WO2018092488A1 - 可逆性記録媒体および可逆性記録媒体用塗料ならびに外装部材 - Google Patents
可逆性記録媒体および可逆性記録媒体用塗料ならびに外装部材 Download PDFInfo
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- WO2018092488A1 WO2018092488A1 PCT/JP2017/037527 JP2017037527W WO2018092488A1 WO 2018092488 A1 WO2018092488 A1 WO 2018092488A1 JP 2017037527 W JP2017037527 W JP 2017037527W WO 2018092488 A1 WO2018092488 A1 WO 2018092488A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/305—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers with reversible electron-donor electron-acceptor compositions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
- B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
- B41M5/3275—Fluoran compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/337—Additives; Binders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/337—Additives; Binders
- B41M5/3375—Non-macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/337—Additives; Binders
- B41M5/3377—Inorganic compounds, e.g. metal salts of organic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/04—Direct thermal recording [DTR]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/41—Base layers supports or substrates
Definitions
- the present disclosure relates to a reversible recording medium capable of recording and erasing an image, a paint for the reversible recording medium, and an exterior member including the same.
- a reversible recording medium is generally composed of a color developing compound having an electron donating property, a developer / color reducing agent having an electron accepting property, and a matrix polymer.
- Patent Document 1 discloses a reversible multicolor recording medium in which the color development sensitivity is improved by using a salicylic acid compound as a developer / color-reducing agent.
- This reversible multicolor recording medium has a plurality of recording layers laminated. Each recording layer is formed to contain a cyanine-based photothermal conversion material in addition to the above materials, thereby selectively changing the hue of the desired recording layer by irradiating light of a specific wavelength. Is possible.
- reversible recording media are required to have stable color development and repeatability.
- a reversible recording medium includes a support base and a recording layer that is provided on the support base and reversibly changes a recording state and an erasing state.
- a photothermal conversion material comprising at least one of a compound having a cyanine skeleton having at least one of a 5-membered ring or a methine chain containing a 6-membered ring and an inorganic compound, a color-forming compound having an electron donating property,
- a developer / color-reducing agent composed of at least one of the compounds represented by the following general formula (1) has an electron accepting property.
- X is —NHCO—, —CONH—, —NHCONH—, —CONHCO—, —NHNHCO—, —CONHNH—, —CONHNHCO—, —NHCOCONH—, —NHCONHCO—, —CONHCONH—, —NHNHCONH—, —NHCONHNH -, -CONHNHCONH-, -NHCONHNHCO-, or -CONHNHCONH-, where R is a linear hydrocarbon group having 25 to 34 carbon atoms.
- the reversible recording medium coating material includes a compound having a phthalocyanine skeleton, a compound having a squarylium skeleton in a solvent, and SbF 6 , PF 6 , BF 4 , ClO 4 , CF 3 SO in the molecule.
- a photothermal conversion material comprising a seed, a color developing compound having an electron donating property, and a developer / color-reducing agent having an electron accepting property and comprising at least one of the compounds represented by the general formula (1). Is included.
- the exterior member according to an embodiment of the present disclosure is provided with the reversible recording medium according to the embodiment of the present disclosure on at least one surface.
- the coating material for a reversible recording medium of one embodiment, and the exterior member of one embodiment, the coloring compound having an electron donating property and the above-described general A developing / color-reducing agent comprising at least one of the compounds represented by the formula (1) was used. Further, a compound having a phthalocyanine skeleton, a compound having a squarylium skeleton, and any counter of SbF 6 , PF 6 , BF 4 , ClO 4 , CF 3 SO 3 and (CF 3 SO 3 ) 2 N in the molecule.
- a photothermal conversion material comprising at least one of a compound having a cyanine skeleton having at least one of an ion and a methine chain containing a 5-membered ring or a 6-membered ring and an inorganic compound is used. Thereby, the heat resistance of the recording layer can be improved.
- the reversible recording medium coating material of one embodiment, and the exterior member of one embodiment, the above general formula (1) is used as a developer / color-reducing agent constituting the recording layer. At least one of the compounds represented by the formula is used.
- a compound having a phthalocyanine skeleton, a compound having a squarylium skeleton, and SbF 6 , PF 6 , BF 4 , ClO 4 , CF 3 SO 3 and (CF 3 SO 3 ) 2 N in the molecule Since at least one of a compound having a cyanine skeleton and / or an inorganic compound having at least one of a counter ion and a methine chain containing a 5-membered ring or a 6-membered ring is used, color development sensitivity is maintained. However, it is possible to improve the color stability and the repeatability of drawing.
- FIG. 3 is a cross-sectional view illustrating an example of a configuration of a reversible recording medium according to a first embodiment of the present disclosure.
- FIG. It is a sectional view showing an example of composition of a reversible recording medium concerning a 2nd embodiment of this indication. It is a sectional view showing an example of composition of a reversible recording medium concerning a modification of this indication. It is a sectional view showing an example of composition of a reversible recording medium concerning a 3rd embodiment of this indication.
- 12 is a perspective view illustrating an example of an appearance of application example 1.
- FIG. 12 is a perspective view illustrating another example of the appearance of application example 1.
- FIG. 12 is a perspective view illustrating an example of an appearance of application example 2.
- FIG. 22 is a perspective view illustrating another example of the appearance of application example 2.
- FIG. 14 is a perspective view illustrating an example of an appearance (front side) of an application example 3.
- FIG. 16 is a perspective view illustrating an example of an appearance (back side) of an application example 3.
- FIG. 10 is an explanatory diagram illustrating a configuration example of an application example 4.
- First Embodiment an example of a reversible recording medium including a developer / color-reducing agent having a salicylic acid skeleton
- Configuration of reversible recording medium 1-2 Method for producing reversible recording medium 1-3. Recording and erasing method of reversible recording medium 1-4.
- Action / Effect Second embodiment an example of a reversible recording medium having a plurality of recording layers
- FIG. 1 illustrates a cross-sectional configuration of a reversible recording medium (reversible recording medium 1) according to the first embodiment of the present disclosure.
- a recording layer 12 capable of reversibly changing a recording state and an erasing state is disposed on a support substrate 11.
- FIG. 1 schematically shows a cross-sectional configuration of the reversible recording medium 1 and may differ from actual dimensions and shapes.
- the support base 11 is for supporting the recording layer 12.
- the support base 11 is made of a material having excellent heat resistance and excellent dimensional stability in the planar direction.
- the support base 11 may have either light transmissive property or non-light transmissive property.
- the support base 11 may be a rigid substrate such as a wafer, or may be composed of flexible thin glass, film, paper, or the like. By using a flexible substrate as the support base 11, a flexible (foldable) reversible recording medium can be realized.
- Examples of the constituent material of the support base 11 include polymer materials such as inorganic materials, metal materials, and plastics.
- the inorganic material include silicon (Si), silicon oxide (SiO x ), silicon nitride (SiN x ), and aluminum oxide (AlO x ).
- Silicon oxide includes glass or spin-on-glass (SOG).
- Examples of the metal material include aluminum (Al), nickel (Ni), and stainless steel
- examples of the polymer material include polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polyethylene. Examples include ruether ketone (PEEK), polyvinyl chloride (PVC), and copolymers thereof.
- a reflective layer (not shown) is preferably provided on the upper surface or the lower surface of the support base 11. By providing the reflective layer, clearer color display is possible.
- the recording layer 12 can reversibly record and erase information by heat.
- the recording layer 12 is made of a material capable of controlling a decoloring state and a coloring state, which can be stably and repeatedly recorded. Specifically, it is formed of, for example, a polymer material containing a color developable compound, a developer / color reducing agent, and a photothermal conversion material.
- the thickness of the recording layer 12 is, for example, 1 ⁇ m or more and 10 ⁇ m or less.
- Examples of the color developing compound include leuco dyes.
- Examples of leuco dyes include existing thermal paper dyes. Specifically, for example, a compound represented by the following formula (2-1), which contains a group having an electron donating property in the molecule, for example, can be given.
- the developing / color-reducing agent is, for example, for developing a colorless coloring compound or decoloring a coloring compound exhibiting a predetermined color.
- a compound having a salicylic acid skeleton represented by the following general formula (1) and having a group having an electron accepting property in the molecule can be given.
- X is —NHCO—, —CONH—, —NHCONH—, —CONHCO—, —NHNHCO—, —CONHNH—, —CONHNHCO—, —NHCOCONH—, —NHCONHCO—, —CONHCONH—, —NHNHCONH—, —NHCONHNH -, -CONHNHCONH-, -NHCONHNHCO-, or -CONHNHCONH-, where R is a linear hydrocarbon group having 25 to 34 carbon atoms.
- the photothermal conversion material generates heat by absorbing light in a predetermined wavelength region in the near infrared region, for example.
- a near-infrared absorbing dye having an absorption peak in a wavelength range of 700 nm to 2000 nm and having almost no absorption in the visible region.
- Specific examples include compounds having a phthalocyanine skeleton (phthalocyanine dyes), compounds having a squarylium skeleton (squarylium dyes), and inorganic compounds, for example.
- examples of inorganic compounds include metal complexes such as dithio complexes, diimonium salts, aminium salts, and inorganic compounds.
- inorganic compounds include graphite, carbon black, metal powder particles, tribasic cobalt oxide, iron oxide, chromium oxide, copper oxide, titanium black, metal oxides such as ITO, metal nitrides such as niobium nitride, tantalum carbide, etc.
- Metal carbides, metal sulfides, and various magnetic powders may be used.
- the excellent light resistance means that it does not decompose during laser irradiation.
- the excellent heat resistance is, for example, that when the film is formed with a polymer material and stored at 150 ° C.
- any counter ion of SbF 6 , PF 6 , BF 4 , ClO 4 , CF 3 SO 3 and (CF 3 SO 3 ) 2 N is included in the molecule.
- those having at least one of a methine chain containing a 5-membered ring or a 6-membered ring are included in the molecule.
- the compound having a cyanine skeleton used in the reversible recording medium of the present embodiment has both of the above counter ions and a cyclic structure such as a 5-membered ring and a 6-membered ring in the methine chain. However, if at least one is provided, sufficient light resistance and heat resistance are ensured.
- the polymer material is preferably one in which a color developing compound, a developer / color reducing agent, and a photothermal conversion material are easily dispersed uniformly.
- the polymer material include a thermosetting resin and a thermoplastic resin.
- the recording layer 12 is configured to contain at least one of each of the above color developable compound, developer / subtractor, and photothermal conversion material.
- developer / subtractor 1: 2 (weight ratio).
- a photothermal conversion agent it changes according to the film thickness of the recording layer 12.
- the recording layer 12 may include various additives such as a sensitizer and an ultraviolet absorber in addition to the above materials.
- a protective layer 13 is preferably formed on the recording layer 12.
- the protective layer 13 is for protecting the surface of the recording layer 12, and is formed using, for example, an ultraviolet curable resin or a thermosetting resin.
- the thickness of the protective layer 13 is, for example, 0.1 ⁇ m or more and 20 ⁇ m or less.
- the reversible recording medium 1 of the present embodiment can be manufactured using, for example, a coating method.
- the manufacturing method demonstrated below is an example and you may manufacture using another method.
- a vinyl chloride / vinyl acetate copolymer is dissolved as a polymer material in a solvent (for example, methyl ethyl ketone).
- a solvent for example, methyl ethyl ketone
- a developer / color reducing agent, a color developing compound and a photothermal conversion material are added and dispersed.
- the reversible recording medium coating material is obtained.
- the reversible recording medium coating material is applied to the support base 11 with a thickness of, for example, 3 ⁇ m and dried at, for example, 70 ° C. to form the recording layer 12.
- an acrylic resin is applied on the recording layer 12 to a thickness of 10 ⁇ m, for example, and then dried to form the protective layer 13.
- the reversible recording medium 1 shown in FIG. 1 is completed.
- the recording layer 12 may be formed using a method other than the above coating.
- the recording layer 12 may be formed by applying the film to another substrate in advance and attaching the film onto the support substrate 11 via, for example, an adhesive film.
- the recording layer 12 may be formed by immersing the support base 11 in a paint.
- recording and erasing method of reversible recording medium for example, recording and erasing can be performed as follows.
- the recording layer 12 is heated to a temperature at which the color developable compound is decolored, for example, at a temperature of 120 ° C., and is previously decolored.
- a temperature at which the color developable compound is decolored for example, at a temperature of 120 ° C.
- near infrared light whose wavelength and output are adjusted is irradiated to a desired position of the recording layer 12 by, for example, a semiconductor laser.
- the photothermal conversion material contained in the recording layer 12 generates heat, a color reaction (color development reaction) occurs between the color developing compound and the color developing / color reducing agent, and the irradiated portion develops color.
- the reversible recording medium 1 is heated at a temperature at which the reversible recording medium 1 is erased, for example, 120 ° C. Thereby, the information recorded on the recording layer 12 is erased collectively. Thereafter, by performing the above-described operation, repeated recording on the recording layer 12 becomes possible.
- the colored state and the decolored state are maintained unless the above-described coloring reaction and decoloring reaction such as near infrared irradiation and heating are performed.
- a reversible recording medium is generally composed of a color-forming compound having an electron donating property, a developer / color-reducing agent having an electron accepting property, and a matrix polymer. Further, the reversible recording medium can be recorded and erased by irradiating light of a specific wavelength by adding a photothermal conversion material.
- the reversible recording medium is assumed to be used for decoration on the surface of a casing of an electronic device or the like, interior or exterior of a building, for example, in addition to printing on an IC card or a label. For this reason, the reversible recording medium is required to have durability, particularly weather resistance.
- the weather resistance refers to “a property that is difficult to change outdoors and resists natural effects such as sunlight, wind and rain, dew, frost, heat, and dryness”.
- humidity and wetness such as wind, rain, dew, and drying can be dealt with by forming a moisture-resistant protective film or the like on the surface of the reversible recording medium.
- Sunlight can be dealt with by forming, for example, a UV-absorbing protective film on the surface of the reversible recording medium.
- temperature temperature
- the reversible recording medium itself is required to have durability (color stability over a long period of time).
- a phenolic compound is used as a developing / color-reducing agent, and attempts have been made to improve the stability of color development by developing a new phenolic compound. Further, in the reversible recording medium described in Patent Document 1, the color development sensitivity is improved by using a salicylic acid-based compound as a developer / color-reducing agent. In this reversible recording medium, it is possible to selectively change the hue of a specific recording layer among a plurality of stacked recording layers by using a photothermal conversion material.
- the above reversible recording medium can perform the first recording (color development), it is difficult to perform the second and subsequent recordings after erasing (erasing), and it is required to improve the drawing performance repeatedly.
- the reversible recording medium 1 of the present embodiment has a color developing compound having an electron donating group and a salicylic acid skeleton represented by the general formula (1), and R has 25 or more carbon atoms.
- the recording layer 12 is formed using a photothermal conversion material of any one of a developer / color-reducing agent having 34 or less linear hydrocarbon groups, a compound having a phthalocyanine skeleton, a compound having a squarylium skeleton, and an inorganic compound. I did it.
- the heat resistance of the recording layer 12 for example, the resistance to high temperatures (for example, higher than 200 ° C.) in laser irradiation during recording and erasing can be improved.
- the reversible recording medium 1 of the present embodiment has the salicylic acid skeleton represented by the general formula (1) as the developer / color-reducing agent constituting the recording layer 12, and R has 25 to 34 carbon atoms.
- a compound having a linear hydrocarbon group was used.
- the photothermal conversion material any one of a compound having a phthalocyanine skeleton, a compound having a squarylium skeleton, and an inorganic compound is used. Thereby, the heat resistance of the recording layer 12 is improved while maintaining the color development sensitivity.
- resistance to high temperatures for example, higher than 200 ° C.
- laser irradiation during recording (during drawing) and erasing can be improved, and repeated drawing characteristics can be improved.
- it is possible to improve the color development stability during storage at a high temperature for example, 60 ° C.
- FIG. 2 illustrates a cross-sectional configuration of a reversible recording medium (reversible recording medium 2) according to the second embodiment of the present disclosure.
- a recording layer 21 capable of reversibly changing a recording state and an erasing state is disposed on a support substrate 11.
- the recording layer 21 includes, for example, three layers (a first layer 22, a second layer 23, and a third layer 24) stacked in this order. Between the layers 22, 23, and 24, a heat insulating layer is formed. 25 and 26 are provided, respectively.
- FIG. 2 schematically shows a cross-sectional configuration of the reversible recording medium 1 and may differ from actual dimensions and shapes.
- the recording layer 21 is capable of reversibly recording and erasing information by heat.
- the first layer 22, the second layer 23, and the third layer 24 are formed from the support base 11 side. It has the structure laminated
- the first layer 22, the second layer 23, and the third layer 24 absorb the light having different colors, the developing / color-reducing agent corresponding to each colorable compound, and light in different wavelength ranges.
- it is made of a polymer material.
- the developer / color-reducing agent is, for example, for developing a colorless coloring compound or decoloring a coloring compound exhibiting a predetermined color.
- the developer / color-reducing agent is selected from, for example, compounds having a salicylic acid skeleton represented by the general formula (1) and containing a group having electron accepting properties in the molecule.
- the photothermal conversion material is selected from a compound having a phthalocyanine skeleton (phthalocyanine dye), a compound having a squarylium skeleton (squarylium dye), an inorganic compound, and the like.
- a compound having a cyanine skeleton having excellent light resistance and heat resistance may be used.
- the first layer 22 includes, for example, a color developing compound that develops a cyan color, a developer / color reducing agent corresponding to the color developing compound, and a photothermal conversion material that absorbs and exhibits infrared light having a wavelength ⁇ 1 , for example. It is configured.
- the second layer 23 includes, for example, a color-forming compound exhibiting a magenta color, a developer / color-reducing agent corresponding thereto, and a photothermal conversion material that generates heat by absorbing infrared light having a wavelength ⁇ 2 , for example.
- the third layer 24 includes, for example, a color developing compound exhibiting a yellow color, a developer / color reducing agent corresponding thereto, and a photothermal conversion material that generates heat by absorbing infrared light having a wavelength ⁇ 3 , for example. Thereby, a display medium capable of multicolor display is obtained.
- the photothermal conversion material it is preferable to select a combination of materials having a narrow light absorption band and not overlapping each other, for example, in a wavelength range of 700 nm to 2000 nm. As a result, a desired layer among the first layer 22, the second layer 23, and the third layer 24 can be selectively developed or decolored.
- the thicknesses of the first layer 22, the second layer 23, and the third layer 24 are, for example, preferably 1 ⁇ m or more and 20 ⁇ m or less, and more preferably 2 ⁇ m or more and 15 ⁇ m or less, for example. This is because if the thickness of each of the layers 22, 23, 24 is less than 1 ⁇ m, a sufficient color density may not be obtained. Moreover, when the thickness of each layer 22, 23, 24 is thicker than 20 ⁇ m, the heat utilization amount of each layer 22, 23, 24 increases, and there is a possibility that the color developability and decoloring property may deteriorate.
- the first layer 22, the second layer 23, and the third layer 24 are configured to include various additives such as a sensitizer and an ultraviolet absorber in addition to the above materials, as in the recording layer 12. It may be.
- heat insulating layers 25 and 26 are provided between the first layer 22 and the second layer 23 and between the second layer 23 and the third layer 24, respectively.
- the heat insulating layers 25 and 26 are made of, for example, a general polymer material having translucency.
- Specific materials include, for example, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethyl cellulose, polystyrene, styrene copolymer, phenoxy resin, polyester, aromatic polyester, polyurethane, polycarbonate, poly Examples thereof include acrylic acid esters, polymethacrylic acid esters, acrylic acid copolymers, maleic acid polymers, polyvinyl alcohol, modified polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, and starch.
- the heat insulation layers 25 and 26 may be comprised including various additives, such as a ultraviolet absorber, for example.
- the heat insulating layers 25 and 26 may be formed using a light-transmitting inorganic material.
- a light-transmitting inorganic material For example, when porous silica, alumina, titania, carbon, or a composite thereof is used, the thermal conductivity is lowered and the heat insulating effect is high, which is preferable.
- the heat insulating layers 25 and 26 can be formed by, for example, a sol-gel method.
- the thickness of the heat insulating layers 25 and 26 is preferably 3 or more and 100 ⁇ m or less, and more preferably 5 ⁇ m or more and 50 ⁇ m or less, for example. If the thickness of the heat insulating layers 25 and 26 is too thin, a sufficient heat insulating effect cannot be obtained. If the thickness is too thick, the thermal conductivity deteriorates or the translucency decreases when the entire reversible recording medium 2 is uniformly heated. It is because.
- recording and erasing can be performed as follows.
- the recording layer 21 will be described as an example in which the first layer 22, the second layer 23, and the third layer 24, which are cyan, magenta, and yellow, respectively, are stacked.
- the recording layer 21 (the first layer 22, the second layer 23, and the third layer 24) is heated at a temperature at which the recording layer 21 is decolored, for example, 120 ° C., and is previously decolored.
- an arbitrary portion of the recording layer 21 is irradiated with infrared light having an arbitrarily selected wavelength and output by, for example, a semiconductor laser.
- an infrared ray having a wavelength of ⁇ 1 is irradiated with energy at which the first layer 22 reaches the coloring temperature.
- the photothermal conversion material contained in the first layer 22 generates heat, a color reaction (color development reaction) occurs between the color developing compound and the developer / color reducing agent, and a cyan color is developed in the irradiated portion.
- a color reaction color development reaction
- an infrared ray having a wavelength ⁇ 2 is irradiated with an energy sufficient for the second layer 23 to reach the coloring temperature.
- an infrared ray having a wavelength ⁇ 3 is irradiated with energy that allows the third layer 24 to reach the coloring temperature.
- the photothermal conversion materials contained in the second layer 23 and the third layer 24 generate heat, respectively, and a color reaction occurs between the color developing compound and the developer / color reducing agent, and magenta and yellow colors respectively appear in the irradiated portion. Color develops.
- information for example, a full-color image
- the first layer 22, the second layer 23, and the third layer 24 that have been colored as described above are erased, infrared rays having wavelengths corresponding to the layers 22, 23, and 24 are set to the decolorization temperature. Irradiate with enough energy. As a result, the photothermal conversion materials contained in the first layer 22, the second layer 23, and the third layer 24 generate heat, and a decoloring reaction occurs between the color former and the developer / color-reducing agent, and coloration of the irradiated portion occurs. Disappears and the record is erased.
- the recording layer 21 is at a temperature at which all of the first layer 22, the second layer 23, and the third layer 24 are erased, for example, By heating at 120 ° C., information recorded on the recording layer 21 (the first layer 22, the second layer 23, and the third layer 24) is erased collectively. Thereafter, by performing the above-described operation, repeated recording on the recording layer 21 becomes possible.
- a color developing compound exhibiting yellow, magenta, or cyan, respectively, a corresponding developer / color-reducing agent, and a photothermal conversion material having different absorption wavelengths for example, a color developing compound exhibiting yellow, magenta, or cyan, respectively, a corresponding developer / color-reducing agent, and a photothermal conversion material having different absorption wavelengths.
- Three types of layers including the first layer 22, the second layer 23, and the third layer 24 were formed and laminated. As a result, it is possible to provide a reversible recording medium that has high color stability and repeatability while maintaining color development sensitivity and is capable of multicolor recording.
- FIG. 3 shows that the recording layer 32 corresponds to, for example, a color-forming compound that exhibits different colors (for example, cyan (C), magenta (M), and yellow (Y)), and each color-forming compound.
- a color-forming compound that exhibits different colors (for example, cyan (C), magenta (M), and yellow (Y)), and each color-forming compound.
- three kinds of microcapsules 32C, 32M, and 32Y each containing a developer / color-reducing agent and a photothermal conversion material that generates heat by absorbing light in different wavelength ranges.
- the recording layer 32 can be formed, for example, by dispersing the microcapsules 32C, 32M, and 32Y in, for example, the polymer material mentioned as the constituent material of the recording layer 12 and applying it onto the support substrate 11. .
- the recording layer 12 and the recording layer 21 are each a single (one type). Although the example formed using a coloring compound was shown, it is not restricted to this.
- the recording layers 12 and 21 each have a different color. You may make it form using a mixture of a plurality of types of color developing compounds.
- CMY of Japan color it is possible to reproduce various colors including CMY of Japan color by forming the recording layer by mixing a plurality of types of color-forming compounds.
- the cyan color can be reproduced by mixing a blue color developing compound and a green color forming compound in a predetermined ratio.
- the magenta color can be reproduced by mixing a red coloring compound and an orange coloring compound at a predetermined ratio.
- the degree of decoloring with respect to temperature changes as compared with the case where a single color forming compound is used. This is due to the difference in acidity (basicity) for each color developing compound.
- the recording layer in the reversible recording medium is composed of a basic color developing compound and an acidic developer / color-reducing agent, and colors when these react, Discolor by dissociation. That is, if the basicity and acidity of the color former and the color developing / subtracting agent are high, the coloration ability increases and the color erasure is difficult.
- the reversible recording medium 1 and the like of the present disclosure since the developer / color reducing agent having a long alkyl chain length (25 to 34 carbon atoms) is used, the intermolecular force between the developer and the color reducing agent is reduced. It becomes higher, and the developer and the color reducing agent in the recording layer 31 are easily arranged, so that the decoloring ability is improved. Therefore, in the reversible recording media 1 and 2 of the present disclosure, even if the recording layers 12 and 21 are formed using a plurality of types of color-forming compounds, they are equivalent to the case where they are formed using a single color-forming compound. The decoloring performance can be obtained. Note that, also in the reversible recording medium 3 of Modification 1, the microcapsules 32C, 32M, and 32Y constituting the recording layer 31 may be formed using a plurality of types of color-forming compounds, respectively.
- FIG. 4 illustrates a cross-sectional configuration of a reversible recording medium (reversible recording medium 4) according to the third embodiment of the present disclosure.
- a recording layer 42 capable of reversibly changing a recording state and an erasing state is disposed on a support substrate 11.
- the recording layer 42 is formed using a compound represented by the following general formula (3) as a color developing compound.
- the support base 11 and the protective layer 13 have the same configuration as that of the reversible recording medium 1 in the first embodiment.
- the recording layer 42 is capable of reversibly recording and erasing information by heat.
- the recording layer 42 is configured using a material capable of controlling a decoloring state and a coloring state, which enables stable repeated recording. Specifically, it is formed of, for example, a polymer material containing a color developable compound, a developer / color reducing agent, and a photothermal conversion material.
- the thickness of the recording layer 42 is, for example, 1 ⁇ m or more and 10 ⁇ m or less.
- Examples of the color developing compound include a compound containing an electron donating group having a phthalide skeleton represented by the following general formula (3).
- R1 and R2 are each independently a phenyl group, an aminophenyl group, an indolyl group, a benzoindolyl group, a juliloindolyl group, a chylolyl group, a quinoline group, a naphthalene group and an alkyl group, or a derivative thereof.
- R1 and R2 may be bonded to each other via carbon (C), nitrogen (N), oxygen (O) and sulfur (S) to form a condensed aliphatic ring or a condensed aromatic ring.
- the developer / color reducing agent As the developer / color reducing agent, the photothermal conversion material, and the polymer material, the same materials as those of the recording layer 12 in the first embodiment can be used.
- the recording layer 42 is configured to include at least one of each of the above color developable compound, the developer / subtractor, and the photothermal conversion material.
- the photothermal conversion agent changes according to the film thickness of the recording layer 42.
- the recording layer 42 may include various additives such as a sensitizer and an ultraviolet absorber other than the above materials.
- the group having a salicylic acid skeleton represented by the general formula (1) and having an electron donating property in the molecule for example, It is desirable to use a compound containing an alkyl chain).
- the light stability may be lowered depending on the structure of the coloring compound.
- a dye having an azaphthalide skeleton which is generally cited as a dye having high light resistance
- the light resistance may be lowered.
- the compound represented by the general formula (2) having a phthalide skeleton in the molecule is used as the color-forming compound having electron donating properties. did. Therefore, in addition to the effect in the first embodiment, the light stability can be improved.
- the reversible recording media 1 to 3 are a part of various electronic devices or clothing items, for example, a so-called wearable terminal, such as a watch (watch), a bag, clothes, a hat, glasses, shoes, etc.
- the type of the electronic device is not particularly limited.
- the present invention can be applied not only to electronic devices and clothing but also to interiors and exteriors such as walls of buildings and exteriors of furniture such as desks as exterior members.
- 5A and 5B show the appearance of an integrated circuit (IC) card with a rewrite function.
- the surface of the card is a printing surface 110, and, for example, a sheet-like reversible recording medium 1 is attached thereto.
- the IC card can appropriately draw and rewrite and erase the printing surface 110 as shown in FIGS. 5A and 5B.
- FIG. 6A illustrates an appearance configuration of the front surface of the smartphone
- FIG. 6B illustrates an appearance configuration of the back surface of the smartphone illustrated in FIG. 6A
- This smartphone includes, for example, a display unit 210 and a non-display unit 220, and a housing 230.
- the reversible recording medium 1 or the like is provided as an exterior member of the housing 230, for example, on one surface of the rear housing 230, thereby displaying various color patterns as shown in FIG. 6B. can do.
- the smart phone was mentioned here as an example, it is not restricted to this, For example, it can apply also to a notebook-type personal computer (PC), tablet PC, etc.
- PC personal computer
- the bag has a storage unit 310 and a handle 320, and the reversible recording medium 1 is attached to the storage unit 310, for example.
- Various characters and designs are displayed on the storage unit 310 by, for example, the reversible recording medium 1.
- various color patterns can be displayed, and the design of the storage unit 310 is changed from the example of FIG. 7A to the example of FIG. 7B. be able to. Electronic devices that are also useful in fashion applications can be realized.
- FIG. 8 shows an example of the configuration of a wristband that can record, for example, attraction boarding history and schedule information in an amusement park.
- This wristband has belt portions 411 and 412 and an information recording portion 420.
- the belt portions 411 and 412 have, for example, a band shape, and are configured such that end portions (not shown) can be connected to each other.
- a reversible recording medium 1 or the like is affixed to the information recording unit 420, and in addition to the attraction boarding history MH2 and schedule information IS (IS1 to IS3), for example, an information code CD is recorded.
- a visitor can record the information by holding a wristband over a drawing device installed at various places such as an attraction boarding reservation spot.
- the boarding history mark MH1 indicates the number of attractions boarded by a visitor wearing a wristband at the amusement park. In this example, the more the star mark is recorded as the boarding history mark MH1 as the boarding the attraction.
- the present invention is not limited to this.
- the color of the mark may be changed depending on the number of attractions on which the visitors have boarded.
- the schedule information IS indicates the schedule of visitors.
- information on all events including events reserved by visitors and events held at an amusement park is recorded as schedule information IS1 to IS3.
- the name of the attraction (attraction 201) where the attendee made the boarding reservation and the scheduled boarding time are recorded as schedule information IS1.
- an event in the park such as a parade and its scheduled start time are recorded as schedule information IS2.
- the restaurant reserved in advance by the visitor 5 and the scheduled meal time are recorded as schedule information IS3.
- identification information IID for identifying a wristband and website information IWS are recorded.
- the reversible recording medium is assumed to be used for decoration on the surface of a casing of an electronic device or the like, interior or exterior of a building, for example, in addition to printing on an IC card or a label.
- the reversible recording medium is desired to have weather resistance that can withstand a weather resistance test that is assumed to be left outdoors under the most severe conditions.
- the accelerated exposure test includes tests that evaluate changes in the color, gloss, strength, etc. of organic materials such as paint, plastic, and rubber (accelerated weather resistance test) and corrosion resistance of inorganic materials such as metal substrates and plating. There are two tests (accelerated corrosion test). Among these, the accelerated weather resistance test corresponds to the evaluation of the weather resistance of the reversible recording medium of the present disclosure.
- Accelerated weathering test is a test in which temperature, humidity, and wetting are incorporated into test conditions using an artificial light source approximated to the spectral distribution of sunlight.
- artificial light sources xenon arc lamps, open frame carbon arc lamps, ultraviolet carbon arc lamps, ultraviolet fluorescent lamps, metal halide lamps and the like are used.
- the artificial light source to be used is often determined by the material of the sample (test piece) and the usage environment.
- the temperature in the test chamber is often based on the temperature of the black panel thrown with the sample for calibration being 63 ⁇ 3 ° C., which is not dependent on the light source.
- test time depends greatly on the usage environment and usage method, so it cannot be clearly defined.
- test time of 1000 hours is defined for plastic plates, safety sign plates, etc. as the most severe conditions.
- the reference value of the color development stability test of the reversible recording medium of the present disclosure is 1000 hours at 63 ⁇ 3 ° C.
- the color developability can be determined based on the color density. When the density is 80% or less from the maximum color development state, the color is visually recognized by human eyes. Therefore, the condition is that the color density is maintained at 80% or more when stored in a temperature of 63 ⁇ 3 ° C. for 1000 hours with the heat-sensitive recording layer being colored.
- a reversible recording medium coating material was prepared, and a recording layer was formed.
- a vinyl chloride / vinyl acetate copolymer was dissolved in methyl ethyl ketone (MEK), and a developer / color-reducing agent K-01 was further added and dispersed using a rocking mill.
- a reversible recording medium coating material was coated on a 50 ⁇ m-thick PET using a wire bar to a thickness of 3 ⁇ m and dried at 70 ° C. for 30 minutes to obtain a recording layer (Experimental Example 1-1).
- the concentration of the photothermal conversion material Y-01 contained in the recording layer was adjusted so that the absorbance value at a wavelength of 920 nm was 1.
- Example 1-2 In Experimental Example 1-2, the above experiment was performed except that nonacosanoic acid (C 28 H 57 COOH) was replaced with C 29 H 59 COOH and a developer / color-reducing agent was synthesized (developed / color-reducing agent K-02). A recording layer was produced in the same manner as in Example 1-1.
- Example 1-3 In Experimental Example 1-3, the above experiment was performed except that nonacosanoic acid (C 28 H 57 COOH) was replaced with C 26 H 53 COOH and a developer / color-reducing agent was synthesized (developed / color-reducing agent K-03). A recording layer was produced in the same manner as in Example 1-1.
- Example 1-4 In Experimental Example 1-4, the above experiment was performed except that nonacosanoic acid (C 28 H 57 COOH) was replaced with C 25 H 51 COOH and a developer / color-reducing agent was synthesized (developed / color-reducing agent K-04). A recording layer was produced in the same manner as in Example 1-1.
- Example 1-5 In Experimental Example 1-5, the above experiment was performed except that nonacosanoic acid (C 28 H 57 COOH) was replaced with C 24 H 49 COOH and a developer / color-reducing agent was synthesized (developed / color-reducing agent K-05). A recording layer was produced in the same manner as in Example 1-1.
- Example 1-6 In Experimental Example 1-6, the above experiment was performed except that nonacosanoic acid (C 28 H 57 COOH) was replaced with C 23 H 47 COOH and a developer / color-reducing agent was synthesized (developed / color-reducing agent K-06). A recording layer was produced in the same manner as in Example 1-1.
- Example 1-7 In Experimental Example 1-7, the above experiment was performed except that nonacosanoic acid (C 28 H 57 COOH) was replaced with C 22 H 45 COOH and a developer / color-reducing agent was synthesized (developed / color-reducing agent K-07). A recording layer was produced in the same manner as in Example 1-1.
- Example 1-8 In Experimental Example 1-8, the above experiment was performed except that nonacosanoic acid (C 28 H 57 COOH) was replaced with C 21 H 43 COOH and a developer / color-reducing agent was synthesized (developed / color-reducing agent K-08). A recording layer was produced in the same manner as in Example 1-1.
- Example 1-9 In Experimental Example 1-9, the above experiment was performed except that nonacosanoic acid (C 28 H 57 COOH) was replaced with C 18 H 37 COOH and a developer / color-reducing agent was synthesized (developed / color-reducing agent K-09). A recording layer was produced in the same manner as in Example 1-1.
- Example 1-10 In Experimental Example 1-10, the above experiment was performed except that nonacosanoic acid (C 28 H 57 COOH) was replaced with C 14 H 29 COOH and a developer / color-reducing agent was synthesized (developed / color-reducing agent K-10). A recording layer was produced in the same manner as in Example 1-1.
- Example 1-11 In Experimental Example 1-11, the recording layer was formed using the same method as in Experimental Example 1-1 except that the photothermal conversion material having a phthalocyanine skeleton was replaced with the photothermal conversion material (Y-02) having a squarylium skeleton. Produced.
- Example 1-12 In Experimental Example 1-12, the recording layer was formed using the same method as in Experimental Example 1-1 except that the photothermal conversion material having a phthalocyanine skeleton was replaced with a photothermal conversion material (Y-03) made of a metal oxide. Was made.
- Example 1-13 In Experimental Example 1-13, except that the photothermal conversion material having a phthalocyanine skeleton was replaced with the photothermal conversion material (Y-04) having a cyanine skeleton using iodine (I) as a counter ion, the above Experimental Example 1-1 A recording layer was prepared using the same method as described above.
- Example 1-14 In Experimental Example 1-14, the photothermal conversion material having a phthalocyanine skeleton was changed to a photothermal conversion material (Y-05) having a cyanine skeleton having a cyclic structure in the methine chain using SbF 6 as a counter ion. A recording layer was produced using the same method as in Experimental Example 1-1.
- Example 1-14 in which SbF 6 was used as a counter ion and a photothermal conversion material (Y-05) having a cyanine skeleton containing a cyclic structure in the methine chain was used, excellent repeatability was obtained. From this, it was found that even a light-to-heat conversion material having a cyanine skeleton can realize excellent repeatability if it has excellent light resistance and heat resistance.
- Example 2 Evaluation of color developability and decolorability by developing / color-reducing agent
- Example 2-1 Same as Experimental Example 1 except that a leuco dye represented by the above formula (2-1) as a color developing compound and a developer / color-reducing agent K-01 as a developer / subtractor were used on the support substrate.
- a recording layer was produced using the same material and the same film formation method.
- Example 2-2 A memory layer was produced in the same manner as in Experimental Example 2-1, except that the leuco dye represented by the above formula (2-2) was used as the color developing compound.
- Example 2-3 A memory layer was produced in the same manner as in Experimental Example 2-1, except that the leuco dye represented by the above formula (2-4) was used as the color developing compound.
- Example 2-4 A memory layer was prepared in the same manner as in Experimental Example 2-1, except that the developer / color-reducing agent K-09 was used.
- Example 2-5 A memory layer was produced in the same manner as in Experimental Example 2-2 except that the developer / color-reducing agent K-09 was used.
- Example 2-6 A memory layer was produced in the same manner as in Experimental Example 2-3 except that the developer / color-reducing agent K-09 was used.
- FIG. 9 is a plot of changes in color density (OD value) against temperature changes in Experimental Examples 2-1 to 2-3.
- FIG. 10 is a plot of changes in color density (OD value) with respect to temperature changes in Experimental Examples 2-4 to 2-6.
- Table 2 shows the temperature at which the color density reaches 0.8 (T1) and the temperature at which the color density reaches 0.2 (T2) when the initial color density of each of Experimental Examples 2-1 to 2-6 is 1.
- the developer / color-reducing agent used in the reversible recording medium is a developer / color-reducing agent having a steep temperature gradient at the time of erasure and a long alkyl chain length in the R part (for example, a developer / color-reducing agent having 28 carbon atoms). It has been found preferable to use K-01).
- FIG. 11 shows the case where K-01 is used as the developer / color-reducing agent, and the two kinds of leuco dyes shown in the formulas (2-1) and (2-4) are used as the color developing compounds.
- the erasing curve of the recording layer mixed at a ratio of The mixing ratio of the two types of leuco dyes (formula (2-1) / formula (2-4)) is 9/1, 8/2, 7/3, and 6/4 in weight ratio, respectively. From FIG. 11, it was found that the use of K-01, which is an example of the developer / color-reducing agent of the present disclosure, has an almost constant erasure curve regardless of the mixing ratio of the leuco dye. That is, the recording layer is composed of a plurality of types of color developing compounds and the developer / decolorizer of the present disclosure, thereby maintaining high color stability and high repeatability while maintaining color sensitivity. And a reversible recording medium having high color reproducibility.
- Example 3 Evaluation of light resistance stability
- a developer / color-reducing agent was synthesized. 10 g of octacosanoic acid (C 27 H 55 COOH), 4.6 g of triethylamine, and 50 ml of toluene were placed in the flask and heated to 40 ° C. Subsequently, after adding 6.3 g of DPPA to reflux, the mixture was allowed to cool to room temperature. Next, the solvent was removed to obtain 16.2 g of octacosyl isocyanate.
- a reversible recording medium coating material was prepared, and a recording layer was formed.
- a vinyl chloride / vinyl acetate copolymer was dissolved in methyl ethyl ketone (MEK), and a developer / color-reducing agent K-11 was further added and dispersed using a rocking mill.
- a reversible recording medium coating material was coated on a 50 ⁇ m-thick PET using a wire bar to a thickness of 3 ⁇ m and dried at 70 ° C. for 30 minutes to obtain a recording layer (Experimental Example 1-1).
- the concentration of the photothermal conversion material Y-01 contained in the recording layer was adjusted so that the absorbance value at a wavelength of 920 nm was 1.
- Example 3-2 In Experimental Example 3-2, recording was performed using the same method as in Experimental Example 3-1, except that the leuco dye represented by Formula (3-1) was replaced with the leuco dye represented by Formula (4-1) below. A layer was made.
- Example 3-3 In Experimental Example 3-3, the same method as in Experimental Example 3-1 was used, except that the leuco dye represented by Formula (3-1) was replaced with the leuco dye represented by Formula (3-2) below. A recording layer was prepared.
- Example 3-4 In Experimental Example 3-4, the same method as in Experimental Example 3-1 was used, except that the leuco dye represented by formula (3-1) was replaced with the leuco dye represented by formula (4-2) below. A recording layer was prepared.
- Example 3-5 In Experimental Example 3-5, the same method as in Experimental Example 3-1 was used, except that the leuco dye represented by formula (3-1) was replaced with the leuco dye represented by formula (3-3) below. A recording layer was prepared.
- Example 3-6 In Experimental Example 3-6, the same method as in Experimental Example 3-1 was used, except that the leuco dye represented by Formula (3-1) was replaced with the leuco dye represented by Formula (2-5) above. A recording layer was prepared.
- Example 3-7 In Experimental Example 3-7, 4-aminomethoxyphenol was used in place of 4-aminosalicylic acid, and the same reaction as in Experimental Example 3-1 was performed. Then, the methoxy group was eliminated, and the following formula (1-2) The developed developer and color-reducing agent were synthesized. Thereafter, a recording layer was produced using the same method as in Experimental Example 3-1.
- Example 3-8 In Experimental Example 3-8, the same method as in Experimental Example 3-7 was used, except that the leuco dye represented by formula (3-1) was replaced with the leuco dye represented by formula (3-2) below. A recording layer was prepared.
- a UV barrier film is provided on a sample that has been colored for color development evaluation, irradiated with a xenon lamp with 60 W illuminance by a light resistance tester manufactured by Q-Lab, and the color density is 80%.
- the decay time was measured. The case where this time exceeded 200 hours was designated as A, and the case where it was less than 200 hours was designated as B.
- Experimental Example 3-7 and Experimental Example 3-8 showed a marked decrease in color developability. This is due to the difference in acidity between the developer and the color reducing agent, and the acidity of the developer and the color reducing agent having the salicylic acid skeleton is higher than that of the phenol skeleton. From this, it was found that it is preferable to use a compound having a salicylic acid skeleton having a higher acidity as the developer / color reducing agent.
- Experimental Example 3 Comparing Experimental Example 3-1 to Experimental Example 3-6, Experimental Example 3 using a leuco dye having a phthalide skeleton represented by Formula (3-1), Formula (3-2), and Formula (3-3) -1, Experimental Example 3-3 and Experimental Example 3-5 are experimental examples using a leuco dye having an azaphthalide skeleton represented by formula (4-1), formula (4-2) and formula (2-5) Light resistance superior to 3-2, Experimental Example 3-4 and Experimental Example 3-6 was confirmed. Therefore, when using a salicylic acid-based developer / color-reducing agent, it is possible to obtain a higher light-resistant stability by using a leuco dye having a phthalide skeleton than a leuco dye having an azaphthalide skeleton. It was found that the part does not significantly affect the light stability.
- a leuco dye having an azaphthalide skeleton has a nitrogen (N) atom in the skeleton.
- N nitrogen
- a vacant electron orbital exists in the N atom part, and that part becomes a reaction point (active point) with the developer / decolorizer.
- a leuco dye having a phthalide skeleton has no N atom in the skeleton, and therefore, it is unlikely that a lactone ring other than the color developing / decoloring point will be a reaction point with the developer / color reducing agent.
- the present disclosure has been described with reference to the first and second embodiments and the first and second modified examples 1 and 2 and the examples. Is possible. For example, it is not necessary to include all the components described in the first embodiment and the second embodiment, and other components may be included. Moreover, the material and thickness of the component mentioned above are examples, and are not limited to what was described.
- a support substrate A recording layer provided on the support substrate and reversibly changing a recording state and an erasing state;
- the recording layer is A compound having a phthalocyanine skeleton, a compound having a squarylium skeleton, containing any of SbF 6 , PF 6 , BF 4 , ClO 4 , CF 3 SO 3 and (CF 3 SO 3 ) 2 N as a counter ion, or a methine chain
- a photothermal conversion material comprising at least one of a compound having a cyanine skeleton containing a 5-membered ring structure or a 6-membered ring structure therein and an inorganic compound;
- a color-forming compound having an electron donating property;
- a reversible recording medium having electron acceptability and a developer / color-reducing agent comprising at least one compound represented by the following general formula (1).
- the recording layer has a first layer and a second layer as a plurality of layers, The reversible recording medium according to any one of [1] to [3], wherein the first layer and the second layer each include a photothermal conversion material having different absorption wavelength regions.
- the recording layer further includes a thermosetting resin or a thermoplastic resin.
- the compound having a cyanine skeleton contains any one of SbF 6 , PF 6 , BF 4 , ClO 4 , CF 3 SO 3 and (CF 3 SO 3 ) 2 N as a counter ion, and is a 5-membered member in the methine chain.
- [8] The reversible recording medium according to any one of [1] to [7], wherein recording on the recording layer and erasing of the recording are performed by irradiating near infrared rays in a predetermined wavelength region.
- the reversible recording medium according to any one of [1] to [8], wherein recording on the recording layer and erasing of the recording are performed by irradiating a semiconductor laser.
- a support substrate A recording layer provided on the support substrate and reversibly changing a recording state and an erasing state;
- the recording layer is A compound having a phthalocyanine skeleton, a compound having a squarylium skeleton, a counter ion of any one of SbF 6 , PF 6 , BF 4 , ClO 4 , CF 3 SO 3 and (CF 3 SO 3 ) 2 N in the molecule;
- a photothermal conversion material comprising at least one of a compound having a cyanine skeleton having at least one of a 5-membered ring or a methine chain containing a 6-membered ring and an inorganic compound;
- a color former compound having an electron donating property and represented by the following general formula (2):
- R1 and R2 are each independently a phenyl group, an aminophenyl group, an indolyl group, a benzoindolyl group, a juliloindolyl group, a chylolyl group, a quinoline group, a naphthalene group and an alkyl group, or a derivative thereof.
- R1 and R2 may be bonded to each other via carbon (C), nitrogen (N), oxygen (O) and sulfur (S) to form a condensed aliphatic ring or a condensed aromatic ring.
- a compound having a phthalocyanine skeleton, a compound having a squarylium skeleton, containing any of SbF 6 , PF 6 , BF 4 , ClO 4 , CF 3 SO 3 and (CF 3 SO 3 ) 2 N as a counter ion, or a methine chain A photothermal conversion material comprising at least one of a compound having a cyanine skeleton containing a 5-membered ring structure or a 6-membered ring structure therein and an inorganic compound; A color-forming compound having an electron donating property; A color-forming compound having an electron donating property; A reversible recording medium coating material having electron acceptability and comprising a developer / color-reducing agent comprising at least one compound selected from the following general formula (1).
- the reversible recording medium is A support substrate; A recording layer provided on the support substrate and reversibly changing a recording state and an erasing state; The recording layer is A compound having a phthalocyanine skeleton, a compound having a squarylium skeleton, containing any of SbF 6 , PF 6 , BF 4 , ClO 4 ,
- X is —NHCO—, —CONH—, —NHCONH—, —CONHCO—, —NHNHCO—, —CONHNH—, —CONHNHCO—, —NHCOCONH—, —NHCONHCO—, —CONHCONH—, —NHNHCONH—, —NHCONHNH -, -CONHNHCONH-, -NHCONHNHCO-, or -CONHNHCONH-, where R is a linear hydrocarbon group having 25 to 34 carbon atoms.
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Abstract
Description
1.第1の実施の形態(サリチル酸骨格を有する顕・減色剤を含む可逆性記録媒体の例)
1-1.可逆性記録媒体の構成
1-2.可逆性記録媒体の製造方法
1-3.可逆性記録媒体の記録および消去方法
1-4.作用・効果
2.第2の実施の形態(複数の記録層を備えた可逆性記録媒体の例)
2-1.可逆性記録媒体の構成
2-2.可逆性記録媒体の記録および消去方法
2-3.作用・効果
3.変形例
3-1.変形例1(1層の記録層で多色表示が可能な可逆性記録媒体の例)
3-2.変形例2(複数種類の呈色性化合物を混合して記録層を形成した例)
4.第3の実施の形態(呈色性化合物としてフタリド骨格を有する化合物を用いた例)
4-1.可逆性記録媒体の構成
4-2.作用・効果
5.適用例
6.実施例
図1は、本開示の第1の実施の形態に係る可逆性記録媒体(可逆性記録媒体1)の断面構成を表したものである。可逆性記録媒体1は、例えば、支持基体11上に、記録状態および消去状態を可逆的に変化させることが可能な記録層12が配置されたものである。なお、図1は、可逆性記録媒体1の断面構成を模式的に表したものであり、実際の寸法、形状とは異なる場合がある。
支持基体11は、記録層12を支持するためのものである。支持基体11は、耐熱性に優れ、且つ、平面方向の寸法安定性に優れた材料により構成されている。支持基体11は、光透過性および非光透過性のどちらの特性を有していてもよい。支持基体11は、例えば、ウェハ等の剛性を有する基板でもよいし、可撓性を有する薄層ガラス、フィルムあるいは紙等により構成してもよい。支持基体11として可撓性基板を用いることにより、フレキシブル(折り曲げ可能)な可逆性記録媒体を実現できる。
本実施の形態の可逆性記録媒体1は、例えば、塗布法を用いて製造することができる。なお、以下に説明する製造方法は一例であり、その他の方法を用いて製造してもよい。
本実施の形態の可逆性記録媒体1では、例えば、以下のようにして記録および消去を行うことができる。
前述したように、印刷物に替わる表示媒体の開発が進められており、その1つとして、熱により可逆的に情報の記録や消去が可能な可逆性記録媒体が注目されている。可逆性記録媒体は、一般に、電子供与性を有する呈色性化合物と、電子受容性を有する顕・減色剤と、マトリクスポリマーとから構成されている。更に、可逆性記録媒体は、光熱変換材料を加えることで、特定の波長の光を照射することで記録および消去が可能となる。
図2は、本開示の第2の実施の形態に係る可逆性記録媒体(可逆性記録媒体2)の断面構成を表したものである。可逆性記録媒体2は、例えば、支持基体11上に、記録状態および消去状態を可逆的に変化させることが可能な記録層21が配置されたものである。この記録層21は、例えば、3つの層(第1層22、第2層23および第3層24)がこの順に積層されたものであり、各層22,23,24の間には、断熱層25,26がそれぞれ設けられている。なお、図2は、可逆性記録媒体1の断面構成を模式的に表したものであり、実際の寸法、形状とは異なる場合がある。
記録層21は、熱により可逆的に情報の記録や消去が可能なものであり、上記のように、例えば、第1層22、第2層23および第3層24が支持基体11側からこの順に積層された構成を有する。第1層22、第2層23および第3層24は、互いに異なる色を呈する呈色性化合物と、各呈色性化合物に対応する顕・減色剤と、互いに異なる波長域の光を吸収して発熱する光熱変換材料とを含む、例えば、高分子材料によって形成されている。顕・減色剤は、上記のように、例えば、無色の呈色性化合物を発色または、所定の色を呈している呈色性化合物を消色させるためのものである。顕・減色剤は、例えば、上記一般式(1)に示したサリチル酸骨格を有し、分子内に電子受容性を有する基を含む化合物から選択される。光熱変換材料は、上記のように、フタロシアニン骨格を有する化合物(フタロシアニン系染料)、スクアリリウム骨格を有する化合物(スクアリリウム系染料)および無機化合物等から選択される。この他、上記第1の実施の形態と同様に、優れた耐光性および耐熱性を有するシアニン骨格を有する化合物(シアニン系染料)を用いてもよい。
本実施の形態の可逆性記録媒体2では、例えば、以下のようにして記録および消去を行うことができる。なお、ここでは記録層21は、上述した、それぞれ、シアン色、マゼンタ色、イエロー色を呈する第1層22、第2層23および第3層24が積層されている場合を例に説明する。
本実施の形態の可逆性記録媒体2では、例えば、それぞれ、イエロー色、マゼンタ色またはシアン色を呈する呈色性化合物と、対応する顕・減色剤と、互いに異なる吸収波長を有する光熱変換材料とを含む3種の層(第1層22、第2層23および第3層24)を形成し、これを積層させるようにした。これにより、発色感度を維持しつつ、高い発色の安定性および繰り返し描画性を有すると共に、多色での記録が可能な可逆性記録媒体を提供することが可能となる。
(3-1.変形例1)
上記第2の実施の形態では、記録層21として、互いに異なる色を呈する層(第1層22、第2層23および第3層24)を形成し、これらを積層した多層構造を有する例を示したが、例えば単層構造でも多色表示が可能な可逆性記録媒体を実現することができる。
上記第1の実施の形態および第2に実施の形態では、記録層12および記録層21(第1層22、第2層23および第3層24)を、それぞれ、単一(1種類)の呈色性化合物を用いて形成する例を示したが、これに限らない。上記第1,第2の実施の形態における可逆性記録媒体1,2では、記録層12,21(第1層22,第2層23,第3層24)を、それぞれ、互いに異なる色を呈する複数種類の呈色性化合物を混合して用いる形成するようにしてもよい。
図4は、本開示の第3の実施の形態に係る可逆性記録媒体(可逆性記録媒体4)の断面構成を表したものである。可逆性記録媒体4は、例えば、支持基体11上に、記録状態および消去状態を可逆的に変化させることが可能な記録層42が配置されたものである。この記録層42は、呈色性化合物として下記一般式(3)で表される化合物を用いて形成されたものである。
支持基体11および保護層13は、上記第1の実施の形態における可逆性記録媒体1と同様の構成を有する。
次に、上記第1の実施の形態、第2の実施の形態および第3の実施の形態ならびに変形例1,2において説明した可逆性記録媒体(例えば、可逆性記録媒体1等)の適用例について説明する。ただし、以下で説明する電子機器の構成はあくまで一例であり、その構成は適宜変更可能である。上記可逆性記録媒体1~3は、各種の電子機器あるいは服飾品の一部、例えば、いわゆるウェアラブル端末として、例えば時計(腕時計)、鞄、衣服、帽子、眼鏡および靴等の服飾品の一部に適用可能であり、その電子機器等の種類は特に限定されない。また、電子機器や服飾品に限らず、例えば、外装部材として、建造物の壁等の内装や外装、机等の家具の外装等にも適用することができる。
図5Aおよび図5Bは、リライト機能付きIntegrated Circuit(IC)カードの外観を表したものである。このICカードでは、カードの表面が印字面110となっており、例えば、シート状の可逆性記録媒体1等が貼付されて構成されている。ICカードは、印字面110に可逆性記録媒体1等を配置することで、図5Aおよび図5Bに示したように、適宜、印字面110に描画およびその書き換え並びに消去が可能となる。
図6Aはスマートフォンの前面の外観構成を、図6Bは、図6Aに示したスマートフォンの背面の外観構成を表したものである。このスマートフォンは、例えば、表示部210および非表示部220と、筐体230とを備えている。背面側の筐体230の例えば一面には、筐体230の外装部材として、例えば可逆性記録媒体1等が設けられており、これにより、図6Bに示したように、様々な色柄を表示することができる。なお、ここでは、スマートフォンを例に挙げたが、これに限らず、例えば、ノート型パーソナルコンピュータ(PC)やタブレットPC等にも適用することができる。
図7Aおよび図7Bは、鞄の外観を表したものである。この鞄は、例えば収納部310と持ち手320とを有しており、例えば、収納部310に、例えば可逆性記録媒体1が取り付けられている。収納部310には、例えば可逆性記録媒体1により、様々な文字や図柄が表示される。また、持ち手320部分に可逆性記録媒体1等が取り付けることで、様々な色柄を表示することができ、図7Aの例から図7Bの例のように、収納部310の意匠を変更することができる。ファッション用途においても有用な電子デバイスを実現可能となる。
図8は、例えばアミューズメントパークにおいて、例えばアトラクションの搭乗履歴やスケジュール情報等を記録可能なリストバンドの一構成例を表したものである。このリストバンドは、ベルト部411,412と、情報記録部420とを有している。ベルト部411,412は、例えば帯形状を有し、端部(図示せず)が互いに接続可能に構成されている。情報記録部420には、例えば可逆性記録媒体1等が貼付されており、上記アトラクションの搭乗履歴MH2やスケジュール情報IS(IS1~IS3)のほか、例えば情報コードCDが記録されている。アミューズメントパークでは、入場者が、アトラクション搭乗予約スポット等の各所に設置された描画装置にリストバンドをかざすことによって上記情報を記録することができる。
次に、本開示の実施例について詳細に説明する。なお、下記実験において作製した可逆性記録媒体は、以下を基準にして評価した。
(実験例1-1)
まず、顕・減色剤を合成した。ノナコサン酸(C28H57COOH)10g、トリエチルアミン4.6g、トルエン50mlをフラスコ内に入れ、40℃まで加熱した。続いて、DPPA6.3gを追加して還流したのち、室温まで放冷した。次に、溶剤を除去してオクタコシルイソシアネート16.2gを得た。続いて、別のフラスコに入れた4-アミノサリチル酸4.2gに、テトラヒドロフラン(THF)に溶かしたオクタコシルイソシアネート16.2gを追加して加熱還流を行った。これを室温まで冷却し、析出した固体をろ取し、洗浄した。これにより、下記式(1-1)で表わされる顕・減色剤K-01を得た。
実験例1-2では、ノナコサン酸(C28H57COOH)をC29H59COOHに替えて顕・減色剤を合成(顕・減色剤K-02)し、これを用いた以外は上記実験例1-1と同様の方法を用いて記録層を作製した。
実験例1-3では、ノナコサン酸(C28H57COOH)をC26H53COOHに替えて顕・減色剤を合成(顕・減色剤K-03)し、これを用いた以外は上記実験例1-1と同様の方法を用いて記録層を作製した。
実験例1-4では、ノナコサン酸(C28H57COOH)をC25H51COOHに替えて顕・減色剤を合成(顕・減色剤K-04)し、これを用いた以外は上記実験例1-1と同様の方法を用いて記録層を作製した。
実験例1-5では、ノナコサン酸(C28H57COOH)をC24H49COOHに替えて顕・減色剤を合成(顕・減色剤K-05)し、これを用いた以外は上記実験例1-1と同様の方法を用いて記録層を作製した。
実験例1-6では、ノナコサン酸(C28H57COOH)をC23H47COOHに替えて顕・減色剤を合成(顕・減色剤K-06)し、これを用いた以外は上記実験例1-1と同様の方法を用いて記録層を作製した。
実験例1-7では、ノナコサン酸(C28H57COOH)をC22H45COOHに替えて顕・減色剤を合成(顕・減色剤K-07)し、これを用いた以外は上記実験例1-1と同様の方法を用いて記録層を作製した。
実験例1-8では、ノナコサン酸(C28H57COOH)をC21H43COOHに替えて顕・減色剤を合成(顕・減色剤K-08)し、これを用いた以外は上記実験例1-1と同様の方法を用いて記録層を作製した。
実験例1-9では、ノナコサン酸(C28H57COOH)をC18H37COOHに替えて顕・減色剤を合成(顕・減色剤K-09)し、これを用いた以外は上記実験例1-1と同様の方法を用いて記録層を作製した。
実験例1-10では、ノナコサン酸(C28H57COOH)をC14H29COOHに替えて顕・減色剤を合成(顕・減色剤K-10)し、これを用いた以外は上記実験例1-1と同様の方法を用いて記録層を作製した。
実験例1-11では、フタロシアニン骨格を有する光熱変換材料を、スクアリリウム骨格を有する光熱変換材料(Y-02)に替えた以外は、上記実験例1-1と同様の方法を用いて記録層を作製した。
実験例1-12では、フタロシアニン骨格を有する光熱変換材料を、金属酸化物からなる光熱変換材料(Y-03)に替えた以外は、上記実験例1-1と同様の方法を用いて記録層を作製した。
実験例1-13では、フタロシアニン骨格を有する光熱変換材料を、カウンターイオンとしてヨウ素(I)を用いたシアニン骨格を有する光熱変換材料(Y-04)に替えた以外は、上記実験例1-1と同様の方法を用いて記録層を作製した。
実験例1-14では、フタロシアニン骨格を有する光熱変換材料を、カウンターイオンとしてSbF6を用い、メチン鎖内に環状構造を含むシアニン骨格を有する光熱変換材料(Y-05)に変えた以外は、上記実験例1-1と同様の方法を用いて記録層を作製した。
(実験例2-1)
支持基体上に、呈色性化合物として上記式(2-1)に示したロイコ色素と、顕・減色剤として、顕・減色剤K-01とを用いた以外は、上記実験例1と同じ材料および同じ成膜方法を用いて記録層を作製した。
呈色性化合物として上記式(2-2)に示したロイコ色素を用いた以外は、実験例2-1と同様の方法を用いて記憶層を作製した。
呈色性化合物として上記式(2-4)に示したロイコ色素を用いた以外は、実験例2-1と同様の方法を用いて記憶層を作製した。
顕・減色剤K-09を用いた以外は、実験例2-1と同様の方法を用いて記憶層を作製した。
顕・減色剤K-09を用いた以外は、実験例2-2と同様の方法を用いて記憶層を作製した。
顕・減色剤K-09を用いた以外は、実験例2-3と同様の方法を用いて記憶層を作製した。
(実験例3-1)
まず、顕・減色剤を合成した。オクタコサン酸(C27H55COOH)10g、トリエチルアミン4.6g、トルエン50mlをフラスコ内に入れ、40℃まで加熱した。続いて、DPPA6.3gを追加して還流したのち、室温まで放冷した。次に、溶剤を除去してオクタコシルイソシアネート16.2gを得た。続いて、別のフラスコに入れた4-アミノサリチル酸4.2gに、テトラヒドロフラン(THF)に溶かしたオクタコシルイソシアネート16.2gを追加して加熱還流を行った。これを室温まで冷却し、析出した固体をろ取し、洗浄した。これにより、上記式(1-1)のRがC27H55の顕・減色剤K-01を得た。
実験例3-2では、式(3-1)で表わされるロイコ色素を下記式(4-1)で表わされるロイコ色素に替えた以外は上記実験例3-1と同様の方法を用いて記録層を作製した。
実験例3-3では、式(3-1)で表されるロイコ色素を下記式(3-2)で表わされるロイコ色素に替えた以外は上記実験例3-1と同様の方法を用いて記録層を作製した。
実験例3-4では、式(3-1)で表されるロイコ色素を下記式(4-2)で表わされるロイコ色素に替えた以外は上記実験例3-1と同様の方法を用いて記録層を作製した。
実験例3-5では、式(3-1)で表されるロイコ色素を下記式(3-3)で表わされるロイコ色素に替えた以外は上記実験例3-1と同様の方法を用いて記録層を作製した。
実験例3-6では、式(3-1)で表されるロイコ色素を上記式(2-5)で表わされるロイコ色素に替えた以外は上記実験例3-1と同様の方法を用いて記録層を作製した。
実験例3-7では、4-アミノサリチル酸の替わりに4-アミノメトキシフェノールを用い、実験例3-1と同様の反応を行った後、メトキシ基を脱離し、下記式(1-2)で表される顕・減色剤を合成した。この後、上記実験例3-1と同様の方法を用いて記録層を作製した。
実験例3-8では、式(3-1)で表されるロイコ色素を下記式(3-2)で表わされるロイコ色素に替えた以外は上記実験例3-7と同様の方法を用いて記録層を作製した。
[1]
支持基体と、
前記支持基体上に設けられると共に、記録状態および消去状態が可逆的に変化する記録層とを備え、
前記記録層は、
フタロシアニン骨格を有する化合物、スクアリリウム骨格を有する化合物、カウンターイオンとしてSbF6,PF6,BF4,ClO4,CF3SO3および(CF3SO3)2Nのいずれかを含む、または、メチン鎖内に5員環または6員環の環状構造を含むシアニン骨格を有する化合物および無機化合物のうちの少なくとも1種からなる光熱変換材料と、
電子供与性を有する呈色性化合物と、
電子受容性を有する共に、下記一般式(1)で表わされる化合物のうちの少なくとも1種からなる顕・減色剤とを含む
可逆性記録媒体。
[2]
前記記録層は、前記呈色性化合物を2種以上含む、前記[1]に記載の可逆性記録媒体。
[3]
前記記録層は複数の層からなる、前記[1]または[2]に記載の可逆性記録媒体。
[4]
前記記録層は、複数の層として第1層および第2層を有し、
前記第1層および前記第2層は、それぞれ、互いに吸収波長領域の異なる光熱変換材料を含む、前記[1]乃至[3]のうちのいずれかに記載の可逆性記録媒体。
[5]
前記光熱変換材料の吸収ピーク波長は、700nm以上2000nm以下である、前記[1]乃至[4]のうちのいずれかに記載の可逆性記録媒体。
[6]
前記記録層は、さらに熱硬化性樹脂または熱可塑性樹脂を含む、前記[1]乃至[5]のうちのいずれかに記載の可逆性記録媒体。
[7]
前記シアニン骨格を有する化合物は、カウンターイオンとしてSbF6,PF6,BF4,ClO4,CF3SO3および(CF3SO3)2Nのいずれかを含み、且つ、メチン鎖内に5員環または6員環の環状構造を含む、前記[1]乃至[6]のうちのいずれかに記載の可逆性記録媒体。
[8]
所定の波長領域の近赤外線を照射することによって前記記録層への記録および前記記録の消去を行う、前記[1]乃至[7]のうちのいずれかに記載の可逆性記録媒体。
[9]
半導体レーザを照射することによって前記記録層への記録および前記記録の消去を行う、前記[1]乃至[8]のうちのいずれかに記載の可逆性記録媒体。
[10]
支持基体と、
前記支持基体上に設けられると共に、記録状態および消去状態が可逆的に変化する記録層とを備え、
前記記録層は、
フタロシアニン骨格を有する化合物、スクアリリウム骨格を有する化合物、分子内に、SbF6,PF6,BF4,ClO4,CF3SO3および(CF3SO3)2Nのうちのいずれかのカウンターイオンと、5員環または6員環を含むメチン鎖との少なくとも一方を有するシアニン骨格を有する化合物および無機化合物のうちの少なくとも1種からなる光熱変換材料と、
電子供与性を有すると共に、下記一般式(2)で表される呈色性化合物と、
電子受容性を有する顕・減色剤とを含む
可逆性記録媒体。
[11]
溶媒中に、
フタロシアニン骨格を有する化合物、スクアリリウム骨格を有する化合物、カウンターイオンとしてSbF6,PF6,BF4,ClO4,CF3SO3および(CF3SO3)2Nのいずれかを含む、または、メチン鎖内に5員環または6員環の環状構造を含むシアニン骨格を有する化合物および無機化合物のうちの少なくとも1種からなる光熱変換材料と、
電子供与性を有する呈色性化合物と、
電子供与性を有する呈色性化合物と、
電子受容性を有する共に、下記一般式(1)で表わされる化合物のうちの少なくとも1種からなる顕・減色剤とを含む
可逆性記録媒体用塗料。
[12]
少なくとも、可逆性記録媒体が設けられた一の面を有し、
前記可逆性記録媒体は、
支持基体と、
前記支持基体上に設けられると共に、記録状態および消去状態が可逆的に変化する記録層とを備え、
前記記録層は、
フタロシアニン骨格を有する化合物、スクアリリウム骨格を有する化合物、カウンターイオンとしてSbF6,PF6,BF4,ClO4,CF3SO3および(CF3SO3)2Nのいずれかを含む、または、メチン鎖内に5員環または6員環の環状構造を含むシアニン骨格を有する化合物および無機化合物のうちの少なくとも1種からなる光熱変換材料と、
電子供与性を有する呈色性化合物と、
電子供与性を有する呈色性化合物と、
電子受容性を有する共に、下記一般式(1)で表わされる化合物のうちの少なくとも1種からなる顕・減色剤とを含む
外装部材。
Claims (12)
- 支持基体と、
前記支持基体上に設けられると共に、記録状態および消去状態が可逆的に変化する記録層とを備え、
前記記録層は、
フタロシアニン骨格を有する化合物、スクアリリウム骨格を有する化合物、分子内に、SbF6,PF6,BF4,ClO4,CF3SO3および(CF3SO3)2Nのうちのいずれかのカウンターイオンと、5員環または6員環を含むメチン鎖との少なくとも一方を有するシアニン骨格を有する化合物および無機化合物のうちの少なくとも1種からなる光熱変換材料と、
電子供与性を有する呈色性化合物と、
電子受容性を有する共に、下記一般式(1)で表わされる化合物のうちの少なくとも1種からなる顕・減色剤とを含む
可逆性記録媒体。
- 前記記録層は、前記呈色性化合物を2種以上含む、請求項1に記載の可逆性記録媒体。
- 前記記録層は複数の層からなる、請求項1に記載の可逆性記録媒体。
- 前記記録層は、複数の層として第1層および第2層を有し、
前記第1層および前記第2層は、それぞれ、互いに吸収波長領域の異なる光熱変換材料を含む、請求項1に記載の可逆性記録媒体。 - 前記光熱変換材料の吸収ピーク波長は、700nm以上2000nm以下である、請求項1に記載の可逆性記録媒体。
- 前記記録層は、さらに熱硬化性樹脂または熱可塑性樹脂を含む、請求項1に記載の可逆性記録媒体。
- 前記シアニン骨格を有する化合物は、分子内に、カウンターイオンとしてSbF6,PF6,BF4,ClO4,CF3SO3および(CF3SO3)2Nのいずれかを含み、且つ、メチン鎖内に5員環または6員環の環状構造を含む、請求項1に記載の可逆性記録媒体。
- 所定の波長領域の近赤外線を照射することによって前記記録層への記録および前記記録の消去を行う、請求項1に記載の可逆性記録媒体。
- 半導体レーザを照射することによって前記記録層への記録および前記記録の消去を行う、請求項1に記載の可逆性記録媒体。
- 支持基体と、
前記支持基体上に設けられると共に、記録状態および消去状態が可逆的に変化する記録層とを備え、
前記記録層は、
フタロシアニン骨格を有する化合物、スクアリリウム骨格を有する化合物、分子内に、SbF6,PF6,BF4,ClO4,CF3SO3および(CF3SO3)2Nのうちのいずれかのカウンターイオンと、5員環または6員環を含むメチン鎖との少なくとも一方を有するシアニン骨格を有する化合物および無機化合物のうちの少なくとも1種からなる光熱変換材料と、
電子供与性を有すると共に、下記一般式(2)で表される呈色性化合物と、
電子受容性を有する顕・減色剤とを含む
可逆性記録媒体。
- 溶媒中に、
フタロシアニン骨格を有する化合物、スクアリリウム骨格を有する化合物、分子内に、SbF6,PF6,BF4,ClO4,CF3SO3および(CF3SO3)2Nのうちのいずれかのカウンターイオンと、5員環または6員環を含むメチン鎖との少なくとも一方を有するシアニン骨格を有する化合物および無機化合物のうちの少なくとも1種からなる光熱変換材料と、
電子供与性を有する呈色性化合物と、
電子供与性を有する呈色性化合物と、
電子受容性を有する共に、下記一般式(1)で表わされる化合物のうちの少なくとも1種からなる顕・減色剤とを含む
可逆性記録媒体用塗料。
- 少なくとも、可逆性記録媒体が設けられた一の面を有し、
前記可逆性記録媒体は、
支持基体と、
前記支持基体上に設けられると共に、記録状態および消去状態が可逆的に変化する記録層とを備え、
前記記録層は、
フタロシアニン骨格を有する化合物、スクアリリウム骨格を有する化合物、分子内に、SbF6,PF6,BF4,ClO4,CF3SO3および(CF3SO3)2Nのうちのいずれかのカウンターイオンと、5員環または6員環を含むメチン鎖との少なくとも一方を有するシアニン骨格を有する化合物および無機化合物のうちの少なくとも1種からなる光熱変換材料と、
電子供与性を有する呈色性化合物と、
電子供与性を有する呈色性化合物と、
電子受容性を有する共に、下記一般式(1)で表わされる化合物のうちの少なくとも1種からなる顕・減色剤とを含む
外装部材。
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KR102485749B1 (ko) | 2023-01-05 |
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