molded articles formed of polyester resin, polycarbonate resin, acrylic resin such as PMMA, ABS resin, etc.

[0418] <Explanation of statements, etc.>

[0419] In this invention, even when referred to as a "membrane", it also includes a "sheet", and even when referred to as a "sheet", it also includes a "membrane".

[0420] In this invention, when referred to as "X to Y" (where X and Y are arbitrary numbers), unless otherwise specified, it includes the meaning of "X or more and Y or less", and also includes the meaning of "preferably greater than X" or "preferably less than Y".

[0421] Furthermore, when it is recorded as "X or above" (where X is any number), unless otherwise specified, it includes the meaning of "preferably greater than X". When it is recorded as "Y or below" (where Y is any number), unless otherwise specified, it includes the meaning of "preferably less than Y".

[0422] Example

[0423] Next, the present invention will be described in further detail through embodiments. However, the present invention is not limited to the embodiments described below.

[0424] <Evaluation Methods>

[0425] The methods for determining and evaluating various physical properties and characteristics are described below.

[0426] (1) Intrinsic viscosity (IV)

[0427] Accurately weigh 1g of polyester, add 100ml of a mixed solvent of phenol / tetrachloroethane = 50 / 50 (mass ratio) to dissolve it, and perform the determination at 30℃.

[0428] (2) Average particle size of particles in the substrate film

[0429] The powder was observed using a scanning electron microscope (HITACHI, "S3400N").

[0430] The size of a particle is determined based on the obtained image data, and the average value of 10 points is taken as the average particle size.

[0431] (3) Number-average particle size of particles (X)

[0432] After the emulsion of microparticles (X) was coated onto a substrate and dried, images of the microparticles were observed using an electron microscope with a magnification of 20,000x or higher. In the images, the diameters of at least 400 microparticles were measured, and their arithmetic mean particle size was calculated.

[0433] (4) Glass transition temperature (Tg) of particle (X)

[0434] Five milligrams of microparticles were weighed onto an aluminum pan, which was then placed in the apparatus. The temperature was increased from -40°C to 200°C at a rate of 5°C / min, and then cooled back to -40°C at a rate of 130°C / min. The glass transition temperature (Tg) was obtained by reading the endothermic peak from the graph obtained by reheating to 200°C at a rate of 5°C / min. It should be noted that the glass transition temperature (Tg) was determined based on the "midpoint glass transition temperature: Tmg" specified in JIS K 7121 "Method for Determination of Transition Temperature of Plastics". Furthermore, when multiple glass transition points (Tg) were identified, the lowest glass transition temperature (Tg) was taken as the glass transition temperature (Tg) of the microparticles.

[0435] (5) Thickness of the cured resin layer (A), cured resin layer (B) and resin layer (C) (after drying and curing)

[0436] The film thicknesses of the cured resin layer (A), cured resin layer (B), and resin layer (C) were measured by cross-sectional observation using SEM. Furthermore, the cured resin layer (B) is impregnated in the voids of the cured resin layer (A), but the thickness of the cured resin layer (B) described in the examples does not include the impregnated portion.

[0437] (6) Arithmetic mean height (Sa)

[0438] The arithmetic mean height (Sa) was measured according to ISO 25178 using a surface shape measurement system (VertScan R5500, Hitachi Advanced Technology & Materials Co., Ltd., registered trademark) at 5x magnification, on the surface of the cured resin layer (A) of the substrate film formed by optical interferometry. Furthermore, corrections and baseline corrections were performed under the following conditions, and the data were read.

[0439] (Calibration conditions)

[0440] Supplementary correction: Complete.

[0441] Baseline correction: Surface correction (polynomial approximation fourth degree).

[0442] (7) Water droplet contact angle

[0443] The water droplet contact angle of the surface of the cured resin layer (C) side of the resin layer (B) was measured using a water droplet contact angle meter (manufactured by Kyowa Interface Science Co., Ltd., "model DMo-501"). A water droplet (volume 1.0 μL) was dropped onto the surface of the cured resin layer (B) before the formation of the resin layer (C), and the contact angle was measured after 60 seconds.

[0444] The water droplet contact angle on the surface of the resin layer (C) on the side of the cured resin layer (B) is considered to be the same as the water droplet contact angle on the opposite side of the resin layer (C) and the surface of the cured resin layer (B). The water droplet contact angle on the surface of the resin layer (C) on the side of the cured resin layer (B) is measured in the same manner as described above.

[0445] (8) Storage modulus of cured resin layer (B)

[0446] For a sample of a cured resin composition (b) with a bottom surface of 10cm × 10cm, produced using Mitsubishi Chemical Co., Ltd.'s "T100-38", a curable resin composition (b) was poured into it to form a film thickness of 5.0mm and cured. The T100-38 was then peeled off to obtain a cured coating monomer. The sample was measured using an IT measuring machine, Ltd.'s "DVA-225", in shear mode according to JIS 7244, at a temperature of -100℃ to 250℃. The storage modulus at 25℃ was recorded.

[0447] (9) Glass transition temperature (Tg) of the cured resin layer (B)

[0448] For a sample prepared by using Mitsubishi Chemical Co., Ltd.'s "T100-38" to create a folded container with a bottom surface of 10cm × 10cm, a curable resin composition (b) was poured into it to form a film thickness of 5.0mm and cured. The T100-38 was then peeled off to form a cured coating monomer. The measurements were performed using an IT measuring machine, Ltd.'s "DVA-225," in shear mode according to JIS 7244, at a temperature of -100℃ to 250℃. The glass transition temperature (Tg) was read.

[0449] (10) Structural colorimetric properties

[0450] After the transfer is applied to the substrate, a visual sensory evaluation is conducted on the color tone of the surface of the transfer laminate after the substrate film has been peeled off, namely the surface of the cured resin layer (A), both when viewed from the front and when viewed at an angle of 45 degrees.

[0451] (11) Peelability of the substrate film after heat sealing test

[0452] The peel test was conducted using the "Heated Temperature Electric Seal OPL-300-10" manufactured by Fuji INPULSE Co., Ltd.

[0453] The manufactured transfer laminate film was cut into TD60mm and MD30mm sizes. The resin layer (C) (heat seal) was overlapped with a PET film "T100-38" manufactured by Mitsubishi Chemical Corporation. After aligning the TD of the film along the long dimension of the heat sealing rod, it was heated from the substrate film side at a specified temperature (160°C for 3 seconds, followed by 40°C for 0.2 seconds) and heat-sealed at a pressure of 0.1MPa for 60 seconds. Then, after standing for 10 seconds, the substrate film was peeled off, and the interface where peeling occurred was visually confirmed and evaluated according to the following evaluation criteria.

[0454] [Evaluation Criteria]

[0455] 〇: Delamination occurred only at the interface between the substrate film and the cured resin layer (A).

[0456] △: Interfacial delamination occurred between the substrate film and the cured resin layer (A), but at the same time, cohesive failure of other layers and interfacial delamination between other layers occurred.

[0457] ×: No interfacial delamination occurred between the substrate film and the cured resin layer (A).

[0458] The raw materials for the transfer laminates in the various embodiments and comparative examples are as follows.

[0459] [Substrate film]

[0460] <Polyester (I)>

[0461] Using terephthalic acid as the dicarboxylic acid component and ethylene glycol as the polyol component, polyester chips with an intrinsic viscosity of 0.62 dl / g and containing 3.5% by mass of silica particles with an average particle size of 4 μm were manufactured by conventional melt polymerization.

[0462] <Polyester (II)>

[0463] Using terephthalic acid as the dicarboxylic acid component and ethylene glycol as the polyol component, polyester chips with an intrinsic viscosity of 0.65 dl / g and without the use of lubricants were manufactured by conventional melt polymerization.

[0464] <Polyester (III)>

[0465] Using terephthalic acid as the dicarboxylic acid component and ethylene glycol as the polyol component, polyester chips with an intrinsic viscosity of 0.63 dl / g and containing no lubricant were manufactured by conventional melt polymerization.

[0466] <Polyester (IV)>

[0467] Using terephthalic acid as the dicarboxylic acid component and ethylene glycol as the polyol component, polyester chips with an intrinsic viscosity of 0.65 dl / g and containing 0.2% by mass of amorphous silica particles with an average particle size of 2.4 μm were manufactured by conventional melt polymerization.

[0468] [Curing Resin Composition]

[0469] <Particle (X)>

[0470] A monomer mixture was prepared by mixing 630 parts by mass of styrene and 9 parts by mass of acrylic acid [i].

[0471] In addition, 101 parts by mass of styrene, 2 parts by mass of acrylic acid, and 43 parts by mass of diacetone acrylamide were mixed to prepare a monomer mixture [ii].

[0472] On the other hand, an auxiliary agent solution was prepared by dissolving 1.2 parts by mass of sodium styrene sulfonate and 1.5 parts by mass of sodium bicarbonate in 16-15 parts by mass of ion-exchanged water.

[0473] The additive solution is added to a reaction vessel equipped with a stirring device, a heating and cooling device, a nitrogen introduction device, a Liebig condenser, and a raw material / additive feeding device, and the internal temperature is raised to 77°C.

[0474] Next, a polymerization initiator solution prepared by dissolving 4.3 parts by mass of ammonium persulfate in 455 parts by mass of ion-exchanged water was added to the reaction vessel, and monomer mixture was added dropwise over 2.5 hours after 5 minutes [i].

[0475] After the addition of monomer mixture [i] is completed, monomer mixture [ii] is added dropwise over 0.5 hours.

[0476] After the addition of monomer mixture [ii] was completed, stirring was continued at 77°C for 1.5 hours, and the internal temperature was raised to 90°C. Then, the Liebig condenser was removed from the apparatus, and stirring was maintained at 90°C for 3 hours while nitrogen was introduced from the nitrogen inlet at a rate of 1 L / min.

[0477] After cooling the internal temperature to 20°C, the polymerization reactants were filtered through nonwoven fabric (treated) to obtain an emulsion of microparticles with ketone and carboxyl groups as reactive functional groups. The pH was adjusted to 7.0 by adding 10% by mass ammonia to the emulsion. Furthermore, deionized water was added appropriately to adjust the solids concentration to 29.0% by mass, thereby obtaining an emulsion of microparticles (X) with ketone and carboxyl groups as reactive functional groups.

[0478] The particle (X) has a number-average particle size of 250 nm and a glass transition temperature (Tg) of 106 °C.

[0479] [Example 1]

[0480] Polyester (I) and (II) were mixed in proportions of 67.7% by mass and 32.3% by mass, respectively. The resulting mixture was fed into an extruder, melted at 280°C, and then extruded in a single layer on a cooling roller set at 47°C to allow it to cool and solidify, resulting in an unstretched sheet. Next, utilizing the difference in roller circumferential speed, the sheet was stretched 3.8 times longitudinally at a film temperature of 80°C and then fed into a tenter frame. It was stretched 4.0 times transversely at 120°C, heat-treated at 234°C, and then relaxed 4% transversely to obtain a semi-transparent polyester film roll (substrate film) with a thickness of 26 μm.

[0481] The arithmetic mean height (Sa) of one side of the cured resin layer (A) of the obtained substrate film is 421 nm.

[0482] On one side of the above-mentioned polyester film roll, the following cured resin composition (a) is applied with a bar coater (#10) to a thickness (after curing) of 7 μm, and dried at 100°C for 1 minute to form a cured resin layer (A).

[0483] (Curing resin composition (a))

[0484] A cured resin composition (a) with a solid content of 26.8% by mass was prepared by mixing 18 parts by mass of an emulsion of microparticles (X), 1.4 parts by mass of a 10% by mass aqueous solution of adipic acid dihydrazide as a crosslinking agent (Y), 0.1 parts by mass of a 4% by mass aqueous solution of polyvinyl alcohol (GOHSENX CKS-50, Mitsubishi Chemical Corporation) as a water-soluble resin, and 0.5 parts by mass of deionized water.

[0485] The cured resin composition (a) contains 2.7 parts by mass of crosslinking agent (Y) relative to 100 parts by mass of the particles (X) and contains 1 equivalent of crosslinking agent (Y) relative to the reactive functional groups of the particles (X).

[0486] Next, the following urethane (meth)acrylate-based curing resin composition (b-1), which serves as curing resin composition (b), was applied onto the curing resin layer (A) using a rod coating method to a thickness (after curing) of 7 μm. The mixture was then dried at 100°C for 15 seconds (0.25 minutes) to form the curing resin layer (B-1). The Tg of the curing resin layer (B-1) was -49.2°C.

[0487] (Curing resin composition (b-1))

[0488] In a four-necked flask equipped with a thermometer, stirrer, and water-cooled condenser, 270.8 parts by weight of isophorone diisocyanate, 6.3 parts by weight of 2,4-diethyl-1,5-pentanediol, 1531.5 parts by weight of polypropylene glycol with a hydroxyl value of 26, 0.8 parts by weight of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.08 parts by weight of dibutyltin dilaurate as a reaction catalyst were added, and the reaction was carried out at 60°C for 8 hours. Then, after adding 191.4 parts by weight of 2-hydroxyethyl acrylate, the reaction was stopped at the time point when the residual isocyanate groups reached 0.3%, yielding a cured resin composition (b-1) as a polyol-based urethane (meth)acrylate resin composition.

[0489] The obtained cured resin composition (b-1) has a mass-average molecular weight of 7300 and a viscosity of 1350 mPa·s at 60°C.

[0490] Furthermore, the following resin composition (c-1) was applied onto the cured resin layer (B-1) by a rod coating method with a thickness (after drying) of 3 μm, and dried at 100°C for 120 minutes to form the resin layer (C-1).

[0491] (Resin composition (c-1))

[0492] "HS1138" manufactured by Henkel Japan Co., Ltd.

[0493] Composition: Polyester resin.

[0494] Solid content concentration: 35.0% by mass.

[0495] The obtained transfer laminate was evaluated as described above. The evaluation results are shown in Table 1.

[0496] [Example 2]

[0497] Polyester (III) and (IV) were mixed at a ratio of 74% by mass and 26% by mass, respectively. The resulting mixture was used as the outermost (surface) layer material, while only polyester (I) was used as the intermediate layer material. Both were fed to two extruders and melted at 290°C. Then, they were co-extruded on cooling rollers set at 25°C with two three-layer structures (surface / intermediate / surface = 1 / 8 / 1 discharge rate (mass ratio)). After cooling and solidification, an unstretched sheet was obtained. Next, using the difference in roller circumferential speed, the film was stretched 3.4 times longitudinally at a film temperature of 88°C and fed into a tenter frame. It was then stretched 4.7 times transversely at 140°C, heat-treated at 230°C, and relaxed 8.3% transversely to obtain a colorless and transparent polyester film roll (substrate film) with a thickness of 38 μm.

[0498] The arithmetic mean height (Sa) of one side of the cured resin layer (A) of the obtained substrate film is 32 nm.

[0499] Except for using the aforementioned substrate film as the substrate film, a transfer laminate film was manufactured in the same manner as in Example 1, and the evaluation was performed in the same manner. The evaluation results are shown in Table 1.

[0500] [Example 3]

[0501] Polyester (III) and (IV) were mixed at a ratio of 87% by mass and 13% by mass, respectively. The resulting mixture was used as the outermost (surface) layer material, while only polyester (I) was used as the intermediate layer material. Both were fed to two extruders and melted at 270°C. Then, they were co-extruded on cooling rollers set at 25°C with two three-layer structures (surface / intermediate / surface = 1 / 8 / 1 discharge rate (mass ratio)). After cooling and solidification, an unstretched sheet was obtained. Next, using the difference in roller circumferential speed, the film was stretched 3.5 times longitudinally at a film temperature of 89°C and fed into a tenter frame. It was then stretched 4.7 times transversely at 140°C. After heat treatment at 237°C, it was relaxed 7% transversely to obtain a colorless and transparent polyester film roll (substrate film) with a thickness of 50 μm.

[0502] The arithmetic mean height (Sa) of one side of the cured resin layer (A) of the obtained substrate film is 14 nm.

[0503] Except for using the aforementioned substrate film as the substrate film, a transfer laminate film was manufactured in the same manner as in Example 1, and the evaluation was performed in the same manner. The evaluation results are shown in Table 1.

[0504] [Example 4]

[0505] Polyester (III) and (IV) were mixed at a ratio of 92% by mass and 8% by mass, respectively. The resulting mixture was used as the outermost (surface) layer material, while polyester (III) was used only as the intermediate layer material. Both mixtures were fed to two extruders, melted at 285°C, and then co-extruded on cooling rollers set at 40–50°C with two different three-layer structures (surface / intermediate / surface = 5 / 90 / 5 discharge ratio). The extrusion was then cooled and solidified to obtain an unstretched sheet. Next, utilizing the difference in roller circumferential speed, the sheet was stretched 3.5 times longitudinally at a film temperature of 85°C, and then coated with a dry coating weight of 0.03 g / m². 2 The release agent composition, which contains the following release agent and crosslinking agent in a mass ratio of 60 / 40, is coated on one side of the longitudinally stretched film. The film is then fed into a tenter frame and stretched 4.3 times in the transverse direction at 100°C. After heat treatment at 230°C, the film is relaxed by 2% in the transverse direction to obtain a colorless and transparent polyester film roll (substrate film) with a release layer and a thickness of 50 μm.

[0506] [Release agent composition]

[0507] Release agent: A compound containing long-chain alkyl groups formed by the addition of polyvinyl alcohol with an average degree of polymerization of 500 and a saponification degree of 88 mol% to octadecyl isocyanate.

[0508] Crosslinking agent: melamine compound (hexamethoxyhydroxymethyl melamine).

[0509] Using the aforementioned substrate film with a release layer as the substrate film, and using water / IPA = 1:1 instead of water as the dilution solution for the curing resin composition (a), the transfer laminate was manufactured in the same manner as in Example 1, and the evaluation was performed in the same manner. The evaluation results are shown in Table 2.

[0510] [Example 5]

[0511] The following curing resin composition (b-2), which is the curing resin composition (b), was applied onto the curing resin layer (A) by a rod coating method with a thickness (after curing) of 7 μm. The layer was dried at 130°C for 2 minutes to form the curing resin layer (B-2). Otherwise, the transfer laminate was manufactured in the same manner as in Example 4, and the evaluation was performed in the same manner. The evaluation results are shown in Table 2.

[0512] (Curing resin composition (b-2))

[0513] Shin-Etsu Chemical Industry Co., Ltd. manufactured "KE109E".

[0514] Composition: Organosilicon resin.

[0515] [Comparative Example 1]

[0516] A transfer laminate was manufactured in the same manner as in Example 1, except that no resin layer (C) was provided on the cured resin layer (B), and the evaluation was performed in the same manner. The evaluation results are shown in Table 1.

[0517] [Table 1]

[0518]

[0519] [Table 2]

[0520]

[0521] As can be seen from Tables 1 and 2, the transfer film of the present invention exhibits excellent transfer of the structural color layer to the substrate through the resin layer (C) with the sealing layer, and excellent peelability of the substrate film after transfer to the substrate.

[0522] The present invention has been described in detail using specific methods, but it will be apparent to those skilled in the art that various modifications can be made within the scope of achieving the inventive effect.

[0523] This application is based on Japanese Patent Application 2024-051893, filed on March 27, 2024, the entire contents of which are incorporated herein by reference.

Claims

1. A transfer laminate, wherein the transfer laminate has a curing resin layer (A), a curing resin layer (B), and a resin layer (C) sequentially formed on one side of a substrate film. The cured resin layer (A) is a structural color layer with structural color development formed from a cured resin composition (a) containing microparticles (X), and the resin layer (C) is a sealing layer.

2. The transfer film according to claim 1, wherein, The arithmetic mean height Sa of the surface of the cured resin layer (A) side of the substrate film is 50 nm to 600 nm.

3. The transfer film according to claim 1, wherein, The contact angle difference between water droplets on the surfaces of the cured resin layer (B) and the resin layer (C) is 0 to 35°.

4. The transfer film according to claim 3, wherein, The storage modulus of the cured resin layer (B) at 25°C is 1.0 × 10⁻⁶. 3 Pa ~ 2.0 × 10 8 Pa.

5. The transfer film according to claim 3, wherein, A release layer is provided between the substrate film and the cured resin layer (A).

6. The transfer film according to claim 1, wherein, The ratio of the combined thickness of the cured resin layer (A) and the cured resin layer (B) to the thickness of the resin layer (C) is in the range of 10:1 to 10:

5.

7. A method for manufacturing a transfer laminated film, the method comprising manufacturing a transfer laminated film according to any one of claims 1 to 6, comprising: A heat treatment process in which the cured resin composition (a) coated on the substrate film is heated to form the cured resin layer (A); A heat treatment process in which the curing resin composition (b) for forming the curing resin layer (B) coated on the curing resin layer (A) is heated to below 130°C to form the curing resin layer (B), or an irradiation process in which the curing resin composition (b) for forming the curing resin layer (B) coated on the curing resin layer (A) is irradiated with active energy rays to form the curing resin layer (B); and The process of coating the resin composition (c) for forming the resin layer (C) onto the cured resin layer (B) and drying it to form the resin layer (C).

8. A transfer method, wherein after the resin layer (C) of the transfer laminated film according to any one of claims 1 to 6 is pressed against and pressed against the substrate, the substrate film is peeled off, and the cured resin layer (A) and the cured resin layer (B) are transferred to the substrate via the resin layer (C).

Images