Laminates, cards, booklets, passports, security cards, and enclosures

Abstract

Provided is a laminated body capable of improving forgery prevention properties.　This laminated body comprises: a substrate; an intermediate layer provided on the substrate and having a housing section; a recording medium provided in the housing section; and an overlay layer provided on the intermediate layer. The housing section is provided at a portion on the surface of the intermediate layer; and the housing section is a through hole that penetrates through the intermediate layer in the thickness direction thereof, or a recess that is indented into the intermediate layer in the thickness direction thereof. The recording medium comprises a color-developing layer containing: a coloring compound having electron-donating properties; a developer having electron-accepting properties; and a matrix resin. The substrate, the intermediate layer, and the overlay layer all contain the same type of resin material. The substrate and the intermediate layer are fused together; and the intermediate layer and the overlay layer are fused together.

Description

[Technical Field]

[0001] This disclosure pertains to laminates, cards booklet, passport, security card And regarding the enclosure. [Background technology]

[0002] In recent years, for cards such as security cards, financial payment cards (e.g., credit cards, cash cards, etc.), ID cards (e.g., employee IDs, membership cards, student IDs, etc.), and personal transaction cards (e.g., prepaid cards, point cards, etc.), there has been consideration to equip them with recording media configured to change their color state in response to external stimuli in order to prevent counterfeiting. For example, Patent Document 1 discloses an anti-counterfeiting structure in which a security device and a transparent protective sheet are sequentially arranged on a color-developing layer having a laser-color-developing section. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2019-38141 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] In recent years, while the widespread use of the various cards mentioned above has brought about increased convenience, their counterfeiting has become a major problem. Furthermore, the circulation of counterfeit medical supplies, automotive parts, toys, food, cosmetics, and electronic devices is also a concern. The circulation of these counterfeit goods not only damages a company's brand and image but also poses a risk to users' health and safety. Therefore, there is a strong demand for improved anti-counterfeiting capabilities for cards and products.

[0005] The purpose of this disclosure is to provide laminates and cards that can improve anti-counterfeiting properties. booklet, passport, security card The objective is to provide an enclosure. [Means for solving the problem]

[0006] To solve the above-mentioned problems, the laminate relating to this disclosure is Substrate and Provided on the base material, at least one A first intermediate layer having a storage area, A recording medium located within the storage compartment, An overlay layer provided on the first intermediate layer and Equipped with, The containment section is provided in a part of the plane of the first intermediate layer. The housing portion is a through hole penetrating in the thickness direction of the first intermediate layer, or a recessed portion in the thickness direction of the first intermediate layer. The recording medium comprises a color-developing layer containing an electron-donating color-developing compound, an electron-accepting color developer, and a matrix resin. The substrate, the first intermediate layer, and the overlay layer are Polycarbonate resin Includes, The substrate and the first intermediate layer are bonded together by fusion, and the first intermediate layer and the overlay layer are bonded together by fusion. 。

[0007] The laminate relating to this disclosure is Substrate and Provided on the base material, at least one A first intermediate layer having a storage area, A recording medium located within the storage compartment, An overlay layer provided on the first intermediate layer and Equipped with, The containment section is provided in a part of the plane of the first intermediate layer. The housing portion is a through hole penetrating in the thickness direction of the first intermediate layer, or a recessed portion in the thickness direction of the first intermediate layer. The recording medium comprises a color-developing layer containing an electron-donating color-developing compound, an electron-accepting color developer, and a matrix resin. The substrate, the first intermediate layer, and the overlay layer are Polycarbonate resin Includes, The laminate is bonded between the base material and the first intermediate layer using a thermal adhesive, and between the first intermediate layer and the overlay layer using a thermal adhesive. [Brief explanation of the drawing]

[0008] [Figure 1] Figure 1 is a perspective view of a laminate according to the first embodiment of this disclosure. [Figure 2] Figure 2 is a cross-sectional view along the line II-II in Figure 1. [Figure 3] Figure 3 is a cross-sectional view of the recording medium. [Figure 4] Figure 4 is a cross-sectional view of a laminate according to the second embodiment of this disclosure. [Figure 5] Figure 5 is a cross-sectional view of a modified example of the first embodiment of the present disclosure. [Figure 6] Figure 6 is a cross-sectional view of a modified recording medium. [Figure 7] Figure 7A is a plan view of the front of the smartphone. Figure 7B is a plan view of the back of the smartphone. [Figure 8] Figure 8 is a perspective view of a notebook personal computer. [Figure 9] Figure 9 is a perspective view of a cosmetic container. [Figure 10] Figure 10 is a cross-sectional view of the recording medium. [Figure 11] Figure 11 shows the test apparatus for the 90-degree peel test. [Figure 12] Figure 12A is a diagram illustrating the preparation steps for the 90-degree peel test. Figure 12B is a diagram of the test apparatus for the 90-degree peel test. [Figure 13] Figure 13 is a perspective view of a laminate according to a third embodiment of the present disclosure. [Figure 14] Figure 14 is a cross-sectional view along the line XIV-XIV in Figure 13. [Figure 15] Figure 15 is a cross-sectional view of the recording medium. [Figure 16] Figure 16 is a cross-sectional view of a laminate according to the fourth embodiment of this disclosure. [Figure 17] Figure 17 is a cross-sectional view of a modified example of the third embodiment of the present disclosure. [Figure 18] Figure 18 is a cross-sectional view of the recording medium. [Figure 19] Figure 19 is a cross-sectional view of the recording medium. [Figure 20] Figure 20 is a cross-sectional view of the recording medium. [Figure 21] Figure 21 is a cross-sectional view of the recording medium. [Figure 22] Figure 22 is a cross-sectional view of the recording medium. [Figure 23] Figure 23 is a cross-sectional view of the recording medium. [Figure 24] Figure 24 is a cross-sectional view of the recording medium. [Figure 25] Figure 25 is a perspective view of the booklet. [Figure 26] Figure 26 is a graph showing the measurement results of the peel strength of the sample. [Modes for carrying out the invention]

[0009] Embodiments of this disclosure will be described in the following order. In all the figures of the embodiments described below, the same or corresponding parts will be denoted by the same reference numerals. 1. First Embodiment (Example of a Laminate) 1.1 Structure of the Laminate 1.2 Method for manufacturing laminates 1.3 Method for recording laminated structures 1.4 Action and Effects 2. Second Embodiment (Example of a Laminate) 2.1 Structure of the Laminate 2.2 Method for manufacturing laminates 2.3 Action and Effects 3. Third Embodiment (Example of a Laminate) 3.1 Structure of the Laminate 3.2 Action and Effects 4. Fourth Embodiment (Example of a Laminate) 4.1 Structure of the Laminate 4.2 Action and Effects 5 Variations 6. Reference Examples and Implements

[0010] <1 First Embodiment> [1.1 Structure of the Laminate] Figure 1 is a perspective view of a laminate 10 according to a first embodiment of the present disclosure. Figure 2 is a cross-sectional view taken along line II-II in Figure 1. The laminate 10 comprises a base material 11, an adhesive layer 12, an intermediate layer 13, an adhesive layer 14, an overlay layer 15, and a recording medium 20. The laminate 10 may be a card such as a security card, a financial settlement card (e.g., a credit card, a cash card, etc.), an ID card (e.g., an employee ID, a membership card, a student ID, etc.), or a personal transaction card (e.g., a prepaid card, a point card, etc.) (hereinafter referred to as "security card, etc.").

[0011] (base material) The base material 11 is a support that supports the recording medium 20 and the intermediate layer 13. The base material 11 may be a card. The base material 11 may have a color such as white. The base material 11 may have a design, picture, photograph, text, or a combination of two or more of these (hereinafter referred to as "design, etc.") printed on one main surface of the base material 11 on the side where the intermediate layer 13 and the recording medium 20 are provided.

[0012] The base material 11 includes, for example, plastic. The base material 11 may optionally contain at least one selected from the group consisting of colorants, antistatic agents, flame retardants, and surface modifiers.

[0013] The plastic includes, for example, at least one selected from the group consisting of ester resins, amide resins, olefin resins, vinyl resins, acrylic resins, imide resins, styrene resins, and engineering plastics. If the substrate 11 contains two or more resins, these two or more resins may be mixed, copolymerized, or laminated.

[0014] Ester resins include, for example, at least one selected from the group consisting of polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), polyethylene terephthalate-isophthalate copolymer, and terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer. Amide resins include, for example, at least one selected from the group consisting of nylon 6, nylon 66, and nylon 610. Olefin resins include, for example, at least one selected from the group consisting of polyethylene (PE), polypropylene (PP), and polymethylpentene (PMP). Vinyl resins include, for example, polyvinyl chloride (PVC).

[0015] Acrylic resins include, for example, at least one selected from the group consisting of polyacrylate, polymethacrylate, and polymethyl methacrylate (PMMA). Imide resins include, for example, at least one selected from the group consisting of polyimide (PI), polyamideimide (PAI), and polyetherimide (PEI). Styrene resins include, for example, at least one selected from the group consisting of polycarbonate (PC), polystyrene (PS), high-impact polystyrene, acrylonitrile-styrene resin (AS resin), and acrylonitrile-butadiene-styrene resin (ABS resin). Engineering plastics include, for example, at least one selected from the group consisting of polycarbonate (PC), polyarylate (PAR), polysulfone (PSF), polyethersulfone (PES), polyphenylene ether (PPE), polyphenylene sulfide (PPS), polyetherketone (PEK), polyether-etherketone (PEEK), polyphenylene oxide (PPO), and polyethersulfite.

[0016] (Middle class) The intermediate layer 13 is provided on one main surface of the base material 11, with an adhesive layer 12 sandwiched between the base material 11 and the intermediate layer 13. The intermediate layer 13 has a housing portion 13A for housing the recording medium 20. The housing portion 13A is provided in a part of the surface of the intermediate layer 13. The housing portion 13A may be a through hole that penetrates in the thickness direction of the intermediate layer 13. The intermediate layer 13 is intended to suppress the step difference formed by the recording medium 20 when the recording medium 20 is sandwiched between the base material 11 and the overlay layer 15. The intermediate layer 13 has approximately the same thickness as the recording medium 20 and covers the area of ​​one main surface of the base material 11 other than the area on which the recording medium 20 is provided.

[0017] The intermediate layer 13 has a film-like structure. The intermediate layer 13 may be transparent. The intermediate layer 13 contains plastic. Examples of plastic materials include those similar to those used for the base material 11.

[0018] (Overlay layer) The overlay layer 15 is provided on the intermediate layer 13 and the recording medium 20, and covers the intermediate layer 13 and the recording medium 20. An adhesive layer 14 is sandwiched between the intermediate layer 13, the recording medium 20 and the overlay layer 15. The overlay layer 15 protects the internal components of the laminate 10 (i.e., the recording medium 20 and the intermediate layer 13) and maintains the mechanical reliability of the laminate 10.

[0019] The overlay layer 15 is film-like. The overlay layer 15 is transparent. The overlay layer 15 contains plastic. Examples of plastic materials include those similar to those used for the base material 11. A design or pattern may be printed on at least one main surface of the overlay layer 15.

[0020] (adhesive layer) Adhesive layer 12 is provided between the substrate 11 and the intermediate layer 13 containing the recording medium 20, and bonds the substrate 11 and the intermediate layer 13 containing the recording medium 20. Adhesive layer 14 is provided between the intermediate layer 13 containing the recording medium 20 and the overlay layer 15, and bonds the intermediate layer 13 containing the recording medium 20 and the overlay layer 15. Adhesive layers 12 and 14 are transparent. Adhesive layers 12 and 14 contain a thermal adhesive. The thermal adhesive contains a thermosetting resin. The thermosetting resin includes, for example, at least one selected from the group consisting of epoxy resins and urethane resins. The curing temperature of the thermal adhesive is preferably in the temperature range of 100°C to 120°C from the viewpoint of reducing damage to the recording medium 20.

[0021] (Recording medium) Figure 3 is a cross-sectional view of the recording medium 20. The recording medium 20 is configured to change its coloring state in response to an external stimulus. This change in coloring state allows, for example, a design to be recorded on the recording medium 20. The external stimulus is laser light. From the viewpoint of improving anti-counterfeiting properties, it is preferable that the change in coloring state is irreversible. That is, it is preferable that the recording medium 20 is write-once, meaning that a design can be written only once. It is preferable that the recording medium 20 is fitted into the housing portion 13A of the intermediate layer 13, so that the recording medium 20 and the intermediate layer 13 are integrated. This makes it difficult to see the boundary between the recording medium 20 and the intermediate layer 13 in the in-plane direction of the laminate 10. Therefore, anti-counterfeiting properties can be improved.

[0022] The recording medium 20 comprises a base material 21, an intermediate layer 32A, a color development layer 24, an intermediate layer 32B, a color development layer 27, an intermediate layer 32C, and a color development layer 30 in this order. More specifically, the recording medium 20 comprises a base material 21, an adhesive layer 22, a heat insulating layer 23, a color development layer 24, an adhesive layer 25, a heat insulating layer 26, a color development layer 27, an adhesive layer 28, a heat insulating layer 29, and a color development layer 30 in this order. The recording medium 20 may further include a protective layer 31 on the color development layer 30, as shown in Figure 3. The recording medium 20 may further include an intermediate layer 32D between the color development layer 30 and the protective layer 31, as shown in Figure 10. The heat insulating layers 23, 26, and 29 are provided as needed and are not required.

[0023] (base material) The substrate 21 is a support for supporting the color-developing layers 24, 27, 30, etc. Preferably, the substrate 21 is made of a material that has excellent heat resistance and excellent dimensional stability in the planar direction. The substrate 21 may have either light-transmitting or light-non-transmitting properties. The substrate 21 may be a rigid substrate such as a wafer, or a flexible thin-layer glass, film, or paper. By using a flexible substrate 21, a flexible (bendable) recording medium can be realized.

[0024] Examples of constituent materials for the base material 21 include inorganic materials, metallic materials, or plastics. Examples of inorganic materials include silicon (Si) and silicon dioxide (SiO₂). X ), silicon nitride (SiN X ) and aluminum oxide (AlO X It includes at least one selected from the group consisting of ) etc. Silicon oxide includes glass and spin-on glass (SOG), etc. Metal materials include, for example, at least one selected from the group consisting of aluminum (Al), nickel (Ni), stainless steel, etc. As for plastics, materials similar to those of the base material 11 can be exemplified.

[0025] Furthermore, a reflective layer (not shown) may be provided on at least one main surface of the substrate 21, or the substrate 21 itself may also function as a reflective layer. Having such a configuration in the substrate 21 enables clearer color display.

[0026] (Middle class) The intermediate layer 32A is provided between the substrate 21 and the color-developing layer 24. The intermediate layer 32A can bond the substrate 21 and the color-developing layer 24 together. The intermediate layer 32A can provide thermal insulation between the substrate 21 and the color-developing layer 24, and may also suppress the diffusion of the constituent materials between the substrate 21 and the color-developing layer 24. The intermediate layer 32A comprises an adhesive layer 22 and a thermal insulation layer 23. The adhesive layer 22 is adjacent to the substrate 21, and the thermal insulation layer 23 is adjacent to the color-developing layer 24. However, the intermediate layer 32A may comprise only the adhesive layer 22.

[0027] The intermediate layer 32B is provided between the color-developing layer 24 and the color-developing layer 27. The intermediate layer 32B can bond the color-developing layer 24 and the color-developing layer 27 together. The intermediate layer 32B can provide thermal insulation between the color-developing layer 24 and the color-developing layer 27, and may also suppress the diffusion of the constituent materials between the color-developing layer 24 and the color-developing layer 27. The intermediate layer 32B comprises an adhesive layer 25 and a thermal insulation layer 26. However, the intermediate layer 32B may comprise only the adhesive layer 25.

[0028] The intermediate layer 32C is provided between the color-developing layer 27 and the color-developing layer 30. The intermediate layer 32C can bond the color-developing layer 27 and the color-developing layer 30 together. The intermediate layer 32C can provide thermal insulation between the color-developing layer 27 and the color-developing layer 30, and may also suppress the diffusion of the constituent materials between the color-developing layer 27 and the color-developing layer 30. The intermediate layer 32C comprises an adhesive layer 28 and a thermal insulation layer 29. However, the intermediate layer 32C may comprise only the adhesive layer 28.

[0029] The intermediate layer 32D is provided between the color-developing layer 30 and the protective layer 31. The intermediate layer 32D can bond the color-developing layer 30 and the protective layer 31 together. The intermediate layer 32D can provide thermal insulation between the color-developing layer 30 and the protective layer 31, and may also suppress the diffusion of the constituent materials between the color-developing layer 30 and the protective layer 31. The intermediate layer 32D comprises an adhesive layer 33 and a thermal insulation layer 34. However, the intermediate layer 32D may comprise only the adhesive layer 33.

[0030] (Coloring layer) The color-developing layers 24, 27, and 30 are configured to change their color state in response to external stimuli such as laser light or heat. The color-developing layers 24, 27, and 30 are constructed using materials that allow for stable recording and control of the color-developing state. The color-developing layers 24, 27, and 30 include an electron-donating color-developing compound, an electron-accepting color developer corresponding to the color-developing compound, a matrix polymer (binder), and a photothermal conversion material. The color-developing layers 24, 27, and 30 may optionally include, in addition to the above materials, at least one additive selected from the group consisting of, for example, sensitizers and ultraviolet absorbers.

[0031] The color-developing layers 24, 27, and 30 contain color-developing compounds with different color hues. That is, the color-developing compounds contained in the color-developing layers 24, 27, and 30 exhibit different colors in the color-developed state. For example, the color-developing compound contained in color-developing layer 24 exhibits a cyan color in the color-developed state. For example, the color-developing compound contained in color-developing layer 27 exhibits a magenta color in the color-developed state. For example, the color-developing compound contained in color-developing layer 30 exhibits a yellow color in the color-developed state. The photothermal conversion materials contained in color-developing layers 24, 27, and 30 absorb laser light in different wavelength ranges (for example, different near-infrared laser light) and generate heat.

[0032] The thickness of each color-developing layer 24, 27, and 30 is preferably 1 μm to 20 μm, and more preferably 2 μm to 15 μm. If each color-developing layer 24, 27, and 30 has a thickness of 1 μm or more, sufficient color density can be obtained. On the other hand, if each color-developing layer 24, 27, and 30 has a thickness of 20 μm or less, it is possible to suppress the excessive heat utilization of each color-developing layer 24, 27, and 30. Therefore, deterioration of color development can be suppressed.

[0033] (color-forming compound) The color-producing compound is, for example, a leuco dye. The leuco dye may be, for example, an existing dye for thermal paper. A specific example is a compound represented by the following formula (1), which contains an electron-donating group in its molecule.

[0034] [ka]

[0035] There are no particular restrictions on the color-developing compounds, and they can be appropriately selected depending on the purpose. Specific examples of color-developing compounds include, in addition to the compound shown in formula (1) above, fluorane compounds, triphenylmethanephthalide compounds, azaphthalide compounds, phenothiazine compounds, leucoauramine compounds, and indolinophthalide compounds. In addition, for example, 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-di(n-butylamino)fluorane, 2-anilino-3-methyl-6-(Nn-propyl-N-methylamino)fluorane, 2-anilino-3-methyl-6-(N-isopropyl-N-methylamino)fluorane, 2-anilino-3-methyl-6-(N-isobutyl-N-methylamino)fluorane, 2-anilino-3-methyl-6-(Nn-amyl-N-methylamino)fluorane, 2-anilino-3-methyl-6-(N-sec-butyl-N-methylamino)fluorane, 2-anilino-3-methyl-6-(Nn-amyl-N-ethylamino)fluorane, 2-anilino-3-methyl-6-( N-iso-amyl-N-ethylamino)fluorane, 2-anilino-3-methyl-6-(Nn-propyl-N-isopropylamino)fluorane, 2-anilino-3-methyl-6-(N-cyclohexyl-N-methylamino)fluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane, 2-anilino-3-methyl-6-(N-methyl-p-toluidino)fluorane, 2-(m-trichloromethylanilino)-3-methyl-6-diethylaminofluorane, 2-(m-trifluoromethylanilino)-3-methyl-6-diethylaminofluorane, 2-(m-trichloromethylanilino)-3-methyl-6-(N-cyclohexyl-N-methylamino)fluorane, 2-(2,4-dimethylanilino)-3-methyl-6-diethylaminofluorane, 2-(N-ethyl-p-toluidino)-3-methyl-6-(N-ethylanilino)fluorane, 2-(N-ethyl-p-toluidino)-3-methyl-6-(N-propyl-p-toluidino)fluorane, 2-anilino-6-(Nn-hexyl-N-ethylamino)fluorane, 2-(o-chloroanilino)-6-diethylaminofluorane, 2-(o-chloroanilino)-6-dibutylaminofluorane, 2-(m-trifluoromethylanilino)-6-diethylaminofluorane, 2,3-dimethyl-6-dimethylaminofluorane, 3-methyl-6-(N-ethyl-p-toluidino)fluorane, 2-chloro-6 -Diethylaminofluorane, 2-bromo-6-diethylaminofluorane, 2-chloro-6-dipropylaminofluorane, 3-chloro-6-cyclohexylaminofluorane, 3-bromo-6-cyclohexylaminofluorane, 2-chloro-6-(N-ethyl-N-isoamylamino)fluorane, 2-chloro-3-methyl-6-diethylaminofluorane, 2-anilino-3-chloro-6-diethylaminofluorane, 2-(o-chloroanilino)-3-chloro-6-cyclohexylaminofluorane, 2-(m-trifluoromethylanilino)-3-chloro-6-diethylaminofluorane, 2-(2,3-dichloroanilino)-3-chloro-6-diethylaminofluorane, 1,2-Benzo-6-diethylaminofluorane, 3-diethylamino-6-(m-trifluoromethylanilino)fluorane, 3-(1-ethyl-2-methylindole-3-yl)-3-(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide, 3-(1-ethyl-2-methylindole-3-yl)-3-(2-ethoxy-4-diethylaminophenyl)-7-azaphthalide, 3-(1-octyl- 2-methylindole-3-yl)-3-(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide, 3-(1-ethyl-2-methylindole-3-yl)-3-(2-methyl-4-diethylaminophenyl)-4-azaphthalide, 3-(1-ethyl-2-methylindole-3-yl)-3-(2-methyl-4-diethylaminophenyl)-7-azaphthalide, 3-(1-ethyl-2-methylin Dol-3-yl)-3-(4-diethylaminophenyl)-4-azaphthalide, 3-(1-ethyl-2-methylindole-3-yl)-3-(4-Nn-amyl-N-methylaminophenyl)-4-azaphthalide, 3-(1-methyl-2-methylindole-3-yl)-3-(2-hexyloxy-4-diethylaminophenyl)-4-azaphthalide, 3,3-bis(2-ethoxy-4-diethylaminophenyl) Phenyl)-4-azaphthalide, 3,3-bis(2-ethoxy-4-diethylaminophenyl)-7-azaphthalide, 2-(p-acetylanilino)-6-(Nn-amyl-Nn-butylamino)fluorane, 2-benzylamino-6-(N-ethyl-p-toluidino)fluorane, 2-benzylamino-6-(N-methyl-2,4-dimethylanilino)fluorane, 2-benzylamino-6-(N-ethyl-2,4-dimethylanilino)fluorane, 2-benzylamino-6-(N-methyl-p-toluidino)fluorane, 2-benzylamino-6-(N-ethyl-p-toluidino)fluorane, 2-(di-p-methylbenzylamino)-6-(N-ethyl-p-toluidino)fluorane, 2-(α-phenylethylamino)-6-(N-ethyl-p-toluidino)fluorane, 2-methylamino-6-(N-methylanilino)fluorane, 2-methylamino-6-(N-ethylanilino)fluorane, 2-methylamino-6-(N-propylanilino)fluorane , 2-ethylamino-6-(N-methyl-p-toluidino)fluorane, 2-methylamino-6-(N-methyl-2,4-dimethylanilino)fluorane, 2-ethylamino-6-(N-ethyl-2,4-dimethylanilino)fluorane, 2-dimethylamino-6-(N-methylanilino)fluorane, 2-dimethylamino-6-(N-ethylanilino)fluorane, 2-diethylamino-6-(N-methyl-p-toluidino)fluorane, 2-diethylamino-6-(N-ethyl-p-toluidino)fluorane, 2-dipropylamino-6-(N-methyl Fluoranilino)fluoran, 2-dipropylamino-6-(N-ethylanilino)fluoran, 2-amino-6-(N-methylanilino)fluoran, 2-amino-6-(N-ethylanilino)fluoran, 2-amino-6-(N-propylanilino)fluoran, 2-amino-6-(N-methyl-p-toluidino)fluoran, 2-amino-6-(N-ethyl-p-toluidino)fluoran, 2-amino-6-(N-propyl-p-toluidino)fluoran, 2-amino-6-(N-methyl-p-ethylanilino)fluoran, 2-amino-6-(N-ethylanilino)fluoran (Tyl-p-ethylanilino)fluoran, 2-amino-6-(N-propyl-p-ethylanilino)fluoran, 2-amino-6-(N-methyl-2,4-dimethylanilino)fluoran, 2-amino-6-(N-ethyl-2,4-dimethylanilino)fluoran, 2-amino-6-(N-propyl-2,4-dimethylanilino)fluoran, 2-amino-6-(N-methyl-p-chloroanilino)fluoran, 2-amino-6-(N-ethyl-p-chloroanilino)fluoran, 2-amino-6-(N-propyl-p-chloroanilino)fluoran, 1,Examples include 2-benzo-6-(N-ethyl-N-isoamylamino)fluorane, 1,2-benzo-6-dibutylaminofluorane, 1,2-benzo-6-(N-methyl-N-cyclohexylamino)fluorane, and 1,2-benzo-6-(N-ethyl-N-toluidino)fluorane. Each of the color-developing layers 24, 27, and 30 may contain one of the above color-developing compounds alone, or two or more.

[0036] (Color developer) A color developer is used, for example, to develop the color of a colorless color-developing compound. The color developer may be in particulate form. Examples of color developers include at least one selected from the group consisting of phenol derivatives, salicylic acid derivatives, and urea derivatives. Specifically, examples include hydroxybenzoic acid type compounds shown in formula (2) below, which contain an electron-accepting group in the molecule. The hydroxybenzoic acid type compound may also be a bis(hydroxybenzoic acid) type compound.

[0037] [ka] (However, X is one of the following: -NHCO-, -CONH-, -NHCONH-, -CONHCO-, -NHNHCO-, -CONHNH-, -CONHNHCO-, -NHCOCONH-, -NHCONHCO-, -CONHCONH-, -NHNHCONH-, -NHCONHNH-, -CONHNHCONH-, -NHCONHNHCO-, and -CONHNHCONH-. R is a linear hydrocarbon group having 25 to 34 carbon atoms.)

[0038] The bonding positions of the hydroxyl group (-OH), carboxyl group (-COOH), and -XR group in formula (2) are not limited. For example, a hydroxybenzoic acid type compound may have a structure in which the hydroxyl group and carboxyl group are bonded to the ortho position of benzene, i.e., a salicylic acid skeleton.

[0039] (Matrix polymer) The matrix polymer (matrix resin) preferably functions as a binder. The matrix polymer is preferably one in which the color-developing compound, color developer, and photothermal conversion material can be homogeneously dispersed. Examples of matrix polymers include at least one selected from the group consisting of thermosetting resins and thermoplastic resins. Specifically, examples include at least one selected from the group consisting of polyvinyl chloride resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, ethylcellulose resins, polystyrene resins, styrene copolymer resins, phenoxy resins, polyester resins, aromatic polyester resins, polyurethane resins, polycarbonate resins, polyacrylic acid ester resins, polymethacrylate resins, acrylic acid copolymer resins, maleic acid polymer resins, polyvinyl alcohol resins, modified polyvinyl alcohol resins, hydroxyethylcellulose resins, carboxymethylcellulose resins, and starch.

[0040] The matrix polymer preferably contains a polycarbonate resin. The inclusion of a polycarbonate resin in the matrix polymer improves the light resistance of the surface of the recording medium 20. Here, a polycarbonate resin is a resin having at least a carbonate group (-O-(C=O)-O-) as a structural unit in its main chain. Therefore, it may also have other structural units in addition to the carbonate group in its main chain.

[0041] The ratio of the color developer to the total amount of the color developer and matrix resin is preferably 16% by mass or less. When the ratio of the color developer is 16% by mass or less, the adhesion between the color-developing layers 24, 27, and 30 and the layers adjacent to the color-developing layers 24, 27, and 30 (especially the heat-insulating layers 23, 26, and 29) can be improved.

[0042] The ratio of the color developer to the total amount of the matrix resin is measured as follows: The composition of the color developer and matrix polymer in the color-developing layer is measured by mapping using a Fourier transform infrared spectrophotometer (micro FTIR). Alternatively, it can be calculated by measuring the weight of each while dissolving them in an appropriate organic solvent, taking advantage of the difference in solubility between the color developer and the matrix polymer.

[0043] From the viewpoint of improving the adhesion between the color-developing layers 24, 27, and 30 and the layers adjacent to them (especially the heat-insulating layers 23, 26, and 29), it is preferable that the matrix polymer content in the color-developing layers 24, 27, and 30 be 84% by mass or more. From the viewpoint of suppressing a decrease in the color development of the color-developing layers 24, 27, and 30, it is preferable that the matrix polymer content be 50% by mass or more and 70% by mass or less, and more preferably 58% by mass or more and 65% by mass or less. When the matrix polymer content is 50% by mass or more and 70% by mass or less, it is preferable to select layers adjacent to the color-developing layers 24, 27, and 30 to obtain good adhesion.

[0044] The matrix polymer content in color-developing layers 24, 27, and 30 is measured as follows: The composition of the color developer and matrix polymer in color-developing layers 24, 27, and 30 is measured by mapping using a Fourier transform infrared spectrophotometer (micro FTIR). Alternatively, it can be calculated by measuring the weight while dissolving each in an appropriate organic solvent, taking advantage of the differences in solubility of the contents in color-developing layers 24, 27, and 30.

[0045] (Photothermal conversion material) Photothermal conversion materials are, for example, materials that absorb light in a predetermined wavelength range in the near-infrared region and generate heat. Preferably, the photothermal conversion material is a near-infrared absorbing dye that has an absorption peak in the wavelength range of 700 nm to 2000 nm and has almost no absorption in the visible region. Specifically, examples include at least one selected from the group consisting of compounds having a phthalocyanine skeleton (phthalocyanine dyes), compounds having a squarylium skeleton (squarylium dyes), and inorganic compounds. Examples of inorganic compounds include at least one selected from the group consisting of metal complexes such as dithio complexes, diimonium salts, aminium salts, and inorganic compounds. Examples of inorganic compounds include at least one selected from the group consisting of graphite, carbon black, metal powder particles, cobalt tetroxide, iron oxide, chromium oxide, copper oxide, titanium black, metal oxides such as ITO (Indium Tin Oxide), metal nitrides such as niobium nitride, metal carbides such as tantalum carbide, metal sulfides, and various magnetic powders. In addition, compounds having a cyanine skeleton with excellent lightfastness and heat resistance (cyanine dyes) may be used. Here, excellent lightfastness means that the compound does not decompose under the usage environment, for example, when exposed to light from a fluorescent lamp. Excellent heat resistance means that, for example, when formed into a film with a polymer material and stored at 150°C for 30 minutes, the maximum absorption peak value of the absorption spectrum does not change by more than 20%. Examples of compounds having such a cyanine skeleton include those having at least one of the following counterions in the molecule: SbF6, PF6, BF4, ClO4, CF3SO3, and (CF3SO3)2N, and a methine chain containing a five-membered ring or a six-membered ring. In the first embodiment, it is preferable that the cyanine skeleton compound used in the recording medium 20 has both one of the above counterions and a cyclic structure such as a five-membered ring or a six-membered ring in the methine chain, but sufficient lightfastness and heat resistance are ensured if at least one of them is present.

[0046] Furthermore, it is preferable to select a photothermal conversion material that has a narrow light absorption band in the wavelength range of 700 nm to 2000 nm, and in which the light absorption bands of the color-developing layers 24, 27, and 30 do not overlap with each other. This makes it possible to selectively color a desired layer among the color-developing layers 24, 27, and 30.

[0047] (Insulation layer) The thermal insulation layer 23 is provided between the substrate 21 and the color-developing layer 24 to insulate the space between the substrate 21 and the color-developing layer 24. The thermal insulation layer 26 is provided between the color-developing layer 24 and the color-developing layer 27 to insulate the space between the color-developing layer 24 and the color-developing layer 27. The thermal insulation layer 29 is provided between the color-developing layer 27 and the color-developing layer 30 to insulate the space between the color-developing layer 27 and the color-developing layer 30. The thermal insulation layer 34 is provided between the color-developing layer 30 and the protective layer 31 to insulate the space between the color-developing layer 30 and the protective layer 31. The thermal insulation layers 23, 26, 29, and 34 include, for example, a general translucent polymer material. Specific materials include, for example, at least one selected from the group consisting of acrylic resins, polyvinyl chloride resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate copolymer resins, ethylcellulose resins, polystyrene resins, styrene copolymer resins, phenoxy resins, polyester resins, aromatic polyester resins, polyurethane resins, polycarbonate resins, polyacrylic acid ester resins, polymethacrylate resins, acrylic acid copolymer resins, maleic acid polymer resins, polyvinyl alcohol resins, modified polyvinyl alcohol resins, hydroxyethylcellulose resins, carboxymethylcellulose resins, and starch. The insulating layers 23, 26, 29, and 34 may also contain various additives such as ultraviolet absorbers.

[0048] The heat insulating layers 23, 26, 29, and 34 may be UV-curable resin layers. The UV-curable resin layer contains a UV-curable resin composition that has undergone a polymerization reaction and solidified. More specifically, for example, the UV-curable resin layer contains a polymer of a polymerizable compound and a polymer that has undergone a structural change when a polymerization initiator generates active species upon irradiation with external energy (ultraviolet light). The UV-curable resin composition includes, for example, at least one selected from the group consisting of radical polymerization type UV-curable resin compositions and cationic polymerization type UV-curable resin compositions. The UV-curable resin composition may optionally contain at least one selected from the group consisting of sensitizers, fillers, stabilizers, leveling agents, defoamers, and viscosity modifiers. The UV-curable resin composition may be a UV-curable resin composition for hard coatings. The UV-curable resin composition may be an acrylic UV-curable resin composition.

[0049] The insulating layers 23, 26, 29, and 34 may contain translucent inorganic materials. For example, using porous silica, alumina, titania, carbon, or composites thereof is preferable as it results in low thermal conductivity and a high insulating effect. The insulating layers 23, 26, and 29 can be formed, for example, by the sol-gel method.

[0050] By adjusting the thickness of the insulating layers 23, 26, 29, and 34, the thickness of the recording medium 20 can be made to match the thickness of the intermediate layer 13, thereby suppressing the occurrence of physical steps. The thickness of the insulating layers 23, 26, 29, and 34 is preferably 3 μm to 100 μm, more preferably 5 μm to 50 μm. If the thickness of the insulating layers 23, 26, 29, and 34 is 3 μm or more, a sufficient heat insulation effect can be obtained. On the other hand, if the thickness of the insulating layers 23, 26, 29, and 34 is 100 μm or less, a decrease in light transmittance can be suppressed. Furthermore, a decrease in the bending resistance of the recording medium 20 can be suppressed, making it less likely for defects such as cracks to occur.

[0051] The pencil hardness of the surfaces of the heat insulating layers 23, 26, 29, and 34 is preferably 2B or higher, more preferably H or higher. When the pencil hardness of the surfaces of the heat insulating layers 23, 26, 29, and 34 is 2B or higher, the density of the heat insulating layers 23, 26, 29, and 34 is high, and the diffusion of substances through the intermediate layers 32A, 32B, 32C, and 32D can be further suppressed. For example, when the pencil hardness of the surfaces of the heat insulating layers 26 and 29 is 2B or higher, the diffusion of color-developing compounds through the intermediate layers 32B and 32C can be further suppressed. Therefore, the change in hue of the color-developing layers 24, 27, and 30 during long-term storage can be further suppressed. As the heat insulating layers 23, 26, 29, and 34 having the above-mentioned pencil hardness, ultraviolet-curable resin layers are preferred.

[0052] The pencil hardness of the surface of the insulation layer 23 is measured as follows: First, the laminate 10 is disassembled to expose the surface of the insulation layer 23. Next, the pencil hardness of the surface of the insulation layer 23 is measured in accordance with JIS K5600-5-4. This measurement is performed in a standard atmosphere with a temperature of 23±1℃ and a relative humidity of 50±5%. The pencil hardness of the surfaces of the insulation layers 26, 29, and 34 is measured using the same procedure as the pencil hardness of the surface of the insulation layer 23.

[0053] (Adhesive layer) The adhesive layer 22 is provided between the base material 21 and the heat insulating layer 23, bonding the base material 21 and the heat insulating layer 23 together. The adhesive layer 25 is provided between the color developing layer 24 and the heat insulating layer 26, bonding the color developing layer 24 and the heat insulating layer 26 together. The adhesive layer 28 is provided between the color developing layer 27 and the heat insulating layer 29, bonding the color developing layer 27 and the heat insulating layer 29 together. The adhesive layer 33 is provided between the color developing layer 30 and the heat insulating layer 34, bonding the color developing layer 30 and the heat insulating layer 34 together. If the recording medium 20 does not have a heat insulating layer 23, the adhesive layer 22 bonds the base material 21 and the color developing layer 24 together. In this case, the adhesive layer 22 may function as a heat insulating layer and / or a diffusion-preventing layer. If the recording medium 20 does not have a heat insulating layer 26, the adhesive layer 25 bonds the color developing layer 24 and the color developing layer 27 together. In this case, the adhesive layer 25 may function as a heat insulating layer and / or a diffusion-preventing layer. If the recording medium 20 does not have a heat insulating layer 29, the adhesive layer 28 bonds the color-developing layer 27 and the color-developing layer 30. In this case, the adhesive layer 28 may function as a heat insulating layer and / or a diffusion-preventing layer. If the recording medium 20 does not have a heat insulating layer 34, the adhesive layer 33 bonds the color-developing layer 30 and the protective layer 31. In this case, the adhesive layer 33 may function as a heat insulating layer and / or a diffusion-preventing layer. In this specification, "and / or" means at least one of the three possibilities: X and / or Y, for example, X only, Y only, or X and Y.

[0054] The adhesive layers 22, 25, 28, and 33 contain an adhesive. The adhesive includes, for example, at least one selected from the group consisting of acrylic resins, silicone resins, urethane resins, epoxy resins, and elastomer materials.

[0055] (protective layer) The protective layer 31 is for protecting the surface of the recording medium 20 and is formed using, for example, at least one of ultraviolet-curable resins and thermosetting resins. The protective layer 31 is preferably a hard coat layer. The thickness of the protective layer 31 is, for example, 0.1 μm or more and 20 μm or less.

[0056] (Average peel strength between layers) The average peel strength at the interfaces between each layer constituting the laminate 10 is preferably 3.5 N / cm or more, more preferably 4.0 N / cm or more, even more preferably 4.5 N / cm or more, and particularly preferably 5.0 N / cm or more. When the average peel strength at the interfaces between each layer is 3.5 N / cm or more, peeling at the interfaces between each layer constituting the laminate 10 can be suppressed. Therefore, the anti-counterfeiting and anti-tampering properties of the laminate 10 can be improved. Here, each layer constituting the laminate 10 may include each layer constituting the recording medium 20.

[0057] The average peel strength at the interface between each layer is determined by performing a 90-degree peel test. Since the method for measuring the average peel strength at the interface between each layer is the same, only the method for measuring the average peel strength at the interface between the heat insulating layer 26 and the coloring layer 27 will be described below with reference to Figure 11.

[0058] First, the laminate 10 is cut into a strip 10 mm wide and 100 mm long to prepare a test piece 60, which is left in a standard atmosphere of 23 ± 1 °C and 50 ± 5% relative humidity for 24 hours or more. When measuring the average peel strength of the interface contained in the recording medium 20, the test piece 60 is cut so as to include the recording medium 20. Hereinafter, the laminate below the interface between the heat insulating layer 26 and the color developing layer 27 of the test piece 60 is referred to as the adherend 60A, and the laminate above the interface is referred to as the adherend 60B (see Figure 3). Next, at one end of the test piece 60 in the longitudinal direction, a notch is made between adherend 60A and adherend 60B with a sharp blade such as a cutter, and adherend 60B is peeled off in the longitudinal direction for a length of 20 mm to create a gripping area. Then, the side of the test piece 60 on the adherend 60A side is fixed to the test stand 71 with a strong adhesive. As an adhesive, one with sufficiently high adhesive strength is selected to prevent the test piece 60 from peeling off the test stand 71 when measuring the peel strength between the heat insulating layer 26 and the color developing layer 27, such as 3M's Scotch® strong adhesive tape.

[0059] Next, one end of the tension member 61 is attached to the surface of the adherend 60B on the side with the coloring layer 27. The tension member 61 is a strip-shaped film with sufficient strength so as not to elongate or break during the measurement of peel strength. In addition, one end of the tension member 61 is attached to the adherend 60B with sufficiently high adhesive force so as not to peel off from the adherend 60A during the measurement of peel strength. Figure 11 shows an example in which the tension member 61 is used as a gripping space, but if there is sufficient stroke before the adherend 60B is clamped by the clamping device (metal plate) 62, the adherend 60B may be clamped directly without using the tension member 61.

[0060] Next, the gripping portion of the tensile member 61 is passed between a pair of movable rolls 73A and 73B of the jig 72, and then the gripping portion is clamped and fixed by 10 mm or more using the clamping device (metal plate) 62 of the tensile and compression testing machine SV-55C 2H manufactured by Imada Seisakusho Co., Ltd. The movable rolls 73A and 73B serve as the fulcrum for peeling during the 90-degree peel test. Next, a 90-degree peel test is performed using the tensile and compression testing machine, and the test force [N / 10 mm] and stroke [mm] are monitored as voltage values, for example, using a data logger manufactured by Keyence Corporation, converted to force, and stored in memory as CSV output data. The above 90-degree peel test is performed at a tensile speed of 5 mm / sec. under standard conditions of a temperature of 23 ± 1 °C and a relative humidity of 50 ± 5%. The stroke is set to 50 mm or more.

[0061] The above 90-degree peel test is performed a total of three times. The point where the peel strength is stable (where the force rises gradually) is used as the starting point (0 mm), and the CSV output data from that point to a relative distance of 50 mm is used to calculate the average value. This allows the average peel strength between the insulation layer 26 and the coloring layer 27 to be determined. However, if there are points (spikes) in the CSV output data where the peel force is suddenly low, these points (spikes) are excluded when calculating the average peel strength.

[0062] The average of the minimum peel strengths between each layer constituting the laminate 10 is preferably 3.5 N / cm or more, more preferably 4.0 N / cm or more, even more preferably 4.5 N / cm or more, and particularly preferably 5.0 N / cm or more. As described above, when the average of the minimum peel strengths is 3.5 N / cm or more, peeling between each layer constituting the laminate 10 can be suppressed. Therefore, the anti-counterfeiting and anti-tampering properties of the laminate 10 can be improved. Here, each layer constituting the laminate 10 may include each layer constituting the recording medium 20.

[0063] The average of the minimum peel strengths between each layer constituting the laminate 10 is determined by performing a 90-degree peel test. The method for measuring the average of the minimum peel strengths between each layer will be explained below with reference to Figures 12A and 12B.

[0064] First, the laminate 10 is cut into strips 10 mm wide and 100 mm long to prepare test specimens 60, which are left in a standard atmosphere of 23 ± 1 °C and 50 ± 5% relative humidity for at least 24 hours. Next, as shown in Figure 12A, the surface of the test specimen 60 facing the base material 11 is fixed to the test stand 71 with a strong adhesive, and the tensile member 61 is attached to the surface of the test specimen 60 facing the overlay layer 15. As the tensile member 61, a strip of film with sufficient strength is used so as not to elongate or break during the measurement of the average peel strength. In addition, one end of the tensile member 61 is attached to the adherend 60B with sufficiently high adhesive strength so as not to peel off from the adherend 60B during the measurement of the average peel strength.

[0065] Next, as shown in Figure 12B, the gripping portion of the tensile member 61 is passed between a pair of movable rolls 73A and 73B of the jig 72, and then the gripping portion is clamped and fixed by 10 mm or more using the clamping device (metal plate) 62 of the tensile and compression testing machine SV-55C 2H manufactured by Imada Seisakusho Co., Ltd. The subsequent steps are the same as the method for measuring the average peel strength at the interface between the heat insulating layer 26 and the coloring layer 27. As a result, the average value of the minimum peel strength among the peel strengths between each layer constituting the laminate 10 can be determined.

[0066] The interface with the lowest average peel strength among the interfaces of the laminate 10 is preferably located between the color-developing layer 24 and the color-developing layer 27, or between the color-developing layer 27 and the color-developing layer 30. When the laminate 10 is disassembled, the recording medium 20 is also disassembled, making it difficult to remove and use the recording medium 20. Therefore, the anti-counterfeiting properties of the laminate 10 can be improved.

[0067] (Combination of materials for the base, intermediate layer, and overlay layer) From the viewpoint of improving adhesion, it is preferable that the base material 11, intermediate layer 13, and overlay layer 15 contain the same type of resin material. The resin material may be a thermoplastic resin. From the viewpoint of environmental consideration, it is preferable that the base material 11, intermediate layer 13, and overlay layer 15 contain polycarbonate (PC) resin or polyethylene terephthalate (PET) resin. From the viewpoint of improving durability, it is preferable that the base material 11, intermediate layer 13, and overlay layer 15 contain polycarbonate (PC) resin or polyvinyl chloride (PVC) resin. From the viewpoint of improving adhesion, environmental consideration, and durability, it is preferable that the base material 11, intermediate layer 13, and overlay layer 15 contain polycarbonate (PC) resin.

[0068] The presence of the same type of resin material in the substrate 11, intermediate layer 13, and overlay layer 15 can be confirmed, for example, as follows: First, the substrate 11, intermediate layer 13, and overlay layer 15 are removed from the laminate 10. Next, the IR spectra of the substrate 11, intermediate layer 13, and overlay layer 15 are obtained by infrared absorption spectroscopy (IR). Then, by comparing the obtained IR spectra of each layer, it is confirmed that the substrate 11, intermediate layer 13, and overlay layer 15 contain the same type of resin material. Furthermore, by using the acquired IR spectra of each layer, it is possible to confirm the types of resin materials contained in the substrate 11, intermediate layer 13, and overlay layer 15, respectively.

[0069] [1.2 Method for manufacturing laminates] Hereinafter, an example of a method for manufacturing the laminate 10 according to the first embodiment of this disclosure will be described.

[0070] First, a thermosetting resin is applied to one main surface of the base material 11 as a thermal adhesive to form an adhesive layer 12. Next, an intermediate layer 13 is placed on the adhesive layer 12, and then the recording medium 20 is fitted into the housing portion 13A of the intermediate layer 13. Alternatively, the intermediate layer 13 with the recording medium 20 already fitted into the housing portion 13A may be placed on the adhesive layer 12. The adhesive layer 12 may also be formed by applying a thermosetting resin to the intermediate layer 13 with the recording medium 20 already fitted into the housing portion 13A, and then placing the intermediate layer 13 on the main surface of the base material 11 with the coating film sandwiched in between. Alternatively, the adhesive layer 12 may be formed by bonding a sheet, which has been formed in advance by applying a thermosetting resin to a separator, to the main surface of the base material 11 or to the intermediate layer 13 with the recording medium 20 already fitted into the housing portion 13A by means of thermal lamination or the like.

[0071] Next, a thermosetting resin is applied to the intermediate layer 13 as a thermal adhesive to form an adhesive layer 14, and then an overlay layer 15 is placed on the adhesive layer 14. Next, the resulting laminate is sandwiched between metal plates and heated and pressurized to heat-cur the adhesive layer 12 and adhesive layer 14. The temperature applied to the laminate during heat curing is preferably 100°C to 120°C from the viewpoint of reducing damage to the recording medium 20. This yields the desired laminate 10. The adhesive layer 14 may also be formed by applying a thermosetting resin to the overlay layer 15 and then placing the overlay layer 15 on the intermediate layer 13 with the coating film in between. Alternatively, the adhesive layer 14 may be formed by bonding a sheet, which has been formed in advance by applying a thermosetting resin to a separator, to the overlay layer 15 or the intermediate layer 13 by means of thermal lamination or the like.

[0072] [1.3 Recording Method for Laminated Structures] In the laminate 10 according to the first embodiment, patterns and the like can be recorded on the recording medium 20, for example, as follows. Here, the case in which the color-developing layers 24, 27, and 30 exhibit cyan, magenta, and yellow colors, respectively, will be described as an example.

[0073] For example, infrared light having a specified wavelength and output is irradiated onto the recording medium 20 via the overlay layer 15 using a semiconductor laser or the like. When coloring the color-developing layer 24, infrared light with wavelength λ1 is irradiated onto the color-developing layer 24 with an energy sufficient to cause the color-developing layer 24 to reach its color-developing temperature. As a result, the photothermal conversion material contained in the color-developing layer 24 generates heat, causing a color reaction (color development reaction) to occur between the color-developing compound and the color developer, and the irradiated area develops a cyan color. Similarly, when coloring the color-developing layer 27, infrared light with wavelength λ2 is irradiated onto the color-developing layer 27 with an energy sufficient to cause the color-developing layer 27 to reach its color-developing temperature. When coloring the color-developing layer 30, infrared light with wavelength λ3 is irradiated onto the color-developing layer 30 with an energy sufficient to cause the color-developing layer 30 to reach its color-developing temperature. As a result, the photothermal conversion materials contained in the color-developing layer 27 and the color-developing layer 30 generate heat, causing a color reaction between the color-developing compound and the color developer, resulting in magenta and yellow colors appearing in the irradiated area, respectively. In this way, by irradiating any area with infrared light of the corresponding wavelength, it becomes possible to record patterns (for example, full-color patterns).

[0074] [1.4 Actions and Effects] As described above, in the laminate 10 according to the first embodiment, the base material 11 and the intermediate layer 13 are bonded together by an adhesive layer 12 containing a thermal adhesive, and the intermediate layer 13 and the overlay layer 15 are bonded together by an adhesive layer 12 containing a thermal adhesive. This allows for a strong bond between the base material 11 and the intermediate layer 13, and between the intermediate layer 13 and the overlay layer 15. Therefore, the anti-counterfeiting properties of the laminate 10 can be improved. Furthermore, the tamper-proof properties of the laminate 10 can also be improved. Thus, the security of the laminate 10 can be improved.

[0075] Since the recording medium 20 is equipped with color-developing layers 24, 27, and 30, it can convert photographic images and the like of a laminated body 10 such as a plastic security card into full color. Since the laminate 10 includes the full-color recording medium 20 in a portion of its surface, costs can be reduced compared to the case where the full-color recording medium 20 is included across the entire surface of the laminate 10. Since the recording medium 20 is fitted into the housing portion 13A of the intermediate layer 13, it is possible to make it difficult to see the boundary between the recording medium 20 and the intermediate layer 13 in the in-plane direction of the laminate 10. Therefore, it becomes difficult to identify where in the plane of the laminate 10 the recording medium 20 is located. Thus, the anti-counterfeiting properties can be improved. Since the recording medium 20 is sealed inside the laminate 10, the effect of moisture on the recording medium 20 can be reduced. Since the recording medium 20 is equipped with thermal insulation layers 23, 26, and 29, the thickness of the recording medium 20 can be made to match the thickness of the intermediate layer 13 by adjusting the thickness of the thermal insulation layers 23, 26, and 29. Therefore, it is possible to suppress the occurrence of a physical step at the boundary between the recording medium 20 and the intermediate layer 13.

[0076] <2 Second Embodiment> [2.1 Structure of the Laminate] Figure 4 is a cross-sectional view of a laminate 40 according to a second embodiment of the present disclosure. The laminate 40 differs from the laminate 10 according to the first embodiment in that it does not have adhesive layers 12 and 14, and the substrate 11 and the intermediate layer 13 and the intermediate layer 13 and the overlay layer 15 are bonded together by fusion.

[0077] In the second embodiment, it is preferable that the base material 11, the intermediate layer 13, and the overlay layer 15 contain a thermoplastic resin as the plastic. By including a thermoplastic resin in the base material 11, the intermediate layer 13, and the overlay layer 15, the interlayer adhesion strength due to fusion can be increased. From the viewpoint of reducing damage to the recording medium 20, it is preferable that the thermoplastic resin is capable of heat-sealing the interlayers of the laminate 40 in a temperature range of 130°C to 200°C.

[0078] The base material 11, the intermediate layer 13, and the overlay layer 15 may contain the same type of thermoplastic resin, or they may not contain the same type of thermoplastic resin. If the base material 11, the intermediate layer 13, and the overlay layer 15 do not contain the same type of thermoplastic resin, one of the base material 11, the intermediate layer 13, and the overlay layer 15 may contain a different type of thermoplastic resin than the other two layers, or each of the base material 11, the intermediate layer 13, and the overlay layer 15 may contain different types of thermoplastic resin.

[0079] When the base material 11, intermediate layer 13, and overlay layer 15 contain the same type of thermoplastic resin, it is preferable that the base material 11, intermediate layer 13, and overlay layer 15 contain at least one selected from the group consisting of semicrystalline thermoplastic resins and amorphous thermoplastic resins, from the viewpoint of improving interlayer adhesion strength by fusion.

[0080] The semi-crystalline thermoplastic resin includes, for example, at least one selected from the group consisting of polypropylene (PP), polyethylene (PE), polyacetal (POM), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyphenylene sulfide (PPS), and polyether ether ketone (PEEK).

[0081] The amorphous thermoplastic resin includes, for example, at least one selected from the group consisting of ABS resin, polycarbonate (PC), polymer alloy of ABS resin and PC (hereinafter referred to as "ABS / PC polymer alloy"), AS resin, polystyrene (PS), polymethyl methacrylate (PMMA), polyphenylene oxide (PPO), polysulfone (PSU), polyvinyl chloride (PVC), polyetherimide (PEI), and polyethersulfone (PES).

[0082] If the base material 11, intermediate layer 13, and overlay layer 15 do not contain the same type of thermoplastic resin, it is preferable that the base material 11, intermediate layer 13, and overlay layer 15 contain an amorphous thermoplastic resin from the viewpoint of improving interlayer adhesion strength through fusion.

[0083] The following combinations of amorphous thermoplastic resins are preferred for the two adjacent layers of the laminate 40. If one of the two adjacent layers of the laminate 40 contains ABS resin, it is preferable that the other layer contains at least one selected from the group consisting of ABS / PC polymer alloy, polycarbonate (PC), AS resin, polystyrene (PS), polymethyl methacrylate (PMMA), and polyvinyl chloride (PVC).

[0084] If one of two adjacent layers of the laminate 40 contains an ABS / PC polymer alloy, it is preferable that the other layer contains at least one selected from the group consisting of ABS resin, polycarbonate (PC), and polymethyl methacrylate (PMMA).

[0085] If one of two adjacent layers of the laminate 40 contains AS resin, it is preferable that the other layer contains at least one selected from the group consisting of ABS resin, polystyrene (PS), polymethyl methacrylate (PMMA), and polyphenylene oxide (PPO).

[0086] If one of two adjacent layers of the laminate 40 contains polymethyl methacrylate (PMMA), it is preferable that the other layer contains at least one selected from the group consisting of ABS resin, ABS / PC polymer alloy, AS resin, and polyphenylene oxide (PPO). If one of two adjacent layers of the laminate 40 contains polyphenylene oxide (PPO), it is preferable that the other layer contains at least one selected from the group consisting of polycarbonate (PC), AS resin, polystyrene (PS), and polymethyl methacrylate (PMMA).

[0087] If one of two adjacent layers of the laminate 40 contains polysulfone (PSU), it is preferable that the other layer contains polycarbonate (PC). If one of two adjacent layers of the laminate 40 contains polyvinyl chloride (PVC), it is preferable that the other layer contains ABS resin.

[0088] [2.2 Method for manufacturing laminates] Hereinafter, an example of a method for manufacturing the laminate 10 according to the second embodiment of this disclosure will be described.

[0089] First, an intermediate layer 13 is placed on one main surface of the base material 11, and then the recording medium 20 is fitted into the housing portion 13A of the intermediate layer 13. Alternatively, the intermediate layer 13 with the recording medium 20 already fitted into the housing portion 13A may be placed on one main surface of the base material 11. Next, an overlay layer 15 is placed on the intermediate layer 13. Then, the resulting laminate is sandwiched between metal plates and heat-fused with pressure while being heated, thereby thermally fusing the base material 11 and the intermediate layer 13, and the intermediate layer 13 and the overlay layer 15. The temperature applied to the laminate during thermal fusion is preferably between 130°C and 200°C, from the viewpoint of reducing damage to the recording medium 20 and achieving sufficient fusion strength. This yields the desired laminate 40.

[0090] [2.3 Effects] As described above, in the laminate 40 according to the second embodiment, the substrate 11 and the intermediate layer 13 and the intermediate layer 13 and the overlay layer 15 are fused together. This allows for a strong bond between the substrate 11 and the intermediate layer 13 and between the intermediate layer 13 and the overlay layer 15. Therefore, the anti-counterfeiting properties of the laminate 40 can be improved. Furthermore, the tamper-proof properties of the laminate 40 can also be improved. Thus, the security of the laminate 40 can be improved.

[0091] <3 Third Embodiment> [3.1 Structure of the Laminate] Figure 13 is a perspective view of a laminate 10A according to a third embodiment of the present disclosure. Figure 14 is a cross-sectional view along line XIV-XIV in Figure 13. The laminate 10A comprises a substrate 11, an adhesive layer 12, an intermediate layer 16, an adhesive layer 14, an overlay layer 15, and a recording medium 20A. In the third embodiment, the same reference numerals are used for parts that are the same as in the first embodiment, and their description is omitted.

[0092] (Middle class) The intermediate layer 16 can protect the side surface of the recording medium 20A. The intermediate layer 16 surrounds the peripheral edge of one main surface of the base material 11. The intermediate layer 16 has a frame-like shape in plan view. In this specification, the peripheral edge of one main surface refers to a region having a predetermined width extending inward from the peripheral edge of one main surface. In this specification, a plan view refers to a plan view when the object is viewed from a direction perpendicular to one main surface of the base material 11.

[0093] The intermediate layer 16 has a housing section 16A. The recording medium 20A is housed in the housing section 16A. The housing section 16A is a through hole that penetrates in the thickness direction of the recording medium 20A. It is preferable that the thickness of the intermediate layer 16 and the recording medium 20A are approximately the same. This makes it possible to suppress the occurrence of a step at the boundary between the intermediate layer 16 and the recording medium 20A when the recording medium 20A is housed in the housing section 16A.

[0094] The intermediate layer 16 has a film-like structure. The intermediate layer 16 may be transparent. The intermediate layer 16 contains plastic. Examples of plastic materials include those similar to those used for the base material 11.

[0095] (Recording medium 20A) Figure 15 is a cross-sectional view of the recording medium 20A. The recording medium 20A comprises a base material 21, an adhesive layer 22, a color development layer 24, an intermediate layer 35A, a color development layer 27, an intermediate layer 35B, a color development layer 30, an intermediate layer 35C, and a protective layer 36 in this order. More specifically, the recording medium 20A comprises a base material 21, an adhesive layer 22, a color development layer 24, a heat insulating layer 26, an adhesive layer 25, a color development layer 27, a heat insulating layer 29, an adhesive layer 28, a color development layer 30, a heat insulating layer 34, an adhesive layer 33, and a protective layer 36 in this order. The heat insulating layers 26, 29, and 34 are provided as needed and may not be provided. The recording medium 20A is housed in the housing portion 16A of the intermediate layer 16 such that the base material 21 faces the adhesive layer 12 and the protective layer 31 faces the adhesive layer 14.

[0096] (Middle class) Intermediate layer 35A is the same as intermediate layer 32B of the recording medium 20, except that the heat insulating layer 26 is adjacent to the color developing layer 24 and the adhesive layer 25 is adjacent to the color developing layer 27. Intermediate layer 35B is the same as intermediate layer 32C of the recording medium 20, except that the heat insulating layer 29 is adjacent to the color developing layer 27 and the adhesive layer 28 is adjacent to the color developing layer 30. Intermediate layer 35C is the same as intermediate layer 32D of the recording medium 20, except that the heat insulating layer 34 is adjacent to the color developing layer 30 and the adhesive layer 33 is adjacent to the protective layer 36.

[0097] (Protective layer 36) The protective layer 36 comprises, in order, an ultraviolet-curable resin layer 36A, a UV-cut layer 36B, an adhesive layer 36C, and a substrate 36D on one main surface of the intermediate layer 35C. The ultraviolet-curable resin layer 36A can protect the surface of the recording medium 20A. The ultraviolet-curable resin layer 36A may also function as a heat insulating layer and / or a diffusion-blocking layer. The UV-cut layer 36B can cut ultraviolet rays incident on the color-developing layers 24, 27, and 30.

[0098] The adhesive layer 36C can bond the UV-cut layer 36B and the substrate 36D. Examples of materials for the adhesive layer 36C include those similar to those used for adhesive layers 22, 25, and 28. The substrate 36D can support the UV-curing resin layer 36A, the UV-cut layer 36B, and the adhesive layer 36C. The substrate 36D can protect the surface of the recording medium 20A. Examples of materials for the substrate 36D include those similar to those used for substrate 11.

[0099] [3.2 Action and Effects] In the laminate 10A according to the third embodiment, the same effects and advantages as the laminate 10 according to the first embodiment can be obtained.

[0100] <4. Fourth Embodiment> [4.1 Structure of the Laminate] Figure 16 is a cross-sectional view of a laminate 40A according to the fourth embodiment of this disclosure. Laminate 40A differs from laminate 40 according to the second embodiment in that it comprises an intermediate layer 16 and a recording medium 20A instead of the intermediate layer 13 and the recording medium 20 (see Figure 4). The intermediate layer 16 and the recording medium 20A are as described in the third embodiment.

[0101] [4.2 Action and Effects] In the laminate 40A according to the fourth embodiment, the same effects and advantages as the laminate 40 according to the second embodiment can be obtained.

[0102] <5 Variations> (Variation 1) In the first embodiment, an example was described in which the housing portion 13A is a through hole that penetrates in the thickness direction of the intermediate layer 13. However, as shown in Figure 5, the housing portion 13A may be a bottomed recess that is recessed in the thickness direction of the intermediate layer 13. In this case, the recess may be provided on the main surface of the intermediate layer 13 that faces the overlay layer 15, or on the main surface that faces the base material 11. Similarly in the second embodiment, the housing portion 13A may be provided with a recess instead of a through hole. Similarly in the third embodiment, as shown in Figure 17, the housing portion 16A may be provided with a recess instead of a through hole. Similarly in the fourth embodiment, the housing portion 17A may be provided with a recess instead of a through hole.

[0103] (Modification 2) In the first, second, third, and fourth embodiments, examples were described in which the laminates 10, 40, 10A, and 40A comprise recording media 20, 20A each having three color-developing layers (color-developing layers 24, 27, and 30) with different color hues. However, recording media may also be provided with a single-layer structure that has color-developing layers capable of multi-color display.

[0104] Figure 6 is a cross-sectional view of a recording medium 50 capable of multi-color display even with a single-layer structure. The recording medium 50 comprises a base material 51, a color-developing layer 52, and a protective layer 53 in this order. The base material 51 and protective layer 53 are the same as the base material 21 and protective layer 31 in the first embodiment, respectively.

[0105] The color-developing layer 52 contains three types of microcapsules 52C, 52M, and 52Y, each exhibiting a different color in its color-developing state. That is, the color-developing layer 52 contains three types of microcapsules 52C, 52M, and 52Y, each exhibiting a different color in its color-developing state. The color-developing layer 52 may optionally contain a first matrix polymer. Each of the three types of microcapsules 52C, 52M, and 52Y contains, for example, a color-developing compound exhibiting a different color (e.g., cyan (C), magenta (M), and yellow (Y)), a color developer corresponding to each color-developing compound, a photothermal conversion material that absorbs light in different wavelength ranges and generates heat, and a second matrix polymer. It is preferable to use a material similar to the material constituting the thermal insulation layers 23, 26, and 29 as the material for the microcapsule wall containing the above materials.

[0106] (Variation 3) In the first, second, third, and fourth embodiments, examples were described in which the recording media 20 and 20A have three color-developing layers (color-developing layers 24, 27, and 30). However, the recording media 20 and 20A may have a single color-developing layer. In this case, the recording media 20 and 20A may comprise a substrate, an adhesive layer, a color-developing layer, and a protective layer in this order. The color-developing layer may exhibit black color when colored.

[0107] Furthermore, the recording media 20, 20A may be provided with a first color-developing layer to an nth color-developing layer (where n is an integer of 2 or more). In this case, the first to nth color-developing layers may contain color-developing compounds with different color hues from each other.

[0108] (Modification 4) In the first and second embodiments, the intermediate layer 13 may be composed of a recording medium that can be rewritten with a pattern or the like by an external stimulus such as laser light or heat. More specifically, it may be composed of a recording medium whose coloring state can be reversibly changed by an external stimulus such as laser light or heat. The recording medium may have a configuration that enables full-color recording, or it may be capable of monochrome or other single-color recording.

[0109] (Modified Example 5) In the first, second, third, and fourth embodiments, the color developer may contain a compound represented by the following formula (3).

Chemical formula

[0110] Since X 0 contains at least one benzene ring, the melting point can be increased compared to the case where X 0 is an aliphatic hydrocarbon group (e.g., a normal alkyl chain), so the color retention property during storage at high temperature and high humidity (hereinafter referred to as "high temperature and high humidity storage property") can be improved. From the viewpoints of improving the high temperature and high humidity storage property and heat resistance, it is preferable that X 0 contains at least two benzene rings. The high temperature and high humidity storage property is, for example, the storage property in an environment of 80°C and 60% RH. When the heat resistance is improved, the resistance of the recording medium 20 to severe processes (e.g., heat pressing or integral molding using a molten resin, etc.) is improved. When X 0 contains at least two benzene rings, the at least two benzene rings may be condensed. For example, it may be naphthalene or anthracene, etc.

[0111] [[ID=​​​Because each of these groups is independently a hydrogen bonding group, the color developers tend to remain somewhat cohesive through hydrogen bonding, thereby improving the stability of the color developers within the color development layers 24, 27, and 30. In this specification, a hydrogen bonding group means a functional group that contains an atom capable of forming hydrogen bonds with other functional groups or atoms present in other compounds.

[0112] The color developer preferably contains a compound represented by the following formula (4). [ka] (However, in equation (4), X 1 Y is a divalent group containing at least one benzene ring. 11 , Y 12 , Y 13 , Y 14 Each of them is an independent, undivided base. Z 11 , Z 12 Each of these is an independent hydrogen bonding group.

[0113] X 1 X contains at least one benzene ring. 1 Since the melting point can be increased compared to when it is an aliphatic hydrocarbon group (e.g., a normal alkyl chain), the high-temperature, high-humidity storage characteristics can be improved. From the viewpoint of improving high-temperature, high-humidity storage characteristics and heat resistance, X 1 However, it is preferable that it contains at least two benzene rings. 1 If it contains at least two benzene rings, at least two benzene rings may be fused together. For example, it may be naphthalene or anthracene, etc.

[0114] Z 11 , Z 12 Because each of these groups is independently a hydrogen bonding group, the color developers tend to remain somewhat cohesive through hydrogen bonding, thereby improving the stability of the color developers within the color development layers 24, 27, and 30.

[0115] When formulas (3) and (4) contain hydrocarbon groups, these hydrocarbon groups are a general term for groups composed of carbon (C) and hydrogen (H), and may be saturated hydrocarbon groups or unsaturated hydrocarbon groups. Saturated hydrocarbon groups are aliphatic hydrocarbon groups that do not have multiple carbon-carbon bonds, and unsaturated hydrocarbon groups are aliphatic hydrocarbon groups that have multiple carbon-carbon bonds (carbon-carbon double bonds or carbon-carbon triple bonds).

[0116] If formulas (3) and (4) contain a hydrocarbon group, the hydrocarbon group may be in the form of a chain or may contain one or more rings. The chain may be linear or branched with one or more side chains, etc.

[0117] (X containing one benzene ring) 0 , X 1 ) X in equation (3) 0 and X in equation (4) 1 This is, for example, a divalent group containing one benzene ring. This divalent group can be represented, for example, by the following formula (5). [ka] (However, in equation (5), X 21 It can be there or not, X 21 If X 21 X is a divalent group. 22 It can be there or not, X 22 If X 22 R is a divalent group. 21 is a single-valued base. n21 is an integer from 0 to 4. If n21 is an integer from 2 to 4, then R 21 These elements may be identical or different. (* indicates a connection point.)

[0118] In equation (5), X relative to the benzene ring 21 and X 22 The bonding position of X is not limited. That is, X relative to the benzene ring. 21 and X 22The bond position may be the ortho, meta, or para position.

[0119] The above divalent group containing one benzene ring is preferably represented by the following formula (6) from the viewpoint of improving high-temperature and high-humidity storage characteristics. [ka] (However, in equation (6), R 22 is a single-valued base. n²² is an integer from 0 to 4. If n²² is an integer from 2 to 4, then R 22 These elements may be identical or different. (* indicates a connection point.)

[0120] X in equation (3) 0 If is a divalent group containing one benzene ring, then in formula (6), Z relative to the benzene ring 01 and Z 02 The bonding position is not limited. That is, Z relative to the benzene ring. 01 and Z 02 The bond position may be the ortho, meta, or para position.

[0121] X in equation (4) 1 If is a divalent group containing one benzene ring, then in formula (6), Z relative to the benzene ring 11 and Z 12 The bonding position is not limited. That is, Z relative to the benzene ring. 11 and Z 12 The bond position may be the ortho, meta, or para position.

[0122] (X 21 , X 22 ) X in equation (5) 21 , X 22Each of these groups can be independently a divalent group and is not particularly limited, but examples include hydrocarbon groups which may have substituents. The hydrocarbon groups are preferably in a chain form. When the hydrocarbon groups are in a chain form, the melting point of the color developer can be reduced, so that the color developer dissolves upon irradiation with laser light and the color-developing compound becomes easier to color. From the viewpoint of reducing the melting point of the color developer, among the chain-like hydrocarbon groups, a n-alkyl chain is particularly preferred.

[0123] The number of carbon atoms in the hydrocarbon group, which may have substituents, is, for example, 1 to 15, 1 to 13, 1 to 12, 1 to 10, 1 to 6, or 1 to 3.

[0124] X in equation (5) 21 , X 22 When the normal alkyl group is a normal alkyl group, the number of carbon atoms in the normal alkyl group is preferably 8 or less, more preferably 6 or less, even more preferably 5 or less, and particularly preferably 3 or less, from the viewpoint of high-temperature storage stability. When the number of carbon atoms in the normal alkyl group is 8 or less, the length of the normal alkyl group is short, so thermal disturbance is less likely to occur in the color developer during high-temperature storage, and the site that interacted with the color-developing compound such as leuco dye during color development is less likely to detach. Therefore, the color-developing compound such as leuco dye is less likely to lose its color during high-temperature storage, thus improving high-temperature storage stability.

[0125] Examples of substituents that a hydrocarbon group may have include halogen groups (e.g., fluorine groups) or alkyl groups having halogen groups (e.g., fluorine groups). A hydrocarbon group that may have substituents may be one in which some of the carbon atoms of the hydrocarbon group (e.g., some of the carbon atoms in the main chain of the hydrocarbon group) are substituted with an element such as oxygen.

[0126] (R 21 ) R in equation (5) 21 This can be any monovalent group and is not particularly limited, but examples include a halogen group or a hydrocarbon group which may have substituents.

[0127] Halogen groups include, for example, fluorine (-F), chlorine (-Cl), bromine (-Br), or iodine (-I).

[0128] The number of carbon atoms in the hydrocarbon group, which may have substituents, is, for example, 1 to 15, 1 to 13, 1 to 12, 1 to 10, 1 to 6, or 1 to 3.

[0129] Examples of substituents that a hydrocarbon group may have include halogen groups (e.g., fluorine groups) or alkyl groups having halogen groups (e.g., fluorine groups). A hydrocarbon group that may have substituents may be one in which some of the carbon atoms of the hydrocarbon group (e.g., some of the carbon atoms in the main chain of the hydrocarbon group) are substituted with an element such as oxygen.

[0130] (R 22 ) R in equation (6) 22 R can be any monovalent group and is not particularly limited, but examples include a halogen group or a hydrocarbon group which may have a substituent. The halogen group and the hydrocarbon group which may have a substituent are R in formula (3) above, respectively. 21 It is similar to that.

[0131] (X containing two benzene rings) 0 , X 1 ) X in equation (3) 0 and X in equation (4) 1 This is, for example, a divalent group containing two benzene rings. This divalent group can be represented, for example, by the following formula (7). [ka] (However, in equation (7), X 31 It can be there or not, X 31 If X 31 X is a divalent group. 32 It can be there or not, X 32 If X 32 X is a divalent group. 33may or may not exist, X 33 When there is, X 33 is a divalent group. R 31 , R 32 are each independently a monovalent group. n31 and n32 are each independently an integer from 0 to 4. When n31 is an integer from 2 to 4, R 31 may be the same as or different from each other. When n32 is an integer from 2 to 4, R 32 may be the same as or different from each other. The * mark represents a bonding site.)

[0132] In formula (7), the bonding positions of X 31 and X 32 to the benzene ring are not limited. That is, the bonding positions of X 31 and X 32 to the benzene ring may be any of the ortho, meta, and para positions. Similarly, in formula (7), the bonding positions of X 32 and X 33 to the benzene ring are not limited. That is, the bonding positions of X 32 and X 33 to the benzene ring may be any of the ortho, meta, and para positions.)

[0133] The divalent group containing two benzene rings is preferably represented by the following formula (8) from the viewpoint of improving the high-temperature and high-humidity storage characteristics.<​​​​​​​​​​​​​​​​

[0134] X in equation (3) 0 If is a divalent group containing two benzene rings, then in formula (8), Z relative to the benzene rings 01 and X 34 The bonding position is not limited. That is, Z relative to the benzene ring. 01 and X 34 The bond position may be the ortho, meta, or para position. Similarly, in formula (8), Z relative to the benzene ring 02 and X 34 The bonding position is not limited. That is, Z relative to the benzene ring. 02 and X 34 The bond position may be the ortho, meta, or para position.

[0135] X in equation (4) 1 If is a divalent group containing two benzene rings, then in formula (8), Z relative to the benzene rings 11 and X 34 The bonding position is not limited. That is, Z relative to the benzene ring. 11 and X 34 The bond position may be the ortho, meta, or para position. Similarly, in formula (8), Z relative to the benzene ring 12 and X 34 The bonding position is not limited. That is, Z relative to the benzene ring. 12 and X 34 The bond position may be the ortho, meta, or para position.

[0136] (X 31 , X 32 , X 33 ) X in equation (7) 31 , X 32 , X 33 Each of these can be a divalent group, and is not particularly limited, but an example would be a hydrocarbon group which may have substituents. The hydrocarbon group is X in formula (5) above. 21 , X 22 It is similar to that.

[0137] (X 34 ) X in equation (8) 34 X can be any divalent group and is not particularly limited, but an example is a hydrocarbon group which may have substituents. The hydrocarbon group is X in formula (5) above. 21 , X 22 It is similar to that.

[0138] (R 31 , R 32 ) R in equation (7) 31 , R 32 R can be any monovalent group and is not particularly limited, but examples include a halogen group or a hydrocarbon group which may have substituents. The halogen group and the hydrocarbon group which may have substituents are R in formula (5) above, respectively. 21 It is similar to that.

[0139] (R 33 , R 34 ) R in equation (8) 33 , R 34 R can be any monovalent group and is not particularly limited, but examples include a halogen group or a hydrocarbon group which may have substituents. The halogen group and the hydrocarbon group which may have substituents are R in formula (5) above, respectively. 21 It is similar to that.

[0140] (Y 01 , Y 02 ) Y in equation (3) 01 , Y 02 Each of these is independently, for example, a hydrogen group (-H), a hydroxyl group (-OH), a halogen group (-X), a carboxyl group (-COOH), an ester group (-COOR), or a hydrocarbon group which may have substituents.

[0141] Halogen groups include, for example, fluorine (-F), chlorine (-Cl), bromine (-Br), or iodine (-I).

[0142] The number of carbon atoms in the hydrocarbon group, which may have substituents, is, for example, 1 to 15, 1 to 13, 1 to 12, 1 to 10, 1 to 6, or 1 to 3.

[0143] Examples of substituents that a hydrocarbon group may have include halogen groups (e.g., fluorine groups) or alkyl groups having halogen groups (e.g., fluorine groups). A hydrocarbon group that may have substituents may be one in which some of the carbon atoms of the hydrocarbon group (e.g., some of the carbon atoms in the main chain of the hydrocarbon group) are substituted with an element such as oxygen.

[0144] In equation (3), (Y 01 ) n01 one of the following, and / or (Y 02 ) n02 It is preferable that one of them is a hydroxyl group (-OH). (Y 01 ) n01 one of the following, and / or (Y 02 ) n02 One of these groups is a hydroxyl group (-OH), which improves label quality and lightfastness.

[0145] (Y 11 , Y 12 , Y 13 , Y 14 ) In equation (4), Y relative to the benzene ring 11 and Y 12 The bonding position is not limited. That is, Y relative to the benzene ring. 11 and Y 12 The bond position of can be any of the ortho, meta, or para positions. Similarly, in formula (4), Y relative to the benzene ring 13 and Y 14 The bonding position is not limited. That is, Y relative to the benzene ring. 13 and Y 14 The bond position may be any of the ortho, meta, or para positions. In formula (4), Y for one of the benzenes 11 and Y 12The bond position of and Y relative to the other benzene 13 and Y 14 The bonding position may be the same as or different from that of the two elements.

[0146] Y in equation (4) 11 , Y 12 , Y 13 , Y 14 Each of these is independently, for example, a hydrogen group (-H), a hydroxyl group (-OH), a halogen group, a carboxyl group (-COOH), an ester group (-COOR), or a hydrocarbon group which may have a substituent. The halogen group and the hydrocarbon group which may have a substituent are Y in formula (3) above, respectively. 01 , Y 02 It is similar to that.

[0147] In equation (4), Y 11 and / or Y 13 It is preferable that it is a hydroxyl group (-OH). 11 and / or Y 13 The presence of a hydroxyl group (-OH) improves both label quality and lightfastness.

[0148] (Z 01 , Z 02 ) Z in equation (3) 01 , Z 02 These are, independently of each other, for example, urea bonds (-NHCONH-), amide bonds (-NHCO-, -OCHN-), or hydrazide bonds (-NHCOCONH-). From the viewpoint of improving high temperature and high humidity storage characteristics, Z 01 , Z 02 It is preferable that it is a urea bond. 01 If it is an amide bond, the nitrogen contained in the amide bond may be bonded to benzene, or the carbon contained in the amide bond may be bonded to benzene. 02 If the bond is an amide bond, the nitrogen contained in the amide bond may be bonded to benzene, or the carbon contained in the amide bond may be bonded to benzene.

[0149] (Z11 , Z 12 ) Z in equation (4) 11 , Z 12 These are, independently of each other, for example, urea bonds (-NHCONH-), amide bonds (-NHCO-, -OCHN-), or hydrazide bonds (-NHCOCONH-). From the viewpoint of improving high temperature and high humidity storage characteristics, Z 11 , Z 12 It is preferable that it is a urea bond. 11 If it is an amide bond, the nitrogen contained in the amide bond may be bonded to benzene, or the carbon contained in the amide bond may be bonded to benzene. 12 If the bond is an amide bond, the nitrogen contained in the amide bond may be bonded to benzene, or the carbon contained in the amide bond may be bonded to benzene.

[0150] (Specific examples of color developers) X in equation (3) 0 and X in equation (4) 1 A color developer containing one benzene ring specifically includes, for example, at least one selected from the group consisting of compounds represented by the following formulas (9-1) to (9-6). [ka]

[0151] X in equation (3) 0 and X in equation (4) 1 A color developer containing two benzene rings specifically includes, for example, at least one selected from the group consisting of compounds represented by the following formulas (10-1) to (10-8). [ka]

[0152] (Experimental variation 6) In the first embodiment, an example was described in which the laminate 10 includes a recording medium 20 (see Figure 3), but the laminate 10 may also include a recording medium 20B shown in Figure 18 instead of the recording medium 20. The recording medium 20B differs from the recording medium 20 in that it includes a protective layer 36 instead of a protective layer 31. The protective layer 36 is as described in the third embodiment. Similarly in the second embodiment, the laminate 40 may also include a recording medium 20B shown in Figure 18 instead of the recording medium 20.

[0153] (Example 7) In the third embodiment, an example was described in which the laminate 10A includes a recording medium 20A, but the laminate 10A may also include a recording medium 20C shown in Figure 19 instead of the recording medium 20A (see Figure 15). The recording medium 20C differs from the recording medium 20A in that it includes intermediate layers 37A, 37B, and 37C instead of intermediate layers 35A, 35B, and 35C. The recording medium 20C may not include a base material 21 and an adhesive layer 22.

[0154] The intermediate layer 37A comprises a heat insulating layer 26A and an adhesive layer 25 in order on one main surface of the coloring layer 24. The heat insulating layer 26A comprises a resin layer 26A1 and an ultraviolet curing resin layer 26A2 in order on one main surface of the coloring layer 24. The resin layer 26A1 is provided between the coloring layer 24 and the ultraviolet curing resin layer 26A2. The resin layer 26A1 can improve the adhesion between the coloring layer 24 and the ultraviolet curing resin layer 26A2. The resin layer 26A1 contains the same type of resin material as the matrix polymer contained in the coloring layer 24. For example, if the coloring layer 24 contains a polycarbonate-based resin as the matrix polymer, the resin layer 26A1 contains a polycarbonate-based resin. The ultraviolet curing resin layer 26A2 is the same as the ultraviolet curing resin layer of the heat insulating layer 26 in the third embodiment.

[0155] The intermediate layer 37B comprises a heat insulating layer 29A and an adhesive layer 28 sequentially on one main surface of the coloring layer 27. The heat insulating layer 29A comprises a resin layer 29A1 and an ultraviolet curing resin layer 29A2 sequentially on one main surface of the coloring layer 27. The resin layer 29A1 is provided between the coloring layer 27 and the ultraviolet curing resin layer 29A2. The resin layer 29A1 can improve the adhesion between the coloring layer 27 and the ultraviolet curing resin layer 29A2. The resin layer 29A1 contains the same type of resin material as the matrix polymer contained in the coloring layer 27. For example, if the coloring layer 27 contains a polycarbonate-based resin as the matrix polymer, the resin layer 29A1 contains a polycarbonate-based resin. The ultraviolet curing resin layer 29A2 is the same as the ultraviolet curing resin layer of the heat insulating layer 29 in the third embodiment.

[0156] The intermediate layer 37C comprises a heat insulating layer 34A and an adhesive layer 33 in order on one main surface of the color development layer 30. The heat insulating layer 34A comprises a resin layer 34A1 and an ultraviolet-curable resin layer 34A2 in order on one main surface of the coloring layer 30. The resin layer 34A1 is provided between the coloring layer 30 and the ultraviolet-curable resin layer 34A2. The resin layer 34A1 can improve the adhesion between the coloring layer 30 and the ultraviolet-curable resin layer 34A2. The resin layer 34A1 contains the same type of resin material as the matrix polymer contained in the coloring layer 30. For example, if the coloring layer 30 contains a polycarbonate-based resin as the matrix polymer, the resin layer 34A1 contains a polycarbonate-based resin. The ultraviolet-curable resin layer 34A2 is the same as the ultraviolet-curable resin layer of the heat insulating layer 34 in the third embodiment.

[0157] The reason why the resin layer 26A1 is provided between the color developing layer 24 and the ultraviolet curable resin layer 26A2 is as follows. When the color developing layer 24 contains particulate developers, the particulate developers are distributed on the surface of the color developing layer 24. Therefore, when the color developing layer 24 and the ultraviolet curable resin layer 26A2 are adjacent to each other, there is a risk of reduced adhesion. As described above, when the resin layer 34A1 is adjacent to the color developing layer 24 and the resin layer 34A1 contains the same type of resin material as the matrix polymer contained in the color developing layer 24, the adhesion at the interface other than the portion where the developers are distributed can be improved. Therefore, it is possible to compensate for the reduction in adhesion due to the particulate developers.

[0158] The reason why the resin layer 29A1 is provided between the color developing layer 27 and the ultraviolet curable resin layer 29A2, and the reason why the resin layer 34A1 is provided between the color developing layer 30 and the ultraviolet curable resin layer 34A2 are the same as the reason why the resin layer 26A1 is provided between the color developing layer 24 and the ultraviolet curable resin layer 26A2.

[0159] (Modification 8) In the third embodiment, an example in which the laminate 10A includes the recording medium 20A has been described. However, instead of the recording medium 20A (see FIG. 15), the laminate 10A may include the recording medium 20D shown in FIG. 20. The recording medium 20D is different from the recording medium 20A in that it includes intermediate layers 38A, 38B, and 38C instead of the intermediate layers 35A, 35B, and 35C.

[0160] The intermediate layer 38A includes a heat insulating layer 26B and an adhesive layer 25 in this order on one main surface of the color developing layer 24. The heat insulation layer 26B includes an adhesive layer 26B1 and an ultraviolet curable resin layer 26B2, which are provided in this order on one main surface of the color developing layer 24. The adhesive layer 26B1 is provided between the color developing layer 24 and the ultraviolet curable resin layer 26B2. The adhesive layer 26B1 can bond the color developing layer 24 and the ultraviolet curable resin layer 26B2 together. By providing the adhesive layer 26B1 between the color developing layer 24 and the ultraviolet curable resin layer 26B2, it is possible to compensate for the decrease in adhesion due to the color former contained in the color developing layer 24. Examples of the material for the adhesive layer 26B1 can be the same materials as those for the adhesive layers 22, 25, and 28.

[0161] The intermediate layer 38B includes a heat insulation layer 29B and an adhesive layer 28, which are provided in this order on one main surface of the color developing layer 27. The heat insulation layer 29B includes an adhesive layer 29B1 and an ultraviolet curable resin layer 29B2, which are provided in this order on one main surface of the color developing layer 27. The adhesive layer 29B1 is provided between the color developing layer 27 and the ultraviolet curable resin layer 29B2. The adhesive layer 29B1 can bond the color developing layer 27 and the ultraviolet curable resin layer 29B2 together. By providing the adhesive layer 29B1 between the color developing layer 27 and the ultraviolet curable resin layer 29B2, it is possible to compensate for the decrease in adhesion due to the color former contained in the color developing layer 27. Examples of the material for the adhesive layer 29B1 can be the same materials as those for the adhesive layers 22, 25, and 28.

[0162] The intermediate layer 38C includes a heat insulation layer 34B and an adhesive layer 33, which are provided in this order on one main surface of the color developing layer 30. The heat insulation layer 34B includes an adhesive layer 34B1 and an ultraviolet curable resin layer 34B2, which are provided in this order on one main surface of the color developing layer 30. The adhesive layer 34B1 is provided between the color developing layer 30 and the ultraviolet curable resin layer 34B2. The adhesive layer 34B1 can bond the color developing layer 30 and the ultraviolet curable resin layer 34B2 together. By providing the adhesive layer 34B1 between the color developing layer 30 and the ultraviolet curable resin layer 34B2, it is possible to compensate for the decrease in adhesion due to the color former contained in the color developing layer 30. Examples of the material for the adhesive layer 34B1 can be the same materials as those for the adhesive layers 22, 25, and 28.

[0163] (Modification Example 9) In the third embodiment, an example was described in which the laminate 10A includes a recording medium 20A, but the laminate 10A may also include a recording medium 20E shown in Figure 21 instead of the recording medium 20A (see Figure 15). The recording medium 20E differs from the recording medium 20A in that it includes intermediate layers 39A, 39B, and 39C instead of intermediate layers 35A, 35B, and 35C. The recording medium 20E may not include a base material 21 and an adhesive layer 22.

[0164] The intermediate layers 39A and 39B are films. Preferably, the films are films that have undergone an easy-adhesion treatment. Examples of film materials include those similar to those used for the substrate 11. Examples of easy-adhesion treatments include priming, active energy ray irradiation, plasma treatment, corona treatment, vapor deposition, etching, and sandblasting. One or more of these can be selected. The priming treatment may be a priming treatment using a resin, silane coupling agent, or tetraalkoxysilane.

[0165] By providing an easily adhesive-treated film as an intermediate layer 39A between the color-developing layer 24 and the color-developing layer 27, the reduction in adhesion caused by the color developer contained in the color-developing layer 24 can be compensated for. By providing an easily adhesive-treated film as an intermediate layer 39B between the color-developing layer 27 and the color-developing layer 30, the reduction in adhesion caused by the color developer contained in the color-developing layer 27 can be compensated for.

[0166] The intermediate layer 39C is an adhesive layer. Examples of materials for the adhesive layer include those similar to those used for adhesive layers 22, 25, and 28. By providing the adhesive layer as the intermediate layer 39C between the color-developing layer 30 and the protective layer 36, the reduction in adhesion caused by the color developer contained in the color-developing layer 30 can be compensated for.

[0167] (Variation 10) In the third embodiment, an example was described in which the laminate 10A includes a recording medium 20A. However, the laminate 10A may also include a recording medium 20F shown in Figure 22 instead of the recording medium 20A (see Figure 15). The recording medium 20F differs from the recording medium 20E in Modification 9 in that it includes an intermediate layer 41B instead of an intermediate layer 39B.

[0168] The intermediate layer 41B comprises a resin layer 41B1 and a resin layer 41B2 in order on one main surface of the coloring layer 27. The resin layer 41B1 contains the same type of resin material as the matrix polymer contained in the coloring layer 27. For example, if the coloring layer 27 contains a polycarbonate-based resin as the matrix polymer, then the resin layer 41B1 contains a polycarbonate-based resin. The resin layer 41B2 is a film. The film is preferably a film that has been treated for easy adhesion. Examples of the film material include materials similar to those of the substrate 11.

[0169] As described above, the resin layer 41B1 is provided between the color development layer 27 and the resin layer 41B2, which compensates for the decrease in adhesion caused by the color developer contained in the color development layer 27.

[0170] (Variation 11) In the third embodiment, an example was described in which the laminate 10A includes a recording medium 20A. However, the laminate 10A may also include a recording medium 20G as shown in Figure 23 instead of the recording medium 20A (see Figure 15). The recording medium 20G differs from the recording medium 20E in the modified example 9 in that it includes an intermediate layer 38A instead of the intermediate layer 39A, and also includes a base material 42.

[0171] The intermediate layer 38A is as described in Modification 8 (see Figure 20). The substrate 42 is provided adjacent to the other surface of the color-developing layer 24. The substrate 42 is a film that has been treated for easy adhesion. As the material of the film, the same material as that of the substrate 11 can be exemplified.

[0172] (Example 12) In the third embodiment, an example was described in which the laminate 10A includes a recording medium 20A. However, the laminate 10A may also include a recording medium 20H as shown in Figure 24 instead of the recording medium 20A (see Figure 15). The recording medium 20H differs from the recording medium 20A in that it includes intermediate layers 42A and 42B instead of intermediate layers 35A and 35B.

[0173] The intermediate layers 42A and 42B are adhesive layers. Examples of materials for the adhesive layers include those similar to those used for adhesive layers 22, 25, and 28.

[0174] (Example 13) In the first and second embodiments, examples were described in which the laminate 10 includes a recording medium 20, but the laminate 10 may also include a recording medium 20A instead of the recording medium 20.

[0175] (Variation 14) In the third and fourth embodiments, an example was described in which the laminate 10A includes a recording medium 20A, but the laminate 10A may also include a recording medium 20 instead of the recording medium 20A.

[0176] (Variation 15) In the above modifications 7, 8, 9, 10, 11, and 12, examples were described in which the laminate 10A according to the third embodiment includes any of the recording media 20C, 20D, 20E, 20F, 20G, and 20H instead of the recording media 20A, but the disclosure is not limited thereto. For example, the laminate 10 according to the first embodiment may include any of the recording media 20C, 20D, 20E, 20F, 20G, and 20H instead of the recording media 20. The laminate 40 according to the second embodiment may include any of the recording media 20C, 20D, 20E, 20F, 20G, and 20H instead of the recording media 20. The laminate 40A according to the fourth embodiment may include any of the recording media 20C, 20D, 20E, 20F, 20G, and 20H instead of the recording media 20A.

[0177] (Variation 16) In the first, second, third, and fourth embodiments and their modifications, examples of applying the laminates 10, 40, 10A, and 40A to cards have been described. However, the laminates 10, 40, 10A, and 40A may be applied to medical supplies, automobile parts, automobiles, toys, foods, cosmetics, ornaments, documents (such as passports, etc.), exterior members, or housings of electronic devices, etc. Specific examples of exterior members include, for example, interior or exterior finishes of building walls, etc., or exterior finishes of furniture such as desks, etc. Specific examples of electronic devices include personal computers (hereinafter referred to as "PCs"), mobile devices, mobile phones (such as smartphones), tablet computers, display devices, photographing devices, audio devices, game devices, industrial tools, medical devices, robots, or wearable terminals, etc. Specific examples of wearable terminals include ornaments such as watches (wristwatches), bags, clothes, hats, glasses, or shoes, etc.

[0178] Hereinafter, specific examples of applying the laminates 10, 40, 10A, and 40A to smartphones, notebook personal computers, and cosmetic containers will be described.

[0179] (Example of a smartphone) FIG. 7A shows the front external configuration of the smartphone 100, and FIG. 7B shows the back external configuration of the smartphone 100 shown in FIG. 7A. This smartphone 100 includes, for example, a display unit 111 and a housing 112. A recording medium 20 is provided on the back side of the housing 112. The housing 112 is composed of a laminate. This laminate is the same as any of the laminates 10, 40, 10A, and 40A according to the first, second, third, and fourth embodiments and their modifications, except that the base material has the shape of the housing of the smartphone 100. Thereby, the forgery prevention property, etc. of the smartphone 100 can be improved.

[0180] (Example of a notebook PC) Figure 8 shows the external configuration of the notebook PC 200. The notebook PC 200 comprises a computer body 210 and a display 220. The computer body 210 comprises a casing 211, a keyboard 212, a wheel / pad operation section 213, and click buttons 214 and 215. A recording medium 20 is provided in the casing 112. The casing 211 is made of a laminate. This laminate is the same as any of the laminates 10, 40, 10A, and 40A relating to the first, second, third, and fourth embodiments and their variations, except that the base material has the shape of the notebook PC 200 casing. This improves the anti-counterfeiting properties of the notebook PC 200.

[0181] (Example of a cosmetic container) Figure 9 shows the external appearance of the cosmetic container 300. This cosmetic container 300 comprises a storage section 311 and a lid 312 that covers the storage section 311. A recording medium 20 is provided on the lid 312. The lid 312 is made of a laminate. This laminate is the same as any of the laminates 10, 40, 10A, and 40A relating to the first, second, third, and fourth embodiments and their variations, except that the base material has a shape corresponding to the lid 312. This improves the anti-counterfeiting properties of the cosmetic container 300.

[0182] (Example of a passport) Figure 25 shows the appearance of booklet 400. Booklet 400 is a passport. A passport is an example of a booklet-type identification document. Booklet 400 comprises a plurality of sheets 410. The plurality of sheets 410 are saddle-stitched. A recording medium 20, etc., is provided on at least one or both sides of a sheet 410. A photograph, etc., is drawn on the recording medium 20, etc. A sheet 410 is the same as any of the laminates 10, 40, 10A, 40A according to the first, second, third, and fourth embodiments and their variations. In this case, the base material 11 may be paper or the like.

[0183] Although embodiments and modifications of the present disclosure have been described in detail above, the present disclosure is not limited to the embodiments and modifications described above, and various modifications based on the technical idea of ​​the present disclosure are possible.

[0184] For example, the configurations, methods, processes, shapes, materials, and numerical values ​​listed in the above-described embodiments and modifications are merely examples, and different configurations, methods, processes, shapes, materials, and numerical values ​​may be used as needed. The configurations, methods, processes, shapes, materials, and numerical values ​​of the above-described embodiments and modifications can be combined with each other, as long as they do not deviate from the spirit of this disclosure.

[0185] In the numerical ranges described stepwise in the embodiments and modifications described above, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range. Unless otherwise specified, the materials exemplified in the embodiments and modifications described above can be used individually or in combination of two or more.

[0186] Furthermore, this disclosure may also adopt the following configuration. (1) Substrate and An intermediate layer provided on the substrate and having a housing portion, A recording medium provided within the aforementioned storage section, An overlay layer provided on the aforementioned intermediate layer and Equipped with, The aforementioned housing section is provided in a part of the plane of the intermediate layer, The aforementioned housing portion is a through hole penetrating in the thickness direction of the intermediate layer, or a recessed area in the thickness direction of the intermediate layer. The recording medium is configured to change its color state in response to external stimuli. A laminate in which the substrate and the intermediate layer are bonded together by fusion or thermal adhesive, and the intermediate layer and the overlay layer are bonded together by fusion or thermal adhesive. (2) The thermal adhesive is a laminate according to (1) comprising a thermosetting resin. (3) The substrate and the intermediate layer and the intermediate layer and the overlay layer are fused together. The laminate according to (1), wherein the substrate, the intermediate layer, and the overlay layer are made of a thermoplastic resin. (4) The recording medium is a laminate according to any one of (1) to (3) fitted into the housing portion. (5) The laminate according to any one of (1) to (4), wherein the external stimulus is laser light. (6) The laminate according to any one of (1) to (5), wherein the change in the colored state is an irreversible change. (7) The recording medium comprises a first color-developing layer to the nth color-developing layer (where n is an integer of 2 or more), The laminate according to any one of (1) to (6), wherein the first to n color-developing layers contain color-developing compounds with different color hues from each other. (8) The recording medium comprises a first color-developing layer, a second color-developing layer, and a third color-developing layer. The laminate according to any one of (1) to (6), wherein the first coloring layer, the second coloring layer, and the third coloring layer each contain a color-producing compound having a different color hue from the others. (9) The recording medium is a laminate according to any one of (1) to (6), comprising a color-developing layer containing three types of microcapsules with different color hues. (10) The recording medium comprises a color-developing layer, The aforementioned color-developing layer is A color-developing compound having electron-donating properties, A color developer having electron-accepting properties, Photothermal conversion materials and A laminate according to any one of (1) to (6), including the following: (11) A card consisting of the laminate described in any one of items (1) through (10). (12) A housing consisting of a laminate as described in any one of items (1) to (10).

[0187] Furthermore, this disclosure may also adopt the following configuration. (twenty one) Substrate and A first intermediate layer provided on the substrate and having a housing portion, A recording medium provided within the aforementioned storage section, An overlay layer provided on the first intermediate layer and Equipped with, The aforementioned housing section is provided in a part of the plane of the first intermediate layer, The receiving portion is a through hole penetrating in the thickness direction of the first intermediate layer, or a recessed portion in the thickness direction of the first intermediate layer. The recording medium comprises a color-developing layer containing an electron-donating color-developing compound, an electron-accepting color developer, and a matrix resin. The substrate, the first intermediate layer, and the overlay layer each contain the same type of resin material. A laminate in which the substrate and the first intermediate layer are bonded together by fusion, and the first intermediate layer and the overlay layer are bonded together by fusion. (twenty two) Substrate and A first intermediate layer provided on the substrate and having a housing portion, A recording medium provided within the aforementioned storage section, An overlay layer provided on the first intermediate layer and Equipped with, The aforementioned housing section is provided in a part of the plane of the first intermediate layer, The receiving portion is a through hole penetrating in the thickness direction of the first intermediate layer, or a recessed portion in the thickness direction of the first intermediate layer. The recording medium comprises a color-developing layer containing an electron-donating color-developing compound, an electron-accepting color developer, and a matrix resin. The substrate, the first intermediate layer, and the overlay layer each contain the same type of resin material. A laminate in which the substrate and the first intermediate layer are bonded together with a thermal adhesive, and the first intermediate layer and the overlay layer are bonded together with a thermal adhesive. (twenty three) The resin material is a laminate according to (21) or (22), comprising a thermoplastic resin. (twenty four) The resin material is a laminate according to (21) or (22), comprising a polycarbonate resin. (twenty five) The resin material is a laminate according to (21) or (22), comprising a polyethylene terephthalate resin. (26) The thermal adhesive is a laminate according to (22) comprising a thermosetting resin. (27) The aforementioned color-developing layer is configured to change its coloring state using laser light. The laminate according to any one of (21) to (26), wherein the change in the colored state is an irreversible change. (28) The aforementioned color-developing layer is A laminate according to any one of (21) to (27), further comprising a photothermal conversion material. (29) The recording medium comprises a plurality of the color-developing layers, The laminate according to any one of (21) to (28), wherein the plurality of color-developing layers contain color-developing compounds with different color hues from each other. (30) The recording medium comprises a plurality of color-developing layers and a plurality of second intermediate layers, The laminate according to any one of (21) to (28), wherein the second intermediate layer is provided between adjacent color-developing layers. (31) The laminate according to (30), wherein at least one of the plurality of second intermediate layers comprises an ultraviolet curing resin layer and an adhesive layer. (32) At least one of the multiple second intermediate layers comprises a resin layer, an ultraviolet curing resin layer, and an adhesive layer. The UV-curing resin layer is provided between the resin layer and the adhesive layer. The laminate according to (30), wherein the resin layer comprises a resin material of the same type as the matrix resin. (33) The laminate according to (30), wherein at least one of the plurality of second intermediate layers comprises, in order, a first adhesive layer, an ultraviolet curing resin layer, and a second adhesive layer. (34) The laminate according to (30), wherein at least one of the plurality of second intermediate layers is a film that has been treated for easy adhesion. (35) The recording medium comprises a plurality of color-developing layers, a plurality of second intermediate layers, and a protective layer. The plurality of color-developing layers include a first color-developing layer, a second color-developing layer, and a third color-developing layer. The first color-developing layer, the second intermediate layer, the second color-developing layer color The layers, the second intermediate layer, the third coloring layer, the second intermediate layer, and the protective layer are laminated in this order. The laminate according to any one of (21) to (28), wherein the first coloring layer, the second coloring layer, and the third coloring layer each contain a color-developing compound having a different color hue from the others. (36) The laminate according to any one of (21) to (35), wherein the ratio of the color developer to the total amount of the color developer and the matrix resin is 16% by mass or less. (37) A card consisting of a laminate as described in any one of items (21) to (36). (38) A housing consisting of a laminate as described in any one of items (21) to (36).

[0188] <6. Reference Examples and Implementation Examples>

[0189] The present disclosure will be described in detail below with reference examples and embodiments, but the present disclosure is not limited to these reference examples and embodiments.

[0190] [Reference example 1-1] First, a first adhesive layer was placed on the substrate, and then an intermediate layer was placed on the first adhesive layer. Next, a second adhesive layer was placed on the intermediate layer, and then an overlay layer was placed on the second adhesive layer to obtain a laminated structure. Next, this laminated structure was heated and pressurized at a temperature of 120°C to bond the substrate and the intermediate layer via the first adhesive layer, and to bond the intermediate layer and the overlay layer via the second adhesive layer. As a result, the desired laminate was obtained.

[0191] The following materials were used as the substrate, first adhesive layer, intermediate layer, second adhesive layer, and overlay layer. Overlay layer: 50 μm thick polycarbonate film (hereinafter referred to as "PC film"). Second intermediate layer: 5 μm thick epoxy resin layer (thermosetting resin layer) Intermediate layer: 100μm thick PC film First adhesive layer: 5 μm thick epoxy resin layer (thermosetting resin layer) Base material: PC film with a thickness of 25 μm

[0192] [Reference example 1-2] A laminate was obtained in the same manner as in Reference 1-1, except that the following materials were used as the base material, intermediate layer, and overlay layer. Overlay layer: 50 μm thick polyvinyl chloride film (hereinafter referred to as "PVC film"). Intermediate layer: 100μm thick PVC vinyl film Base material: 25μm thick PVC vinyl film

[0193] [Reference example 1-3] A laminate was obtained in the same manner as in Reference 1-1, except that the following materials were used as the base material, intermediate layer, and overlay layer. Overlay layer: 50 μm thick polyethylene terephthalate film (hereinafter referred to as "PET film"). Intermediate layer: PET film with a thickness of 100 μm Substrate: PET film with a thickness of 25 μm

[0194] [Reference example 1-4] A laminate was obtained in the same manner as in Reference 1-1, except that the following materials were used as the base material, intermediate layer, and overlay layer. Overlay layer: 50μm thick PC film Intermediate layer: 100μm thick PVC film Base material: PC film with a thickness of 25 μm

[0195] [Reference examples 2-1, 2-2, 2-3, 2-4] After obtaining a laminated structure by sequentially stacking a base material, an intermediate layer, and an overlay layer, the laminate was obtained in the same manner as in Reference Examples 1-1, 1-2, 1-3, and 1-4, except that the laminated structure was heated and pressurized at a temperature of 180°C to fuse the base material-intermediate layer and the intermediate layer-overlay layer.

[0196] [evaluation] The adhesion, environmental friendliness, and durability of the laminate obtained as described above were evaluated as follows.

[0197] (Adhesion) First, the average peel strength between the substrate and the intermediate layer, and the average peel strength between the intermediate layer and the overlay layer were measured. The average peel strength was measured using the method for measuring the average peel strength of a laminate described in the first embodiment. Next, the measured average peel strength was evaluated according to the following criteria. The evaluation results are shown in Table 1. ◎: The average peel strength between the substrate and the intermediate layer, and the average peel strength between the intermediate layer and the overlay layer, are both 5.0 N / cm or higher. ○: The average peel strength between the substrate and the intermediate layer, and the average peel strength between the intermediate layer and the overlay layer, are both 3.5 N / cm or higher. ×: The average peel strength between the substrate and the intermediate layer, and the average peel strength between the intermediate layer and the overlay layer, are both less than 3.5 N / cm.

[0198] (Environmental considerations) The environmental friendliness of the laminate was evaluated according to the following criteria. The evaluation results are shown in Table 1. ○: There is no possibility of harmful substances (especially dioxins) being generated when processing laminates with inadequate equipment. ×: Processing laminates with inadequate equipment may generate harmful substances (especially dioxins).

[0199] (durability) In accordance with ISO / IEC 10373-1, the durability of the laminate was evaluated according to the following criteria. The evaluation results are shown in Table 1. ○: No change in appearance (warping) after heating. ×: If a change in appearance (warping) occurs after heating.

[0200] [Table 1]

[0201] The following can be seen from Table 1. By bonding the substrate to the intermediate layer and the intermediate layer to the overlay layer using thermosetting resin or fusion bonding, good adhesion can be obtained. From the viewpoint of improving adhesion, it is preferable to bond the substrate to the intermediate layer and the intermediate layer to the overlay layer by fusion. From an environmental perspective, it is preferable to use PC film or PET film as the base material, intermediate layer, and overlay layer. From the viewpoint of improving durability, it is preferable to use PC film or PVC film as the base material, intermediate layer, and overlay layer. From the viewpoint of environmental considerations and improved durability, it is preferable to use PC film as the base material, intermediate layer, and overlay layer.

[0202] (Examples 1-3) First, a recording medium having the layer configuration shown in Figure 15 was fabricated by laminating the layers shown in Table 2. Next, a 100 μm thick PET film with a frame-like structure (see Figure 16) was prepared as an intermediate layer, and the recording medium was fitted into the frame of this PET film. The thickness of the recording medium and the PET film were set to be approximately the same. Next, a laminate was obtained in the same manner as in Reference Example 2-1, except that an intermediate layer with the recording medium fitted in as described above was used. The interface of the recording medium is also bonded by a heating and pressing process after lamination of the substrate, intermediate layer, and overlay layer.

[0203] (Example 4) A laminate was obtained in the same manner as in Example 1, except that a recording medium having the layer configuration shown in Figure 24 was fabricated by stacking each layer shown in Table 3.

[0204] (Example 5) A laminate was obtained in the same manner as in Example 1, except that a recording medium having the layer configuration shown in Figure 19 was fabricated by stacking each layer shown in Table 3.

[0205] (Example 6) A laminate was obtained in the same manner as in Example 1, except that a recording medium having the layer configuration shown in Figure 20 was fabricated by stacking each layer shown in Table 3.

[0206] (Example 7) A laminate was obtained in the same manner as in Example 1, except that a recording medium having the layer configuration shown in Figure 21 was fabricated by stacking each layer shown in Table 4.

[0207] (Example 8) A laminate was obtained in the same manner as in Example 1, except that a recording medium having the layer configuration shown in Figure 22 was fabricated by stacking each layer shown in Table 4.

[0208] (Example 9) A laminate was obtained in the same manner as in Example 1, except that a recording medium having the layer configuration shown in Figure 21 was fabricated by stacking each layer shown in Table 4.

[0209] (Example 10) A laminate was obtained in the same manner as in Example 1, except that a recording medium having the layer configuration shown in Figure 23 was fabricated by stacking each layer shown in Table 4.

[0210] [evaluation] The adhesion and durability of the laminate obtained as described above were evaluated as follows.

[0211] (Adhesion) First, the average peel strength between each layer of the laminate was measured. This average peel strength was measured using the method for measuring the average peel strength of a laminate described in the first embodiment. Next, the measured average peel strength was evaluated according to the following criteria. The lowest average peel strength between each layer of the laminate is shown in Tables 2, 3, and 4. The location of the interface with the lowest average peel strength is also shown in Tables 2, 3, and 4. ○: The average peel strength between each layer is 3.5 N / cm or higher. ×: At least one of the average peel strengths between each layer is less than 3.5 N / cm.

[0212] (Anti-counterfeiting) The anti-counterfeiting properties of the laminate were evaluated according to the following criteria. ○: Satisfies at least one of the following conditions (1) and (2). ×: Does not meet either condition (1) or condition (2) below. Condition (1): The average peel strength between each layer of the laminate is 3.5 N / cm or higher. Condition (2): The interface with the lowest average peel strength is located between the color-developing layers.

[0213] (Maximum color intensity OD) First, the maximum color OD of the laminate was measured using the eXact spectrophotometer (manufactured by X-Rite). Next, the color development was evaluated according to the following criteria. The evaluation results are shown in Tables 2, 3, and 4. ○: The maximum color rendering OD is 1.0 or higher. The standard is an OD value of 1.0, which is the value at which a person can be recognized when drawing a person. ×: The maximum color OD is less than 1.0. When the OD value is less than 1.0, it becomes difficult to recognize people when drawing them.

[0214] (Color gamut retention rate after heating) First, the color gamut retention rate after heating was measured using the eXact spectrophotometer and densitometer. Next, the color gamut retention rate after heating was evaluated according to the following criteria. The evaluation results are shown in Tables 2, 3, and 4. ○: The color gamut retention rate after heating is 80% or higher. ×: The color gamut retention rate after heating is less than 80%. Furthermore, a color gamut retention rate of 80% or higher ensures sufficient color representation when depicting people.

[0215] [Table 2]

[0216] [Table 3]

[0217] [Table 4]

[0218] Details of each component listed in Tables 2, 3, and 4 are as follows. PC: PC film PET: PET film Easy-adhesion treated PET: PET film treated with an easy-adhesion process (manufactured by Mitsubishi Chemical Corporation, Diafoil® registered trademark) OCA: Optical Clear Adhesive UV Resin: UV-curing resin layer (acrylic resin layer for hard coating) Matrix polymer layer: A resin layer (specifically, a polycarbonate-based resin layer) composed of the same type of polymer as the matrix polymer contained in the adjacent coloring layer. Coloring layer Y1: A coloring layer containing a yellow leuco dye, a color developer, and a polycarbonate resin, wherein the polycarbonate resin content in the coloring layer is 58% by mass. Coloring layer Y2: A coloring layer containing a yellow leuco dye, a color developer, and a polycarbonate resin, with the polycarbonate resin content in the coloring layer being 58% by mass. Coloring layer C1: A coloring layer containing a cyan-coloring leuco dye, a color developer, and a polycarbonate resin, wherein the polycarbonate resin content in the coloring layer is 65% by mass. Coloring layer C2: A coloring layer containing a cyan-coloring leuco dye, a color developer, and a polycarbonate resin, wherein the polycarbonate resin content in the coloring layer is 65% by mass. Coloring layer M1: A coloring layer containing a magenta-colored leuco dye, a color developer, and a polycarbonate-based resin, wherein the polycarbonate-based resin content in the coloring layer is 58% by mass. Coloring layer M2: Contains a magenta-colored leuco dye, a color developer, and a polycarbonate resin, with the polycarbonate resin content in the coloring layer being 58% by mass.

[0219] From Tables 2, 3, and 4, the following can be seen. If the intermediate layer between the color-developing layers is composed of a matrix polymer layer, an ultraviolet-curable resin layer, and an adhesive layer, the adhesion between the color-developing layer and the intermediate layer can be improved (see evaluation results in Example 5). If the intermediate layer between the color-developing layers is composed of an adhesive layer, an ultraviolet-curable resin layer, and another adhesive layer, the adhesion between the color-developing layer and the intermediate layer can be improved (see evaluation results in Examples 6 and 10). When the intermediate layer between the color-developing layers is composed of a matrix polymer layer and a film, the adhesion between the color-developing layer and the intermediate layer can be improved (see evaluation results in Example 8). If the intermediate layer between the color-developing layers is made of an easily adhesive treated film, the adhesion between the color-developing layer and the intermediate layer can be improved (see evaluation results in Examples 9 and 10).

[0220] (Reference examples 3-1~3-8) Samples were obtained by laminating a 25 μm thick PC film, a 5 μm thick polycarbonate resin-containing layer, and a 25 μm thick PC film, then heating and pressurizing them at 180°C to fuse them together. The polycarbonate resin-containing layer used had the composition shown in Table 5.

[0221] (Adhesion) First, the average peel strength between each layer of the sample was measured. This average peel strength was measured using the method for measuring the average peel strength of a laminate described in the first embodiment. Next, the measured average peel strength was evaluated according to the following criteria. ○: The average peel strength between each layer is 3.5 N / cm or higher. ×: At least one of the average peel strengths between each layer is less than 3.5 N / cm. The evaluation results are shown in Table 5 and Figure 26. Note that the average peel strength listed in Table 5 represents the average peel strength between the polycarbonate resin-containing layer and the PC film.

[0222] [Table 5]

[0223] Details of each component and material listed in Table 5 are as follows: OCA: Optical Clear Adhesive UV-curing resin layer: Acrylic resin layer for hard coating. Matrix polymer: Polycarbonate-based resin Chromogen: Compound represented by formula (3)

[0224] Table 5 and Figure 26 show that when the ratio of the developer to the total amount of the developer and matrix polymer is 16% by mass or less, the peel strength can be increased to 3.5 N / cm or more. [Explanation of Symbols]

[0225] 10, 10A, 40, 40A laminate 11, 21, 51 Base material 12, 14 Adhesive layer 13, 16 Middle class 13A, 16A Accommodation Section 15 Overlay Layers 20, 20A, 20B, 20C, 20D, 20E, 20F, 20G, 20H, 50 recording media 22, 25, 28, 33 Adhesive layer 23, 26, 29, 34, 26A, 29A, 34A, 26B, 29B, 34B Insulation layer 24, 27, 30, 52 Color-developing layers 26A1, 29A1, 34A1 resin layer 26A2, 29A2, 34A2, 26B2, 29B2, 34B2 UV curing resin layer 26B1, 29B1, 34B1 Adhesive layer 31, 36 protective layer 32A, 32B, 32C, 35A, 35B, 35C, 37A, 37B, 37C, 38A, 38B, 38C Intermediate layer 36A UV curing resin layer 36B UV-cut layer 36C Adhesive layer 36D base material 52C, 52M, 52Y microcapsules 60 test specimens 60A, 60B Adherent 61 Tensile members 62 Clamping device 71 Test bench 72 Jigs 73A, 73B Movable Roll 100 Smartphones 200 Notebook Personal Computers 300 cosmetic containers 400 booklets

Claims

1. Substrate and A first intermediate layer provided on the substrate and having at least one housing portion, A recording medium provided within the aforementioned storage section, An overlay layer provided on the first intermediate layer and Equipped with, The housing portion is provided in a part of the plane of the first intermediate layer, The housing portion is a through hole penetrating in the thickness direction of the first intermediate layer, or a recessed portion in the thickness direction of the first intermediate layer. The recording medium comprises a color-developing layer containing an electron-donating color-developing compound, an electron-accepting color developer, and a matrix resin. The substrate, the first intermediate layer, and the overlay layer each contain a polycarbonate resin. A laminate in which the substrate and the first intermediate layer are bonded together by fusion, and the first intermediate layer and the overlay layer are bonded together by fusion.

2. Substrate and A first intermediate layer provided on the substrate and having at least one housing portion, A recording medium provided within the aforementioned storage section, An overlay layer provided on the first intermediate layer and Equipped with, The housing portion is provided in a part of the plane of the first intermediate layer, The housing portion is a through hole penetrating in the thickness direction of the first intermediate layer, or a recessed portion in the thickness direction of the first intermediate layer. The recording medium comprises a color-developing layer containing an electron-donating color-developing compound, an electron-accepting color developer, and a matrix resin. The substrate, the first intermediate layer, and the overlay layer each contain a polycarbonate resin. A laminate in which the substrate and the first intermediate layer are bonded together with a thermal adhesive, and the first intermediate layer and the overlay layer are bonded together with a thermal adhesive.

3. The aforementioned color-developing layer is configured to change its coloring state using laser light. The laminate according to claim 1 or 2, wherein the change in the colored state is an irreversible change.

4. The laminate according to claim 1 or 2, further comprising a photothermal conversion material in the color-developing layer.

5. The recording medium comprises a plurality of the color-developing layers, The laminate according to claim 1 or 2, wherein the plurality of color-developing layers contain color-developing compounds with different color hues from each other.

6. The recording medium comprises a plurality of color-developing layers, a plurality of second intermediate layers, and a protective layer. The plurality of color-developing layers include a first color-developing layer, a second color-developing layer, and a third color-developing layer. The first color-developing layer, the second intermediate layer, the second color-developing layer, the second intermediate layer, the third color-developing layer, the second intermediate layer, and the protective layer are laminated in this order. The laminate according to claim 1 or 2, wherein the first color-developing layer, the second color-developing layer, and the third color-developing layer each contain a color-developing compound having a different color hue.

7. The laminate according to claim 1 or 2, wherein the ratio of the color developer to the total amount of the color developer and the matrix resin is 16% by mass or less.

8. The laminate according to claim 1 or 2, wherein the electron-donating color-producing compound comprises a leuco dye.

9. The laminate according to claim 1 or 2, wherein the first intermediate layer is rewritable by an external stimulus such as laser light or heat.

10. The laminate according to claim 1 or 2, wherein the first intermediate layer is formed in a frame-like shape surrounding the peripheral edge of one main surface of the substrate.

11. The laminate according to claim 1 or 2, wherein the aforementioned housing section has at least two or more parts.

12. The recording medium comprises a plurality of color-developing layers and a plurality of second intermediate layers. The laminate according to claim 1 or 2, wherein the second intermediate layer is provided between adjacent color-developing layers.

13. The laminate according to claim 12, wherein at least one of the plurality of second intermediate layers comprises an ultraviolet curing resin layer and an adhesive layer.

14. At least one of the plurality of the above second intermediate layers comprises a resin layer, an ultraviolet curing resin layer, and an adhesive layer. The UV-curing resin layer is provided between the resin layer and the adhesive layer. The laminate according to claim 12, wherein the resin layer and the matrix resin include a polycarbonate-based resin.

15. The laminate according to claim 12, wherein at least one of the plurality of second intermediate layers comprises, in order, a first adhesive layer, an ultraviolet curing resin layer, and a second adhesive layer.

16. The laminate according to claim 12, wherein at least one of the plurality of second intermediate layers is a film that has been treated for easy adhesion.

17. The laminate according to claim 2, wherein the thermal adhesive comprises a thermosetting resin.

18. A card, booklet, passport, security card, or enclosure comprising the laminate described in any one of claims 1 to 17.

Images