WO2023281843A1 - 記録媒体、カードおよび冊子 - Google Patents
記録媒体、カードおよび冊子 Download PDFInfo
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- WO2023281843A1 WO2023281843A1 PCT/JP2022/012809 JP2022012809W WO2023281843A1 WO 2023281843 A1 WO2023281843 A1 WO 2023281843A1 JP 2022012809 W JP2022012809 W JP 2022012809W WO 2023281843 A1 WO2023281843 A1 WO 2023281843A1
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- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910003468 tantalcarbide Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B41M5/3372—Macromolecular compounds
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
- B42D25/23—Identity cards
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
- B42D25/24—Passports
-
- 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
-
- 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
- B41M5/34—Multicolour thermography
Definitions
- the present disclosure relates to a recording medium, a card and a booklet having the same.
- Patent Document 1 describes the use of a bis(hydroxybenzoic acid) type compound (bisurea compound) represented by a specific formula as a color developer.
- the non-recording portion (hereinafter sometimes referred to as "background”) may be colored.
- An object of the present disclosure is to provide a recording medium capable of suppressing coloring of the background, and a card and a booklet having the recording medium.
- the first disclosure is A record containing an electron-donating color former, an electron-accepting color developer, an amine compound, at least one compound selected from an epoxy compound and a carbodiimide compound, and a polycarbonate resin. with layers,
- the developer is a recording medium containing at least one of the compounds represented by formulas (1A) and (1B) below.
- Z1 and Z2 are each independently a hydrogen bonding group.
- Y1 is a divalent group.
- Z3 and Z4 are each independently a hydrogen-bonding group.
- the second disclosure is A recording layer comprising an electron-donating color former, an electron-accepting color developer, an amine compound, at least one compound selected from an epoxy compound and a carbodiimide compound, and a matrix resin.
- the developer is a recording medium containing at least one of the compounds represented by formulas (1A) and (1B) below.
- Z1 and Z2 are each independently a hydrogen bonding group.
- Y1 is a divalent group.
- Z3 and Z4 are each independently a hydrogen-bonding group.
- a third disclosure is a card comprising the recording medium of the first or second disclosure.
- a fourth disclosure is a booklet comprising the recording medium of the first or second disclosure.
- FIG. 1 is a cross-sectional view showing an example of the configuration of a recording medium according to the first embodiment.
- FIG. 2 is a cross-sectional view showing an example of the configuration of a recording medium according to the second embodiment.
- FIG. 3 is a cross-sectional view showing an example of the configuration of a recording medium according to the third embodiment.
- 4A is a plan view showing an example of the appearance of Application Example 1.
- FIG. 4B is a cross-sectional view taken along line IVB--IVB of FIG. 4A.
- FIG. 5 is a perspective view showing an example of the appearance of Application Example 2.
- FIG. 6A is a plan view showing an example of the appearance (surface side) of Application Example 3.
- FIG. 6B is a plan view showing an example of the appearance (rear side) of Application Example 3.
- FIG. 7A is a plan view showing an example of the appearance (surface side) of Application Example 4.
- FIG. 7B is a plan view showing an example of the appearance (rear side) of Application Example 4.
- FIG. 8A is a perspective view showing an example of the appearance (front side) of Application Example 5.
- FIG. 8B is a perspective view showing an example of the appearance (rear side) of Application Example 5.
- FIG. 9A is a plan view showing an example of the appearance (first surface side) of Application Example 6.
- FIG. 9B is a plan view showing an example of the appearance (second surface side) of Application Example 6.
- FIG. 10A is a plan view showing an example of the appearance (upper surface side) of Application Example 7.
- FIG. 10A is a plan view showing an example of the appearance (upper surface side) of Application Example 7.
- FIG. 10B is a plan view showing an example of the appearance (side surface side) of Application Example 7.
- FIG. 11 is a plan view showing an example of the appearance of Application Example 8.
- FIG. 12 is a perspective view showing an example of the appearance of Application Example 9.
- FIG. 13A is a plan view showing an example of the appearance of Application Example 10.
- FIG. 13B is a cross-sectional view along line XIIIB-XIIIB of FIG. 13A.
- the recording medium 10 is configured to be able to change its coloring state by laser light irradiation (external stimulus).
- an image or the like can be drawn on the recording medium 10 by changing the coloring state.
- the image includes not only images such as patterns, colors, and photographs, but also text such as characters and symbols.
- the laser light is preferably near-infrared laser light.
- the change in coloring state may be a reversible change or an irreversible change. That is, the system of the recording medium 10 may be a rewritable system in which an image or the like can be rewritten, or a write-once system in which an image or the like can be written only once. From the viewpoint of anti-counterfeiting, the change in coloring state is preferably irreversible.
- the recording medium 10 includes a base material 11 and a recording layer 12 provided on the base material 11 .
- the recording medium 10 may further include a protective layer 13 provided on the recording layer 12 .
- the substrate 11, the recording layer 12, and the protective layer 13 will be described in order below.
- the base material 11 is a support for supporting the recording layer 12 .
- the base material 11 is preferably made of a material having excellent heat resistance and excellent dimensional stability in the planar direction.
- the substrate 11 may have either light transmissive or non-light transmissive properties.
- the base material 11 may have a predetermined color such as white.
- the substrate 11 has, for example, a plate shape or a film shape. In the present disclosure, film is defined to include sheet.
- the base material 11 may have rigidity or flexibility, for example.
- a material having flexibility is used as the base material 11, a flexible recording medium 10 can be realized.
- the rigid base material 11 include a wafer and a glass substrate.
- the flexible substrate 11 include flexible glass, film, and paper.
- constituent materials of the base material 11 include inorganic materials, metal materials, and polymer materials.
- the inorganic material includes, for example, at least one selected from the group consisting of silicon (Si), silicon oxide ( SiOx ), silicon nitride ( SiNx ) and aluminum oxide ( AlOx ).
- Silicon oxide includes, for example, at least one selected from the group consisting of glass, spin-on-glass (SOG), and the like.
- the metal material includes, for example, at least one selected from the group consisting of aluminum (Al), nickel (Ni), stainless steel, and the like.
- the polymeric material is, for example, at least one selected from the group consisting of polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethyletherketone (PEEK), polyvinyl chloride (PVC), and the like. include.
- PC polycarbonate
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- PEEK polyethyletherketone
- PVC polyvinyl chloride
- a reflective layer (not shown) may be provided on at least one main surface of the substrate 11, or the substrate 11 itself may also function as a reflective layer. Since the base material 11 has such a structure, more vivid color display is possible.
- the recording layer 12 in an unrecorded state is in an erased state.
- the recording layer 12 can change from a decolored state to a colored state by irradiation with a laser beam.
- the recording layer 12 can exhibit a predetermined color in a colored state. Predetermined colors include, for example, black, cyan, magenta, yellow, red, green, or blue, but are not limited to these colors.
- the thickness of the recording layer 12 is preferably 1 ⁇ m or more and 20 ⁇ m or less, more preferably 2 ⁇ m or more and 15 ⁇ m or less. When the thickness of the recording layer 12 is 1 ⁇ m or more, sufficient color density can be obtained. On the other hand, when the thickness of the recording layer 12 is 20 ⁇ m or less, it is possible to prevent the heat utilization amount of the recording layer 12 from becoming too large. Therefore, it is possible to suppress the deterioration of color developability.
- the recording layer 12 includes an electron-donating color former, an electron-accepting developer, an amine compound, at least one compound selected from an epoxy compound and a carbodiimide compound, and photothermal conversion. agent and matrix resin.
- the recording layer 12 may contain, if necessary, at least one additive selected from the group consisting of sensitizers, ultraviolet absorbers, etc., in addition to the above materials.
- the color former can develop color by reacting with a developer.
- a color former is, for example, a leuco dye.
- the lactone ring in the molecule of the leuco dye reacts with an acid, the lactone ring becomes a ring-opened state and develops color.
- the lactone ring in the ring-open state reacts with a base, the leuco dye becomes a ring-closed state and loses its color.
- Leuco dyes can be, for example, existing thermal paper dyes.
- the leuco dye is not particularly limited and can be appropriately selected according to the purpose.
- Specific leuco dyes include, for example, fluoran-based compounds, triphenylmethanephthalide-based compounds, azaphthalide-based compounds, phenothiazine-based compounds, leuco auramine-based compounds, and indolinophthalide-based compounds.
- 2-anilino-3-methyl-6-diethylaminofluorane 2-anilino-3-methyl-6-di(n-butylamino)fluorane, 2-anilino-3-methyl-6-(N -n-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-methyl amino) fluorane, 2-anilino-3-methyl-6-(Nn-amyl-N-ethylamino) fluorane, 2-anilino-3-methyl-6-(N-iso-
- a developer is, for example, for developing a colorless color former.
- Developers include compounds of the bis(hydroxybenzoic acid) type that contain electron-accepting groups in the molecule.
- the bis(hydroxybenzoic acid) type compound includes at least one of the compounds represented by the following formulas (1A) and (1B).
- the acidic group (hydroxybenzoic acid) of the bis(hydroxybenzoic acid) type compound reacts with the lactone ring of the color former (e.g., leuco dye), and the lactone ring is opened, resulting in color development of the color former. .
- Z 1 and Z 2 are each independently a hydrogen bonding group.
- Y 1 is a divalent group.
- Z 3 and Z 4 are each independently a hydrogen bonding group.
- the bonding positions of the hydroxy group (--OH) and the carboxyl group (--COOH) with respect to benzene are not limited. That is, the bonding position of the hydroxy group and carboxyl group to benzene may be any of the ortho, meta and para positions. In formulas (1A) and (1B), the bonding position of the hydroxyl group and the carboxyl group for one benzene and the bonding position of the hydroxyl group and the carboxyl group for the other benzene may be the same or different. .
- Z 1 and Z 2 in formula (1A) are each independently, for example, a urea bond (--NHCONH--), an amide bond (--NHCO--, --OCHN--) or a hydrazide bond (--NHCOCONH--).
- Z 1 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.
- Z2 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.
- Z 3 and Z 4 in formula (1B) are each independently, for example, a urea bond (--NHCONH--), an amide bond (--NHCO--, --OCHN--) or a hydrazide bond (--NHCOCONH--).
- Z3 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.
- Z 4 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.
- Y 1 is not particularly limited as long as it is a divalent group, but for example, it is a hydrocarbon group which may have a substituent.
- a portion of the carbon atoms in the hydrocarbon group (for example, a portion of the carbon atoms in the main chain of the hydrocarbon group) may be substituted with an element such as oxygen.
- a hydrocarbon group is a general term for groups composed of carbon (C) and hydrogen (H), and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
- the saturated hydrocarbon group is an aliphatic hydrocarbon group having no carbon-carbon multiple bond
- the unsaturated hydrocarbon group is an aliphatic hydrocarbon group having a carbon-carbon multiple bond (carbon-carbon double bond or carbon-carbon triple bond).
- the hydrocarbon group is a group hydrocarbon group.
- the hydrocarbon group may be chain-shaped or may contain one or more rings, but chain-shaped is preferred.
- the chain may be linear or branched having one or more side chains or the like. If the hydrocarbon group is chain-like, the melting point of the color developer can be lowered, so that the color developer melts upon irradiation with a laser beam, making it easier for the color former to develop color. From the viewpoint of reducing the melting point of the color developer, a normal alkyl chain is particularly preferred among chain hydrocarbon groups.
- the carbon number of the hydrocarbon group is, for example, 1 or more and 15 or less, 1 or more and 13 or less, 1 or more and 12 or less, 1 or more and 10 or less, 1 or more and 6 or less, or 1 or more and 3 or less.
- 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. is.
- the number of carbon atoms in the normal alkyl group is 8 or less, the length of the normal alkyl group is short, so that the color developer is less likely to be thermally disturbed during high-temperature storage, and interacts with a color former such as a leuco dye during color development. It is thought that it becomes difficult to remove the part that was attached. Therefore, the color-developing compound such as the leuco dye is less likely to decolor during high-temperature storage, thereby improving the high-temperature storage stability.
- the melting point of a developer with an odd number of carbon atoms in the normal alkyl group is normal In general, the melting point tends to be lower than the melting point of the developer having an even number of carbon atoms in the alkyl group. Therefore, in order to improve color development, it is preferable that the number of carbon atoms in the normal alkyl group is an odd number.
- the number of carbon atoms in the normal alkyl group is preferably an odd number of 7 or less, more preferably an odd number of 5 or less, and even more preferably an odd number of 3 or less.
- Examples of the substituent that the hydrocarbon group may have include a halogen group (eg, fluorine group) or an alkyl group having a halogen group (eg, fluorine group).
- a halogen group eg, fluorine group
- an alkyl group having a halogen group eg, fluorine group
- the bis(hydroxybenzoic acid) type color developer contains at least one compound selected from the group consisting of compounds represented by the following formulas (1-1) to (1-19): You can
- the amine-based compound caps the acidic groups (hydroxybenzoic acid) of the developer (bis(hydroxybenzoic acid) type compound). This suppresses the reaction of the acidic group of the developer with the color former (eg, the lactone ring of the leuco dye), thereby suppressing the coloring of the background. Therefore, the color representation of the recording medium 10 can be improved. For example, when the substrate 11 has white color, the white representation of the recording medium 10 can be improved.
- An amine-based compound is a compound containing at least one amine in one molecule.
- the two or more amines may be of the same type or of different types.
- Amines function as adsorptive groups.
- Amines are, for example, primary amines (--NH 2 ), secondary amines (--NHR), or tertiary amines (--NRR').
- Amines may have a salt structure.
- the amine-based compound preferably has a branched structure. Since the amine compound has a branched structure, when the amine compound caps the acidic group (hydroxybenzoic acid) of the color developer (bis(hydroxybenzoic acid) type compound), the amine compound can enhance the steric hindrance effect of Therefore, the acidic group of the developer is prevented from reacting with the color former (eg, the lactone ring of the leuco dye), so that the coloring of the background is further suppressed.
- the color former eg, the lactone ring of the leuco dye
- a branched structure is, for example, a comb-shaped molecular structure, a star-shaped molecular structure, or a dendritic molecular structure.
- the amine-based compound may be a comb-shaped molecule having an amino group, a star-shaped molecule having an amino group, or a dendritic molecule having an amino group.
- the recording layer 12 may contain two or more amine compounds with different branch structures.
- the amine-based compound having a branched structure may be an amine-based dispersant.
- the amine-based compound may be an amine-based polymer.
- the term "polymer" refers to a polymer having a number average molecular weight (Mn) of 1,000 or more.
- the amine-based compound may be a hindered amine-based compound.
- the hindered amine-based compound is represented, for example, by the following formula (2). However, in formula (2), the position represented by * bonds with an atom such as a hydrogen atom or another structure.
- the hindered amine compound may be a polymer containing the above structure in one or both of its main chain and side chains.
- the content of the amine compound in the recording layer 12 is preferably 100 parts by mass of the developer. 3 parts by mass or more and 25 parts by mass or less, more preferably 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the color developer, still more preferably 8 parts by mass or more and 15 parts by mass with respect to 100 parts by mass of the color developer parts or less, most preferably about 10 parts by weight per 100 parts by weight of developer.
- the content of the amine compound in the recording layer 12 is measured as follows. First, the recording medium 10 is disassembled to expose the recording layer 12 . Next, by immersing the exposed recording layer 12 in an organic solvent, the material constituting the recording layer 12 is extracted. Methanol is particularly preferred as the organic solvent. However, if the material is not sufficiently extracted with methanol, organic solvents such as acetone, methylethylketone, dimethylsulfoxide, dimethylformamide, tetrahydrofuran, chloroform, and acetonitrile can also be used.
- organic solvents such as acetone, methylethylketone, dimethylsulfoxide, dimethylformamide, tetrahydrofuran, chloroform, and acetonitrile can also be used.
- the extract is analyzed by LC/MS (liquid chromatography mass spectrometry) to identify the components contained in the extract and determine the content of the components. If it is difficult to identify the components and determine the content of the components only by LC/MS, infrared spectroscopy, pyrolysis GC/MS (gas chromatography mass spectrometry), NMR (nuclear magnetic resonance), etc. may be used in combination with the organic analysis method. Methanol or acetonitrile is particularly preferred as the mobile phase for LC/MS analysis, but organic solvents such as 2-propanol, ethanol or acetone can also be used.
- LC/MS liquid chromatography mass spectrometry
- the recording layer 12 contains an amine-based compound, there is a risk that the reliability of the coloring portion during high-temperature, high-humidity storage may deteriorate.
- the cause of this decrease in reliability is that the amine-based compound acts on the color developer bound to the color former, causing a neutralization reaction and dissociation between the color former and the developer. presumed to be for
- the recording layer 12 contains at least one compound selected from epoxy compounds and carbodiimide compounds together with the amine compound, it is possible to suppress deterioration in the reliability of the coloring portion during storage at high temperature and high humidity.
- the following four actions are presumed to be the cause of the manifestation of this inhibitory effect.
- (1) Decoloration due to moisture is suppressed by reacting the above-described compound with moisture that has entered the recording layer 12 .
- (2) The compound reacts with the color former and the color developer to form a crosslinked structure, thereby inhibiting mass transfer in the recording layer 12 and suppressing the dissociation of the color developer and the color former. .
- the above-mentioned compound reacts with the color-developing compound, thereby stabilizing the color-developing structure.
- the acid group of the developer acts as a catalyst for decoloring of the color former, and the compound reacts with the acid site of the color developer to deactivate it, thereby suppressing the decoloration.
- An epoxy-based compound is a compound containing at least one epoxy group in one molecule.
- the epoxy-based compound may be an epoxy resin.
- the epoxy-based compound is, for example, an alicyclic epoxy-based compound.
- An alicyclic epoxy compound is a compound having at least one epoxy group bonded to an alicyclic ring in one molecule.
- the alicyclic epoxy compound is, for example, a compound containing a structure represented by the following formula (3) (where n represents the number of repeating units).
- Specific examples of the compound containing the structure represented by formula (3) include 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol (stock EHPE3150 manufactured by Daicel Corporation).
- the carbodiimide-based compound may be a polymer.
- the lower limit of the content of at least one compound selected from the epoxy-based compound and the carbodiimide-based compound in the recording layer 12 is preferably set at 10 parts by weight or more per 100 parts by weight of the developer, more preferably 50 parts by weight or more per 100 parts by weight of the developer.
- the upper limit of the content of at least one of the epoxy-based compound and the carbodiimide-based compound in the recording layer 12 is preferably from the viewpoint of ensuring the uniformity of the coating film when the coating material for forming the recording layer is applied. is 150 parts by mass or less, more preferably 110 parts by mass or less, and even more preferably 100 parts by mass or less.
- the content of at least one of the epoxy-based compound and the carbodiimide-based compound in the recording layer 12 is measured in the same manner as the content of the amine-based compound in the recording layer 12 described above.
- the photothermal conversion agent generates heat by absorbing light in a predetermined wavelength range such as the near-infrared region.
- a near-infrared absorbing dye that has an absorption peak in the wavelength range of 700 nm or more and 2000 nm or less and has almost no absorption in the visible region.
- inorganic compounds include metal complexes such as dithio complexes, diimmonium salts, aminium salts, graphite, carbon black, metal powder particles, tricobalt tetraoxide, iron oxide, chromium oxide, copper oxide, titanium black, ITO (Indium Tin oxide), metal nitrides such as niobium nitride, metal carbides such as tantalum carbide, metal sulfides and various magnetic powders.
- metal complexes such as dithio complexes, diimmonium salts, aminium salts, graphite, carbon black, metal powder particles, tricobalt tetraoxide, iron oxide, chromium oxide, copper oxide, titanium black, ITO (Indium Tin oxide), metal nitrides such as niobium nitride, metal carbides such as tantalum carbide, metal sulfides and various magnetic powders.
- excellent light resistance means that the material does not decompose under the environment of use, for example, by irradiation with light from a fluorescent lamp or the like.
- Excellent heat resistance means that, for example, when a film is formed together 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 20% or more.
- Compounds having such a cyanine skeleton include, for example, counter ions of SbF 6 , PF 6 , BF 4 , ClO 4 , CF 3 SO 3 and (CF 3 SO 3 ) 2 N in the molecule. and a methine chain containing a 5- or 6-membered ring.
- the compound having a cyanine skeleton used in the recording medium 10 in the first 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. is preferable, but if at least one of them is provided, sufficient light resistance and heat resistance are ensured.
- the matrix resin preferably functions as a binder.
- the matrix resin is preferably one in which the color former, developer, amine-based compound, epoxy-based compound, carbodiimide-based compound and photothermal conversion agent are easily dispersed homogeneously.
- the matrix resin contains, for example, at least one selected from the group consisting of thermosetting resins and thermoplastic resins.
- the matrix resin preferably contains a polycarbonate-based resin.
- the matrix resin may be polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethyl cellulose, polystyrene, styrene copolymer, phenoxy resin, polyester, fragrance, in place of the polycarbonate resin or together with the polycarbonate resin.
- the protective layer 13 is for protecting the surface of the recording layer 12 .
- the protective layer 13 contains, for example, at least one cured material selected from the group consisting of ultraviolet curable resins and thermosetting resins.
- the protective layer 13 may contain fine particles and the like.
- the thickness of the protective layer 13 is, for example, 0.1 ⁇ m or more and 20 ⁇ m or less.
- the reaction causes the lactone ring to open, and the color former develops color.
- the portion irradiated with the laser light develops color, and a desired image is drawn on the recording layer 12 .
- the laser light it is preferable to use near-infrared laser light.
- the matrix resin is dissolved in a solvent (eg, methyl ethyl ketone).
- a decolorized color former, a developer, at least one compound selected from an epoxy compound and a carbodiimide compound, and a photothermal conversion agent are added to the solution and dispersed.
- a coating material for forming a recording layer is obtained.
- the recording layer 12 is formed by coating the recording layer forming coating material on the substrate 11 and drying it.
- the substrate 11 and the recording layer 12 may be integrated by hot pressing.
- a coating for forming a protective layer is applied onto the recording layer 12 and cured.
- the protective layer-forming paint contains, for example, at least one selected from the group consisting of ultraviolet-curable resins and thermosetting resins. As described above, the recording medium 10 shown in FIG. 1 is obtained.
- the recording medium 10 includes at least one of an electron-donating color former, an electron-accepting developer, an amine-based compound, an epoxy-based compound, and a carbodiimide-based compound.
- a recording layer 12 containing a seed compound and a matrix resin is provided.
- the recording layer 12 contains an amine-based compound
- the amine-based compound caps the acidic group (hydroxybenzoic acid) of the color developer (bis(hydroxybenzoic acid) type compound).
- the color former for example, the lactone ring of the leuco dye
- the recording layer 12 contains an amine-based compound, the reliability of the color-developing portion during high-temperature and high-humidity storage may deteriorate.
- the above compound it is possible to suppress deterioration in the reliability of the coloring part during high-temperature and high-humidity storage due to the amine-based compound.
- the developer contains at least one of the compounds represented by formula (1A) and formula (1B) above. Since the above compound is a compound with strong acidity, once it reacts with the color former, it is difficult to separate. In addition, since the above compounds tend to exist together to some extent through hydrogen bonding, the stability of the color developer in the recording layer 12 can be improved. Therefore, the storage stability of the recording medium 10 can be improved. In addition, since the energy required to dissolve the color developer in the recording layer 12 increases, the recording medium 10 can withstand high temperature press (for example, 150° C. high temperature press). Here, “capable of withstanding high-temperature press” means that color change (transmittance change) due to high-temperature press can be suppressed.
- high temperature press for example, 150° C. high temperature press
- the matrix resin contains a polycarbonate-based resin
- the polycarbonate-based resin is less likely to generate acid by photodecomposition, it is possible to suppress the acid generated from the matrix resin from reacting with the coloring compound. Therefore, it is possible to suppress the coloring of the background (unrecorded portion) of the recording medium 10 . Therefore, the light resistance of the background of the recording medium 10 can be improved.
- the compounds represented by the above formulas (1A) and (1B) have an alkyl chain and a benzene ring in the molecule in addition to the hydrogen bonding group, so they are highly compatible with polycarbonate resins. Therefore, the compounds represented by the above formulas (1A) and (1B) can easily be made to have a particle size of 1 ⁇ m or less during dispersion, and are hardly visible in the transparent polycarbonate resin. Therefore, the transparency of the recording layer 12 can be improved.
- the recording medium has one recording layer.
- the recording medium has three recording layers each having a different color hue. do.
- the recording medium 10A includes a substrate 11, three recording layers 12A, 12B, 12C, and two intermediate layers 14A, 14B.
- the three recording layers 12A, 12B, 12C and the two intermediate layers 14A, 14B are laminated on the substrate 11 in the order of the recording layer 12A, the intermediate layer 14A, the recording layer 12B, the intermediate layer 14B, and the recording layer 12C.
- the recording medium 10A may further include a protective layer 13 on the recording layer 12C.
- the recording layers 12A, 12B, and 12C in an unrecorded state are in an erased state.
- the recording layers 12A, 12B, and 12C can change from a decolored state to a colored state by irradiation with laser light.
- the recording layers 12A, 12B, and 12C can exhibit hues different from each other in the colored state.
- the recording layer 12A can exhibit a magenta color in a colored state.
- the recording layer 12B can exhibit a cyan color in a colored state.
- the recording layer 12C can exhibit a yellow color in a colored state.
- Magenta, cyan, and yellow are examples of first, second, and third colors, respectively.
- the first color, second color, and third color may be colors other than magenta, cyan, and yellow.
- the laser light capable of changing the recording layer 12A to a colored state, the laser light capable of changing the recording layer 12B to a colored state, and the laser light capable of changing the recording layer 12C to a colored state are: Each has a different peak wavelength.
- each of the recording layers 12A, 12B, and 12C is preferably 1 ⁇ m or more and 20 ⁇ m or less, more preferably 2 ⁇ m or more and 15 ⁇ m or less.
- the thickness of the recording layers 12A, 12B, and 12C is 1 ⁇ m or more, the color density can be improved.
- the thickness of the recording layers 12A, 12B, and 12C is 20 ⁇ m or less, it is possible to suppress an increase in the amount of heat utilization of the recording layers 12A, 12B, and 12C, thereby suppressing deterioration of the coloring properties.
- the recording layer 12A includes a first electron-donating color former, a first electron-accepting developer, a first amine-based compound, a first epoxy-based compound, and a first It contains at least one compound among carbodiimide compounds, a first photothermal conversion agent, and a first matrix resin.
- the recording layer 12B includes an electron-donating second color former, an electron-accepting second color developer, a second amine-based compound, a second epoxy-based compound and a second It contains at least one compound among carbodiimide compounds, a second photothermal conversion agent, and a second matrix resin.
- the recording layer 12C includes an electron-donating third color former, an electron-accepting third color developer, a third amine-based compound, a third epoxy-based compound, and a third It contains at least one compound among carbodiimide compounds, a third photothermal conversion agent, and a third matrix resin.
- the recording layers 12A, 12B, and 12C contain at least one additive selected from the group consisting of, for example, a sensitizer and an ultraviolet absorber, in addition to the above materials. good too.
- the first, second, and third color formers can exhibit different hues in the developed state. Specifically, the first color former can exhibit a magenta color in a colored state. The second color former can exhibit a cyan color in a colored state. The third color former can exhibit a yellow color in a colored state. Magenta, cyan, and yellow are examples of first, second, and third colors, respectively. The first color, second color, and third color may be colors other than magenta, cyan, and yellow.
- the first color developer is for developing the color of the decolorized first color former compound.
- the second developer is for developing the color of the decolored second color former.
- the third color developer is for developing the color of the third color former in a decolored state. Examples of the first, second, and third color developers are the same as those contained in the recording layer 12 of the first embodiment. The types of the first, second and third developers may be the same, or the types of the first, second and third developers may be different.
- the first, second, and third amine compounds are the same as the matrix resin contained in the recording layer 12 of the first embodiment.
- the types of the first, second and third amine compounds may be the same, or the types of the first, second and third amine compounds may be different.
- the first, second, and third epoxy compounds are the same as the epoxy compounds contained in the recording layer 12 of the first embodiment.
- the types of the first, second and third epoxy compounds may be the same, or the types of the first, second and third epoxy compounds may be different.
- the first, second, and third carbodiimide compounds are the same as the carbodiimide compounds contained in the recording layer 12 of the first embodiment.
- the types of the first, second and third carbodiimide compounds may be the same, or the types of the first, second and third carbodiimide compounds may be different.
- the first, second, and third photothermal conversion agents generate heat by absorbing light in a predetermined wavelength range such as the near-infrared region.
- the first, second and third photothermal conversion agents have different absorption wavelength peaks. Specifically, the first photothermal conversion agent has an absorption wavelength peak at wavelength ⁇ 1.
- the second photothermal conversion agent has an absorption wavelength peak at wavelength ⁇ 2.
- the third photothermal conversion agent has an absorption wavelength peak at wavelength ⁇ 3.
- the wavelengths ⁇ 1 , ⁇ 2 and ⁇ 3 are different.
- the absorption wavelength peak is preferably in the near-infrared region.
- the near-infrared region is, for example, a wavelength range of 700 nm or more and 2000 nm or less.
- the first, second, and third photothermal conversion agents have absorption wavelength peaks different from each other, so that a desired layer among the recording layers 12A, 12B, and 12C is selectively colored by irradiation with a laser beam.
- the first, second, and third photothermal conversion agents the same photothermal conversion agents as those contained in the recording layer 12 of the first embodiment can be exemplified.
- the first, second and third matrix resins are the same as the matrix resins contained in the recording layer 12 of the first embodiment.
- the types of the first, second and third matrix resins may be the same, or the types of the first, second and third matrix resins may be different.
- the intermediate layer 14A is provided between the recording layer 12A and the recording layer 12B.
- the intermediate layer 14A is a heat insulating layer that can insulate between the recording layer 12A and the recording layer 12B.
- the intermediate layer 14B is provided between the recording layer 12B and the recording layer 12C.
- the intermediate layer 14B is a heat insulating layer that can insulate between the recording layer 12B and the recording layer 12C.
- the intermediate layers 14A and 14B are made of, for example, a general translucent polymeric material.
- Specific materials include, for example, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethyl cellulose, polystyrene, styrenic copolymer, phenoxy resin, polyester, aromatic polyester, polyurethane, polycarbonate, poly At least one selected from the group consisting of acrylic acid esters, polymethacrylic acid esters, acrylic acid-based copolymers, maleic acid-based polymers, polyvinyl alcohol, modified polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, starch, and the like.
- the intermediate layers 14A and 14B may contain various additives such as ultraviolet absorbers.
- the intermediate layers 14A and 14B may be made of a translucent inorganic material.
- porous silica, alumina, titania, carbon, or a composite of these because the thermal conductivity is low and the heat insulating effect is high.
- the intermediate layers 14A, 14B can be formed by, for example, a sol-gel method.
- the thickness of the intermediate layers 14A and 14B is preferably 3 to 100 ⁇ m, more preferably 5 to 50 ⁇ m. If the thickness of the intermediate layers 14A, 14B is too thin, there is a possibility that a sufficient heat insulation effect cannot be obtained. On the other hand, if the thickness of the intermediate layers 14A and 14B is too thick, there is a possibility that the translucency will be lowered. In addition, there is a fear that the bending resistance of the recording medium 10B is lowered, and defects such as cracks are likely to occur.
- the recording layer 12A is colored magenta as follows.
- a predetermined position of the recording layer 12A is irradiated with a near-infrared laser beam having a peak wavelength of ⁇ 1
- the photothermal conversion agent contained in the portion irradiated with the laser beam absorbs the near-infrared laser beam and generates heat.
- This heat causes the color developer to melt, causing a color reaction (color development reaction) between the color developer and the color former, and the laser beam irradiated portion to develop a magenta color.
- the recording layer 12B is colored cyan in the following manner.
- a predetermined position of the recording layer 12B is irradiated with a near - infrared laser beam having a peak wavelength of ⁇ 2
- the portion irradiated with the laser beam develops a cyan color due to the reaction similar to that of the recording layer 12A.
- the recording layer 12C is colored yellow in the following manner.
- a predetermined position of the recording layer 12B is irradiated with a near - infrared laser beam having a peak wavelength of ⁇ 3
- the portion irradiated with the laser beam develops a yellow color due to the reaction similar to that of the recording layer 12A.
- predetermined positions of the recording layers 12A, 12B, and 12C are colored magenta, cyan, and yellow, respectively, so that a desired full-color image is drawn on the recording medium 10A.
- the recording layers 12A, 12B, and 12C can exhibit magenta, cyan, and yellow, respectively, in the colored state. Therefore, a desired image can be drawn in full color.
- the recording medium 10B includes a base material 11 and a recording layer 15 provided on the base material 11. As shown in FIG. The recording medium 10B may further include a protective layer 13 provided on the recording layer 15 .
- symbol is attached
- the recording layer 15 contains three types of microcapsules 15A, 15B, 15C and a matrix resin.
- Microcapsules 15A, 15B, and 15C can change their coloring state by irradiation with laser light.
- Each of the microcapsules 15A, 15B, and 15C can present different hues in the colored state.
- the microcapsules 15A can exhibit a magenta color in the colored state.
- the microcapsules 15B can exhibit a cyan color in the colored state.
- the microcapsules 15C can exhibit a yellow color in the colored state.
- Magenta, cyan, and yellow are examples of first, second, and third colors, respectively.
- the first color, second color, and third color may be colors other than magenta, cyan, and yellow.
- the laser light capable of changing the microcapsules 15A into a colored state, the laser light capable of changing the microcapsules 15B into a colored state, and the laser light capable of changing the microcapsules 15C into a colored state are: Each has a different peak wavelength.
- the microcapsule 15A includes a first microcapsule wall, a first color former having electron-donating properties, a first color developer having electron-accepting properties, a first amine compound, and a first at least one of the epoxy-based compound and the first carbodiimide-based compound, a first photothermal conversion agent, and a first matrix resin.
- the first microcapsule wall encloses the various materials described above.
- the microcapsule 15B includes a second microcapsule wall, a second color former having an electron-donating property, a second color developer having an electron-accepting property, a second amine compound, and a second a second photothermal conversion agent; and a second matrix resin.
- a second microcapsule wall encloses the various materials described above.
- the microcapsule 15C includes a third microcapsule wall, a third electron-donating color former, a third electron-accepting developer, a third amine compound, and a third and at least one compound selected from the epoxy-based compound and the third carbodiimide-based compound, a third photothermal conversion agent, and a third matrix resin.
- a third microcapsule wall encloses the various materials described above.
- the first, second, and third microcapsule walls are made of, for example, a translucent polymeric material.
- Specific materials for the microcapsule wall include, for example, polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethyl cellulose, polystyrene, styrenic copolymer, phenoxy resin, polyester, aromatic polyester, and polyurethane.
- first, second and third microcapsule walls may be the same, or the materials of the first, second and third microcapsule walls may be different.
- the first, second and third electron-donating dyes are the same as in the second embodiment.
- the first, second and third developers are the same as in the second embodiment.
- the first, second, and third epoxy compounds are the same as in the second embodiment.
- the first, second and third photothermal conversion agents are the same as in the second embodiment.
- the first, second and third matrix resins are the same as in the second embodiment.
- the recording layer 15 is colored magenta as follows. A predetermined position of the recording layer 15 is irradiated with a near-infrared laser beam having a peak wavelength of ⁇ 1. The microcapsules 15A contained in the laser beam irradiated portion develop a magenta color. As a result, the portion irradiated with the laser light develops a magenta color.
- the recording layer 15 is colored cyan in the following manner.
- a predetermined position of the recording layer 15 is irradiated with a near - infrared laser beam having a peak wavelength of ⁇ 2.
- the microcapsules 15B contained in the laser beam irradiated portion develop a cyan color.
- the portion irradiated with the laser light develops a cyan color.
- the recording layer 15 is colored yellow in the following manner.
- a predetermined position of the recording layer 15 is irradiated with a near - infrared laser beam having a peak wavelength of ⁇ 3.
- the microcapsules 15C included in the laser light irradiated portion develop a yellow color.
- the portion irradiated with the laser light develops a yellow color.
- a desired full-color image is drawn on the recording medium 10B by developing magenta, cyan, and yellow colors at predetermined positions of the recording layer 15, respectively.
- the recording layer 15 includes three types of microcapsules 15A, 15B, and 15C.
- Microcapsules 15A, 15B, and 15C are capable of exhibiting magenta, cyan, and yellow colors, respectively, in the colored state. Therefore, a desired image can be drawn in full color.
- Modification 1 Modification 1
- the intermediate layers 14A and 14B are heat insulating layers. It may be a laminate, or a laminate comprising a heat insulating layer and bonding layers provided on both sides of the heat insulating layer.
- the bonding layer is, for example, an adhesive layer or an adhesive layer.
- the recording medium 10A includes three recording layers 12A, 12B, 12C and two intermediate layers 14A, 14B.
- the recording layer 12 and a plurality of intermediate layers 14 other than two may be provided.
- the plurality of recording layers 12 and the plurality of intermediate layers 14 may be stacked such that the recording layers 12 and the intermediate layers 14 are alternately positioned.
- Each of the plurality of recording layers 12 may be capable of exhibiting different hues in the colored state.
- the color former contained in each of the plurality of recording layers 12 may be capable of presenting different hues in the colored state.
- the photothermal conversion agents contained in each of the plurality of recording layers 12 may have different absorption wavelength peaks.
- the recording layer 15 includes three types of microcapsules 15A, 15B, and 15C has been described, but it may include a plurality of types of microcapsules other than the three types.
- Each of the plurality of types of microcapsules may be capable of presenting different hues in a colored state.
- the color former contained in each of the plurality of types of microcapsules may be capable of exhibiting different hues in the state of color development.
- the photothermal conversion agents contained in each of the plurality of types of microcapsules may have absorption wavelength peaks different from each other.
- Modification 4 In the third embodiment, an example in which the microcapsules 15A, 15B, and 15C respectively contain the first matrix resin, the second matrix resin, and the third matrix resin has been described. , may not contain a matrix resin.
- the bis(hydroxybenzoic acid) type color developer contains at least one of the compounds represented by formulas (1A) and (1B) above.
- the bis(hydroxybenzoic acid) type developer may include at least one of the compounds represented by formulas (1C) and (1D) below.
- the bis(hydroxybenzoic acid) type color developer may include at least one of the compounds represented by Formula (1A), Formula (1B), Formula (1C) and Formula (1D).
- Z 5 and Z 6 are each independently a hydrogen bonding group.
- Y 2 is a divalent group.
- R 1 and R 2 are each independently , is a divalent group.
- Z 7 is a hydrogen bonding group.
- R 3 and R 4 are each independently a divalent group.
- Z 5 and Z 6 in formula (1C) are each independently, for example, a urea bond (--NHCONH--), an amide bond (--NHCO--, --OCHN--) or a hydrazide bond (--NHCOCONH--).
- Z5 is an amide bond
- the nitrogen contained in the amide bond may be bonded to R1
- the carbon contained in the amide bond may be bonded to R1
- Z6 is an amide bond
- the nitrogen contained in the amide bond may be bonded to R2
- the carbon contained in the amide bond may be bonded to R2 .
- Z 7 in formula (1D) is, for example, a urea bond (--NHCONH--), an amide bond (--NHCO--, --OCHN--) or a hydrazide bond (--NHCOCONH--).
- Y 2 in formula (1C) is the same as Y 1 in formula (1A).
- R 1 and R 2 in formula (1C) are not particularly limited as long as they are divalent groups, but for example, they are hydrocarbon groups which may have a substituent. Some of the carbons in the hydrocarbon group (for example, some of the carbons in the main chain of the hydrocarbon group) may be substituted with elements such as oxygen (O), sulfur (S) or nitrogen (N). .
- a hydrocarbon group is a general term for groups composed of carbon (C) and hydrogen (H), and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
- the saturated hydrocarbon group is an aliphatic hydrocarbon group having no carbon-carbon multiple bond
- the unsaturated hydrocarbon group is an aliphatic hydrocarbon group having a carbon-carbon multiple bond (carbon-carbon double bond or carbon-carbon triple bond).
- the hydrocarbon group may be chain-shaped or may contain one or more rings. The chain may be linear or branched having one or more side chains or the like.
- a saturated hydrocarbon group containing one ring includes, for example, a phenylene group.
- R 1 and R 2 have a hydrocarbon group
- the number of carbon atoms in the hydrocarbon group is, for example, 1 or more and 15 or less, 1 or more and 13 or less, 1 or more and 12 or less, 1 or more and 10 or less, 1 or more and 6 or less, or 1 or more. 3 or less.
- R 3 and R 4 in formula (1D) are not particularly limited as long as they are divalent groups, but for example, they are hydrocarbon groups which may have a substituent. Some of the carbons in the hydrocarbon group (for example, some of the carbons in the main chain of the hydrocarbon group) may be substituted with elements such as oxygen (O), sulfur (S) or nitrogen (N). .
- a hydrocarbon group is a general term for groups composed of carbon (C) and hydrogen (H), and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group.
- the saturated hydrocarbon group is an aliphatic hydrocarbon group having no carbon-carbon multiple bond
- the unsaturated hydrocarbon group is an aliphatic hydrocarbon group having a carbon-carbon multiple bond (carbon-carbon double bond or carbon-carbon triple bond).
- the hydrocarbon group may be chain-shaped or may contain one or more rings. The chain may be linear or branched having one or more side chains or the like.
- R 3 and R 4 have a hydrocarbon group
- the number of carbon atoms in the hydrocarbon group is, for example, 1 or more and 15 or less, 1 or more and 13 or less, 1 or more and 12 or less, 1 or more and 10 or less, 1 or more and 6 or less, or 1 or more. 3 or less.
- the bis(hydroxybenzoic acid) type color developer contains at least one selected from the group consisting of compounds represented by the following formulas (1-20) and (1-21). You can stay.
- the upper limit or lower limit of the numerical range at one stage may be replaced with the upper limit or lower limit of the numerical range at another stage.
- the color developer contains at least one of the compounds represented by the following formulas (1A) and (1B).
- Z1 and Z2 are each independently a hydrogen bonding group.
- Y1 is a divalent group.
- Z3 and Z4 are each independently a hydrogen-bonding group.
- a plurality of the recording layers are provided, The recording medium according to any one of (1) to (7), wherein the color former contained in each of the plurality of recording layers can exhibit different hues in a colored state.
- a plurality of the recording layers containing a photothermal conversion agent The recording medium according to (8), wherein the photothermal conversion agents contained in each of the plurality of recording layers have different absorption wavelength peaks.
- the recording layer includes a plurality of types of capsules,
- the plurality of types of capsules include the color former, the developer, the amine compound, the at least one compound, and the polycarbonate resin,
- the plurality of types of capsules contain a photothermal conversion agent, The recording medium according to (10), wherein the photothermal conversion agents contained in each of the plurality of types of capsules have absorption wavelength peaks different from each other.
- (12) further comprising a base material, The recording medium according to any one of (1) to (11), wherein the recording layer is provided on the base material.
- a recording layer comprising an electron-donating color former, an electron-accepting color developer, an amine compound, at least one compound selected from an epoxy compound and a carbodiimide compound, and a matrix resin.
- In formula (1B), Z3 and Z4 are each independently a hydrogen-bonding group.)
- a card comprising the recording medium according to any one of (1) to (13).
- a booklet comprising the recording medium according to any one of (1) to (13).
- the recording media 10, 10A, and 10B are applicable to various electronic devices and part of furnishings, and the types of the electronic devices and furnishings are not particularly limited. Specifically, for example, as a wearable terminal, it can be applied to a part of accessories such as watches (watches), bags, clothes, hats, glasses, and shoes.
- the present invention is not limited to electronic devices and furnishings, and can be applied to, for example, exterior members for inner walls or outer walls of buildings, exterior members for furniture such as desks, and the like.
- FIG. 4A shows the appearance of a card-type identification card.
- FIG. 4B is a cross-sectional view taken along line IVB--IVB of FIG. 4A.
- a card-type identification is an example of a card or identification.
- a card-type identification card comprises a substrate 21, a bonding layer 22, a recording medium 23, a bonding layer 24, and an overlay layer 25 in this order.
- the recording medium 23 is provided on one side of the base material 21 will be described, but the recording medium 23 may be provided on both sides of the base material 21 .
- the base material 21 is a support base material that supports the recording medium 23 .
- the base material 21 is, for example, a plastic substrate.
- the recording medium 23 is the recording medium 10 .
- the bonding layer 22 bonds the base material 21 and the recording medium 23 together.
- the bonding layer 24 bonds the recording medium 23 and the overlay layer 25 together.
- Overlay layer 25 protects recording medium 23 .
- Overlay layer 25 covers one side of recording medium 23 .
- card-type identification examples include a driver's license, health insurance card, basic resident register card, or individual number card (my number card).
- FIG. 5 shows the appearance of a booklet-type identification card.
- a booklet-type identification card is an example of a booklet.
- a booklet-type identification card has a plurality of sheets 31 . The plurality of sheets 31 are saddle-stitched.
- a recording medium 10 is provided on at least one surface of the sheet 31 . On the recording medium 10, characters, numerical values, facial photographs, and the like are drawn.
- a specific example of a booklet-type identification card is, for example, a passport.
- 6A and 6B show the appearance of an integrated circuit (IC) card with a rewrite function.
- This IC card has a printed surface 110 on its surface, and a sheet-like recording medium 10 is provided on the printed surface 110 .
- a sheet-like recording medium 10 is provided on the printed surface 110 .
- FIGS. 7A and 7B show the appearance of a credit card with an IC chip.
- a credit card with an IC chip is another example of an IC card.
- the credit card has an IC chip 121 on its front surface (first surface) 120B and a portrait 122 on its back surface (second surface) 120A.
- FIG. 8A shows the external configuration of the front surface of the smartphone.
- FIG. 8B shows the external configuration of the back surface of the smartphone shown in FIG. 8A.
- This smartphone includes, for example, a display section 210 , a non-display section 220 , and a housing 230 .
- a recording medium 10 is provided as an exterior member of the housing 230 on, for example, one surface of the housing 230 on the back side, so that various colors and patterns can be displayed as shown in FIG. 8B. can.
- a smart phone is taken as an example here, the present invention is not limited to this, and can be applied to, for example, a notebook personal computer (PC), a tablet PC, and the like.
- PC notebook personal computer
- FIGS. 9A and 9B show the appearance of the bag.
- This bag has, for example, a storage portion 310 and a handle 320 , and the recording medium 10 is provided in the storage portion 310 .
- the recording medium 10 is provided in the storage portion 310 .
- by attaching the recording medium 10 to the handle 320 portion various colored patterns can be displayed.
- the design of the storage portion 310 can be changed. It becomes possible to realize an electronic device that is also useful for fashion applications.
- FIG. 10A shows the appearance of the top surface of the automobile
- FIG. 10B shows the appearance of the side surface of the automobile.
- the recording medium 10 can display various colors and patterns by providing it in the interior of an automobile, for example, a steering wheel or a dashboard.
- FIG. 11 shows the appearance of the cosmetic container.
- This cosmetic container has a container 510 and a lid 520 covering the container 510 , and the recording medium 10 is provided on the lid 520 .
- the lid 520 is decorated with patterns, colors, characters, or the like as shown in FIG.
- the pattern, color pattern, characters, etc. of the lid 520 can be written by a predetermined drawing device.
- the recording medium 10 can be attached not only to the surface (cover 520) of the cosmetic container, but also to the back surface (accommodating section 510) or the like.
- FIG. 12 shows the appearance of the nail tip.
- a nail tip is an example of an exterior member.
- the nail tip has a recording medium 10 on its surface.
- the recording medium 10 By providing the recording medium 10 on the surface of the nail tip in this manner, various colored patterns can be displayed.
- the configuration in which the nail tip has the recording medium 10 on its surface has been described, but the configuration of the nail tip is not limited to this, and the recording medium 10 itself may be the nail tip.
- the substrate 11 has a nail-like shape.
- FIG. 13A shows the appearance of the nail seal.
- FIG. 13B shows a cross section along line XIIIB-XIIIB in FIG. 13A.
- a nail seal is an example of an exterior member.
- the nail seal includes a recording medium 610 with an adhesive layer and a release sheet 620.
- a recording medium 610 with an adhesive layer includes the recording medium 10 and an adhesive layer 611 .
- the adhesive layer 611 is provided on the surface of the recording medium 10 on the substrate 11 side.
- the recording medium 10 may further include a protective layer 13 on the recording layer 12 .
- the recording medium 10 and the like have a plurality of nail seal portions 612 to be attached to the fingernails of both hands.
- the nail seal portion 612 is held in a cut or half-cut state with respect to the nail seal, and is configured to be peelable at the interface between the adhesive layer 611 and the release sheet 620 .
- the recording layer 12 may be directly formed on a natural nail (human nail) as a supporting base material.
- the recording layer 12 may be formed by applying a coating material to the ground nail and curing it, or the self-supporting recording layer 12 may be separately formed and attached to the ground nail.
- the content of each of the amine-based compound, the epoxy-based compound, and the carbodiimide-based compound in the recording layer of the completed recording medium is a value determined by the measurement method described in the first embodiment. is.
- a photothermal conversion agent having a phthalocyanine skeleton was added to the solution.
- the amount of the photothermal conversion agent was adjusted so that the absorbance at the time of coating was 0.2.
- an amine-based compound and an epoxy-based compound were added to the solution to prepare a coating material for forming a recording layer.
- the blending amount of the amine compound was adjusted so that the content of the amine compound in the recording layer of the completed recording medium was 10 parts by mass with respect to 100 parts by mass of the color developer.
- the epoxy compound was adjusted so that the content of the epoxy compound in the recording layer of the completed recording medium was 100 parts by mass with respect to 100 parts by mass of the color developer.
- leuco dye As the leuco dye, amine-based compound, and epoxy-based compound, the following materials as shown in Table 1 were used.
- Leuco dye Leuco dye (amine compound) capable of exhibiting magenta color Amine compounds having a comb-shaped molecular structure: SOLSPERSE 24000GR (Example 1), SOLSPERSE 35000 (Example 2), SOLSPERSE 71000 (Example 3), SOLSPERSE 72700 (Example 4), SOLSPERSE 76700 (Example 5) , SOLSPERSE M387 (Example 6), SOLSPERSE X300 (Examples 7, 16, 18) (all manufactured by Lubrizol Co., Ltd.)
- Epoxy resin EHPE3150 (1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol) (manufactured by Daicel Corporation, epoxy equivalent 170 to 190 g/mol)
- Step of forming recording layer a 5 ⁇ m-thick recording layer coating composition was applied on a 50 ⁇ m-thick PET film (supporting substrate) using a wire bar and dried at 110° C. for 5 minutes to obtain a recording layer.
- a colored portion and an uncolored portion (background) were formed by irradiating the recording layer with a laser beam. The output of the laser light was adjusted so that the OD (Optical Density) at the time of color development was 1.1. As described above, the intended recording medium was obtained.
- Example 8 A recording medium was obtained in the same manner as in Example 1, except that the following amine compounds were used.
- (Amine compound) DISPERBYK-145 (Example 8), DISPERBYK-161 (Example 9), DISPERBYK-166 (Example 10), DISPERBYK-2155 (Example 11), BYK-9076 (Example 12) (both BYK-Chemie Japan Co., Ltd.)
- Example 13 A recording medium was obtained in the same manner as in Example 1, except that the following amine compounds were used.
- Example 14 A recording medium was obtained in the same manner as in Example 1, except that the following amine compounds were used.
- Example 15 A recording medium was obtained in the same manner as in Example 7, except that the following carbodiimide compound was used in place of the epoxy compound. The amount of the carbodiimide compound compounded was adjusted so that the content of the carbodiimide compound in the recording layer of the finished recording medium was 100 parts by mass with respect to 100 parts by mass of the color developer.
- Carbodiimide compound Carbodiimide oligomer (manufactured by Nisshinbo Chemical Co., Ltd., Carbodilite V-09GB, carbodiimide equivalent 200 g / mol)
- Example 16 A recording medium was obtained in the same manner as in Example 7, except that the following leuco dyes were used. (leuco dye) Leuco dye capable of exhibiting cyan color
- Example 17 A recording medium was obtained in the same manner as in Example 16, except that the following carbodiimide compound was used in place of the epoxy compound.
- carbodiimide compound Carbodiimide compound
- Carbodiimide oligomer manufactured by Nisshinbo Chemical Co., Ltd., Carbodilite V-09GB, carbodiimide equivalent 200 g / mol
- Example 18 A recording medium was obtained in the same manner as in Example 7, except that the following leuco dyes were used. (leuco dye) Leuco dye capable of exhibiting yellow color
- Example 19 A recording medium was obtained in the same manner as in Example 18, except that the following carbodiimide compound was used instead of the epoxy compound.
- carbodiimide compound Carbodiimide compound
- Carbodiimide oligomer manufactured by Nisshinbo Chemical Co., Ltd., Carbodilite V-09GB, carbodiimide equivalent 200 g / mol
- Example 1 A recording medium was obtained in the same manner as in Example 7, except that the recording layer-forming coating composition was prepared without adding an epoxy compound in the recording layer-forming coating composition preparation step.
- Example 2 A recording medium was obtained in the same manner as in Example 7, except that the coating for forming the recording layer was prepared without adding the amine compound in the preparation process of the coating for forming the recording layer.
- Example 3 A recording medium was obtained in the same manner as in Example 7, except that the coating for forming the recording layer was prepared without adding the amine-based compound and the epoxy-based compound in the preparation process of the coating for forming the recording layer.
- Example 4 A recording medium was obtained in the same manner as in Example 16, except that in the step of preparing the recording layer-forming paint, the recording layer-forming paint was prepared without adding the amine-based compound and the epoxy-based compound.
- Example 5 A recording medium was obtained in the same manner as in Example 18, except that in the step of preparing the recording layer-forming paint, the recording layer-forming paint was prepared without adding the amine-based compound and the epoxy-based compound.
- Table 1 shows the following. Since the recording layer contains an amine-based compound and an epoxy-based compound or a carbodiimide-based compound, it is possible to suppress the coloring of the background and to suppress the deterioration of the reliability of the coloring part during high-temperature and high-humidity storage. Yes (see Examples 1-19). If the recording layer contains an amine compound but does not contain an epoxy compound or a carbodiimide compound, the coloring of the background can be suppressed, but the reliability of the colored portion during high temperature and high humidity storage decreases ( See Comparative Example 1).
- the recording layer does not contain an amine-based compound but does contain an epoxy-based compound
- the reliability of the colored portion does not decrease during high-temperature, high-humidity storage, but the background is colored (see Comparative Example 2).
- the recording layer does not contain an amine-based compound, an epoxy-based compound, or a carbodiimide-based compound
- the reliability of the color-developing portion during high-temperature and high-humidity storage does not deteriorate, or hardly deteriorates, but the background is colored (comparative See Examples 3-5).
- the content of the amine-based compound in the recording layer is preferably based on 100 parts by mass of the color developer, from the viewpoint of both suppression of coloring of the background and suppression of deterioration in the reliability of the coloring portion during high-temperature and high-humidity storage. 3 parts by mass or more and 25 parts by mass or less, more preferably 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the color developer, still more preferably 8 parts by mass or more and 15 parts by mass with respect to 100 parts by mass of the color developer It is below.
- Table 3 shows the following.
- the content of the epoxy-based compound in the recording layer is preferably 10 parts by weight or more, more preferably 10 parts by weight or more per 100 parts by weight of the color developer, from the viewpoint of suppressing deterioration in the reliability of the coloring portion during storage at high temperature and high humidity. It is 50 parts by mass or more with respect to 100 parts by mass of the colorant.
- Reference Signs List 10 10A, 10B Recording medium 11, 21 Substrate 12, 12A, 12B, 12C, 15 Recording layer 13 Protective layer 14A, 14B Thermal insulation layer 15A, 15B, 15C Microcapsule 22, 24 Bonding layer 25 Overlay layer 31
- Sheet 110 Printed surface 120A Back surface 120B Front surface 121 IC chip 122 Photograph 210 Display unit 220 Non-display unit 230 Housing 310 Storage unit 320 Handle 411 Bonnet 412 Bumper 413 Roof 414 Trunk cover 415 Front door 416 Rear door 417 Rear bumper 510 Storage unit 520 Lid 610 recording medium with adhesive layer 620 release sheet 611 adhesive layer 612 nail seal portion
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Abstract
Description
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色剤と、アミン系化合物と、エポキシ系化合物およびカルボジイミド系化合物のうちの少なくとも1種の化合物と、ポリカーボネート系樹脂とを含む記録層を備え、
顕色剤は、下記の式(1A)および式(1B)で表される化合物のうちの少なくとも1種を含む記録媒体である。
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色剤と、アミン系化合物と、エポキシ系化合物およびカルボジイミド系化合物のうちの少なくとも1種の化合物と、マトリックス樹脂とを含む記録層を備え、
顕色剤は、下記の式(1A)および式(1B)で表される化合物のうちの少なくとも1種を含む記録媒体である。
1 第1の実施形態(記録媒体の例)
1.1 記録媒体の構成
1.2 記録媒体の記録方法
1.3 記録媒体の製造方法
1.4 作用効果
2 第2の実施形態(記録媒体の例)
2.1 記録媒体の構成
2.2 記録媒体の記録方法
2.3 作用効果
3 第3の実施形態(記録媒体の例)
3.1 記録媒体の構成
3.2 記録媒体の記録方法
3.3 作用効果
4 変形例
5 適用例
6 実施例
[1.1 記録媒体の構成]
以下、図1を参照して、第1の実施形態に係る記録媒体10の構成の一例について説明する。記録媒体10は、レーザー光の照射(外部刺激)により着色状態を変化可能に構成されている。この着色状態の変化により、例えば、画像等を記録媒体10に描画可能である。ここで、画像には、図柄、色柄、写真等のイメージに限らず、文字、記号等のテキスト等も含まれる。
基材11は、記録層12を支持するための支持体である。基材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ことが好ましい。基材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。基材11は、白色等の所定の色を有していてもよい。基材11は、例えば、板状またはフィルム状を有する。本開示においては、フィルムには、シートも含まれるものと定義する。
未記録状態(初期状態)の記録層12は、消色状態にある。記録層12は、レーザー光の照射により消色状態から発色状態に変化することが可能である。記録層12は、発色状態において所定の色を呈することが可能である。所定の色としては、例えば、ブラック、シアン、マゼンタ、イエロー、レッド、グリーンまたはブルーが挙げられるが、これらの色に限定されるものではない。
呈色性化合物は、顕色剤と反応することで発色することが可能である。呈色性化合物は、例えば、ロイコ色素である。ロイコ色素は、分子内に有するラクトン環が酸と反応すると、ラクトン環が開環状態となり発色する。また、ロイコ色素は、開環状態のラクトン環が塩基と反応すると、閉環状態となり消色する。ロイコ色素は、例えば、既存の感熱紙用染料であってもよい。
顕色剤は、例えば、無色の呈色性化合物を発色させるためのものである。顕色剤は、分子内に電子受容性を有する基を含む、ビス(ヒドロキシ安息香酸)型の化合物を含む。ビス(ヒドロキシ安息香酸)型の化合物は、下記の式(1A)および式(1B)で表される化合物のうちの少なくとも1種を含む。ビス(ヒドロキシ安息香酸)型の化合物の酸性基(ヒドロキシ安息香酸)が呈色性化合物(例えばロイコ色素)のラクトン環と反応し、ラクトン環が開環することで、呈色性化合物が発色する。
記録層12がアミン系化合物を含むと、アミン系化合物が、顕色剤(ビス(ヒドロキシ安息香酸)型の化合物)の酸性基(ヒドロキシ安息香酸)をキャップする。これにより、顕色剤の酸性基が呈色性化合物(例えばロイコ色素のラクトン環)と反応することが抑制されるので、地肌の着色を抑制することができる。したがって、記録媒体10の色表現を改善することができる。例えば、基材11が白色を有する場合には、記録媒体10の白色表現を改善することができる。
記録層12がアミン系化合物を含むと、高温高湿保管時の発色部の信頼性が低下する虞がある。この信頼性の低下の原因は、呈色性化合物と結合した顕色剤に対してアミン系化合物が作用することで、中和反応が進行し、呈色性化合物と顕色剤の解離が進行するためであると推定される。
(1)記録層12中に侵入した水分と上記化合物が反応することにより、水分による消色が抑制される。
(2)上記化合物が呈色性化合物や顕色剤と反応し架橋構造を形成することにより、記録層12中の物質移動が阻害され、顕色剤と呈色性化合物の解離が抑制される。
(3)上記化合物が、発色した呈色性化合物と反応することにより、発色構造が安定化される。
(4)呈色性化合物の消色に顕色剤の酸性基が触媒として作用しており、上記化合物が顕色剤の酸点と反応し失活させることにより、消色が抑制される。
光熱変換剤は、近赤外線領域等の所定の波長域の光を吸収して発熱するものである。光熱変換剤としては、例えば波長700nm以上2000nm以下の範囲に吸収ピークを有し、可視領域にほとんど吸収を持たない近赤外線吸収色素を用いることが好ましい。具体的には、例えば、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なる群より選ばれた少なくとも1種が挙げられる。
マトリックス樹脂は、バインダとしての機能を有していることが好ましい。マトリックス樹脂は、呈色性化合物、顕色剤、アミン系化合物、エポキシ系化合物、カルボジイミド系化合物および光熱変換剤が均質に分散しやすいものが好ましい。マトリックス樹脂が、例えば、熱硬化性樹脂および熱可塑性樹脂からなる群より選ばれた少なくとも1種を含む。マトリックス樹脂は、ポリカーボネート系樹脂を含むことが好ましい。ここで、ポリカーボネート系樹脂とは、少なくとも主鎖にカーボネート基(-O-(C=O)-O-)を構造単位として有する樹脂である。したがって、主鎖にカーボネート基以外に他の構造単位を有していてもよい。
保護層13は、記録層12の表面を保護するためのものである。保護層13は、例えば、紫外線硬化性樹脂および熱硬化性樹脂からなる群より選ばれた少なくとも1種の硬化物を含む。保護層13が、微粒子等を含んでいてもよい。保護層13の厚みは、例えば、0.1μm以上20μm以下である。
以下、第1の実施形態に係る記録媒体の記録方法の一例について説明する。
例えば半導体レーザーにより、記録層12の所定の位置にレーザー光が照射されると、記録層12のレーザー光照射部分に含まれる光熱変換剤がレーザー光を吸収して発熱する。この発熱により顕色剤が融解し、顕色剤と呈色性化合物との間で呈色反応(発色反応)が起こる。具体的には、顕色剤としてのビス(ヒドロキシ安息香酸)型の化合物が溶融し、ビス(ヒドロキシ安息香酸)型の化合物のヒドロキシ安息香酸が呈色性化合物(例えばロイコ色素)のラクトン環と反応し、ラクトン環が開環することで、呈色性化合物が発色する。これにより、レーザー光照射部分が発色し、記録層12に所望の画像が描画される。レーザー光としては、近赤外レーザー光を用いることが好ましい。
以下、第1の実施形態に係る記録媒体10の製造方法の一例について説明する。ここでは、塗布法を用いて記録媒体10を製造する例について説明する。
第1の実施形態に係る記録媒体10は、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色剤と、アミン系化合物と、エポキシ系化合物およびカルボジイミド系化合物のうちの少なくとも1種の化合物と、マトリックス樹脂とを含む記録層12を備える。
上記第1の実施形態では、記録媒体が1つの記録層を備える例について説明したのに対して、第2の実施形態では、発色状態における発色色相がそれぞれ異なる3つの記録層を備える例について説明する。
以下、図2を参照して、第2の実施形態に係る記録媒体10Aの構成の一例について説明する。記録媒体10Aは、基材11と、3つの記録層12A、12B、12Cと、2つの中間層14A、14Bとを備える。3つの記録層12A、12B、12Cと、2つの中間層14A、14Bとは、記録層12A、中間層14A、記録層12B、中間層14B、記録層12Cの順序で基材11上に積層されている。記録媒体10Aは、記録層12C上に保護層13をさらに備えていてもよい。
未記録状態(初期状態)の記録層12A、12B、12Cは、消色状態にある。記録層12A、12B、12Cは、レーザー光の照射により消色状態から発色状態に変化することが可能である。記録層12A、12B、12Cはそれぞれ、発色状態において互いに異なる色相を呈することが可能である。具体的には、記録層12Aは、発色状態においてマゼンタ色を呈することが可能である。記録層12Bは、発色状態においてシアン色を呈することが可能である。記録層12Cは、発色状態においてイエロー色を呈することが可能である。マゼンタ色、シアン色、イエロー色はそれぞれ、第1の色、第2の色、第3の色の一例である。第1の色、第2の色、第3の色は、マゼンタ色、シアン色、イエロー色以外の色であってもよい。記録層12Aを発色状態に変化させることが可能なレーザー光、記録層12Bを発色状態に変化させることが可能なレーザー光、および記録層12Cを発色状態に変化させることが可能なレーザー光は、それぞれ異なるピーク波長を有している。
第1、第2、第3の呈色性化合物は、発色状態において互いに異なる色相を呈することが可能である。具体的には、第1の呈色性化合物は、発色状態においてマゼンタ色を呈することが可能である。第2の呈色性化合物は、発色状態においてシアン色を呈することが可能である。第3の呈色性化合物は、発色状態においてイエロー色を呈することが可能である。マゼンタ色、シアン色、イエロー色はそれぞれ、第1の色、第2の色、第3の色の一例である。第1の色、第2の色、第3の色は、マゼンタ色、シアン色、イエロー色以外の色であってもよい。
第1の顕色剤は、消色状態の第1の呈色性化合物を発色させるためのものである。第2の顕色剤は、消色状態の第2の呈色性化合物を発色させるためのものである。第3の顕色剤は、消色状態の第3の呈色性化合物を発色させるためのものである。第1、第2、第3の顕色剤としては、第1の実施形態の記録層12に含まれる顕色剤と同様のものを例示することができる。第1、第2、第3の顕色剤の種類は同一であってもよいし、第1、第2、第3の顕色剤の種類はそれぞれ異なっていてもよい。
第1、第2、第3のアミン系化合物は、第1の実施形態の記録層12に含まれるマトリックス樹脂と同様である。第1、第2、第3のアミン系化合物の種類は同一であってもよいし、第1、第2、第3のアミン系化合物の種類はそれぞれ異なっていてもよい。
第1、第2、第3のエポキシ系化合物は、第1の実施形態の記録層12に含まれるエポキシ系化合物と同様である。第1、第2、第3のエポキシ系化合物の種類は同一であってもよいし、第1、第2、第3のエポキシ系化合物の種類はそれぞれ異なっていてもよい。
第1、第2、第3のカルボジイミド系化合物は、第1の実施形態の記録層12に含まれるカルボジイミド系化合物と同様である。第1、第2、第3のカルボジイミド系化合物の種類は同一であってもよいし、第1、第2、第3のカルボジイミド系化合物の種類はそれぞれ異なっていてもよい。
第1、第2、第3の光熱変換剤は、近赤外線領域等の所定の波長域の光を吸収して発熱するものである。第1、第2、第3の光熱変換剤は、互いに異なる吸収波長ピークを有する。具体的には、第1の光熱変換剤は、波長λ1に吸収波長ピークを有する。第2の光熱変換剤は、波長λ2に吸収波長ピークを有する。第3の光熱変換剤は、波長λ3に吸収波長ピークを有する。波長λ1、λ2、λ3は、異なっている。吸収波長ピークは、近赤外線領域にあることが好ましい。近赤外線領域は、例えば、波長700nm以上2000nm以下の範囲である。上記のように、第1、第2、第3の光熱変換剤が互いに異なる吸収波長ピークを有することで、レーザー光の照射により記録層12A、12B、12Cのうち所望の層を選択的に発色させることができる。第1、第2、第3の光熱変換剤としては、第1の実施形態の記録層12に含まれる光熱変換剤と同様のものを例示することができる。
第1、第2、第3のマトリックス樹脂は、第1の実施形態の記録層12に含まれるマトリックス樹脂と同様である。第1、第2、第3のマトリックス樹脂の種類は同一であってもよいし、第1、第2、第3のマトリックス樹脂の種類はそれぞれ異なっていてもよい。
中間層14Aは、記録層12Aと記録層12Bとの間に設けられている。中間層14Aは、記録層12Aと記録層12Bとの間を断熱することが可能な断熱層である。中間層14Bは、記録層12Bと記録層12Cとの間に設けられている。中間層14Bは、記録層12Bと記録層12Cとの間を断熱することが可能な断熱層である。
以下、第2の実施形態に係る記録媒体10Aの記録方法の一例について説明する。
第2の実施形態に係る記録媒体10Aでは、第1の実施形態に係る記録媒体10と同様の作用効果を得ることができる。
上記第2の実施形態では、記録媒体が3つの記録層を備え、フルカラーの画像を描画可能である例について説明したのに対して、第3の実施形態では、記録媒体が3種類のマイクロカプセルを含む記録層を備え、フルカラーの画像を描画可能である例について説明する。
以下、図3を参照して、第3の実施形態に係る記録媒体10Bの構成の一例について説明する。記録媒体10Bは、基材11と、基材11上に設けられた記録層15とを備える。記録媒体10Bは、記録層15上に設けられた保護層13をさらに備えていてもよい。なお、第3の実施形態において、第1の実施形態と同様の箇所には同一の符号を付して説明を省略する。
記録層15は、3種類のマイクロカプセル15A、15B、15Cとマトリックス樹脂とを含む。マイクロカプセル15A、15B、15Cは、レーザー光の照射により着色状態を変化させることが可能である。マイクロカプセル15A、15B、15Cはそれぞれ、発色状態において互いに異なる色相を呈することが可能である。具体的には、マイクロカプセル15Aは、発色状態においてマゼンタ色を呈することが可能である。マイクロカプセル15Bは、発色状態においてシアン色を呈することが可能である。マイクロカプセル15Cは、発色状態においてイエロー色を呈することが可能である。マゼンタ色、シアン色、イエロー色はそれぞれ、第1の色、第2の色、第3の色の一例である。第1の色、第2の色、第3の色は、マゼンタ色、シアン色、イエロー色以外の色であってもよい。マイクロカプセル15Aを発色状態に変化させることが可能なレーザー光、マイクロカプセル15Bを発色状態に変化させることが可能なレーザー光、およびマイクロカプセル15Cを発色状態に変化させることが可能なレーザー光は、それぞれ異なるピーク波長を有している。
第1、第2、第3のマイクロカプセル壁は、例えば、透光性を有する高分子材料により構成されている。マイクロカプセル壁の具体的な材料としては、例えば、ポリ塩化ビニル、ポリ酢酸ビニル、塩化ビニル-酢酸ビニル共重合体、エチルセルロース、ポリスチレン、スチレン系共重合体、フェノキシ樹脂、ポリエステル、芳香族ポリエステル、ポリウレタン、ポリカーボネート、ポリアクリル酸エステル、ポリメタクリル酸エステル、アクリル酸系共重合体、マレイン酸系重合体、ポリビニルアルコール、変性ポリビニルアルコール、ヒドロキシエチルセルロース、カルボキシメチルセルロースおよびデンプン等からなる群より選ばれた少なくとも1種が挙げられる。第1、第2、第3のマイクロカプセル壁の材料は同一であってもよいし、第1、第2、第3のマイクロカプセル壁の材料はそれぞれ異なっていてもよい。
第1、第2、第3の電子供与性色素は、第2の実施形態と同様である。
第1、第2、第3の顕色剤は、第2の実施形態と同様である。
第1、第2、第3のアミン系化合物は、第2の実施形態と同様である。
第1、第2、第3のエポキシ系化合物は、第2の実施形態と同様である。
第1、第2、第3のカルボジイミド系化合物は、第2の実施形態と同様である。
第1、第2、第3の光熱変換剤は、第2の実施形態と同様である。
第1、第2、第3のマトリックス樹脂は、第2の実施形態と同様である。
以下、第3の実施形態に係る記録媒体10Bの記録方法の一例について説明する。
第3の実施形態に係る記録媒体10Bでは、第1の実施形態に係る記録媒体10と同様の作用効果を得ることができる。
(変形例1)
第2の実施形態では、中間層14A、14Bが断熱層である例について説明したが、中間層14A、14Bが、断熱層と、断熱層の一方の面に設けられた貼合層とを備える積層体であってもよいし、断熱層と、断熱層の両面に設けられた貼合層とを備える積層体であってもよい。貼合層は、例えば、粘着層または接着層である。
第2の実施形態では、記録媒体10Aが、3つの記録層12A、12B、12Cと、2つの中間層14A、14Bとを備える例について説明したが、記録媒体10Aが、3つ以外の複数の記録層12と、2つ以外の複数の中間層14とを備えるようにしてもよい。複数の記録層12と複数の中間層14は、記録層12と中間層14とが交互に位置するように積層されていてもよい。複数の記録層12はそれぞれ、発色状態において互いに異なる色相を呈することが可能であってもよい。すなわち、複数の記録層12それぞれに含まれる呈色性化合物は、発色状態において互いに異なる色相を呈することが可能であってもよい。複数の記録層12それぞれに含まれる光熱変換剤は、互いに異なる吸収波長ピークを有していてもよい。
第3の実施形態では、記録層15が、3種類のマイクロカプセル15A、15B、15Cを含む例について説明したが、3種類以外の複数種類のマイクロカプセルを含んでいてもよい。複数種類のマイクロカプセルはそれぞれ、発色状態において互いに異なる色相を呈することが可能であってもよい。すなわち、複数種類のマイクロカプセルそれぞれに含まれる呈色性化合物は、発色状態において互いに異なる色相を呈することが可能であってもよい。複数種類のマイクロカプセルそれぞれに含まれる光熱変換剤は、互いに異なる吸収波長ピークを有していてもよい。
第3の実施形態では、マイクロカプセル15A、15B、15Cがそれぞれ、第1のマトリックス樹脂、第2のマトリックス樹脂、第3のマトリックス樹脂を含む例について説明したが、マイクロカプセル15A、15B、15Cが、マトリックス樹脂を含んでいなくてもよい。
第1から第3の実施形態では、記録媒体10、10A、10Bが基材11を備える例について説明したが、記録媒体10、10A、10Bが基材11を備えていなくてもよい。
上記第1、第2、第3の実施形態では、ビス(ヒドロキシ安息香酸)型の顕色剤が、上記式(1A)および式(1B)で表される化合物のうちの少なくとも1種を含む例について説明したが、ビス(ヒドロキシ安息香酸)型の顕色剤は、下記の式(1C)および式(1D)で表される化合物のうちの少なくとも1種を含んでもよい。あるいは、ビス(ヒドロキシ安息香酸)型の顕色剤は、式(1A)、式(1B)、式(1C)および式(1D)で表される化合物のうちの少なくとも1種を含んでもよい。
以上、本開示の実施形態および変形例について具体的に説明したが、本開示は、上記の実施形態および変形例に限定されるものではなく、本開示の技術的思想に基づく各種の変形が可能である。
(1)
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色剤と、アミン系化合物と、エポキシ系化合物およびカルボジイミド系化合物のうちの少なくとも1種の化合物と、ポリカーボネート系樹脂とを含む記録層を備え、
前記顕色剤は、下記の式(1A)および式(1B)で表される化合物のうちの少なくとも1種を含む記録媒体。
(2)
前記アミン系化合物は、分枝構造を有する(1)に記載の記録媒体。
(3)
前記アミン系化合物は、アミノ基を有するくし形分子である(1)に記載の記録媒体。
(4)
前記アミン系化合物は、ヒンダードアミン系化合物である(1)から(3)のいずれかに記載の記録媒体。
(5)
前記エポキシ系化合物は、エポキシ樹脂である(1)から(4)のいずれかに記載の記録媒体。
(6)
前記記録層中における前記アミン系化合物の含有量は、前記顕色剤100質量部に対して3質量部以上25質量部以下である(1)から(5)のいずれかに記載の記録媒体。
(7)
前記記録層中における前記少なくとも1種の化合物の含有量は、前記顕色剤100質量部に対して10質量部以上150質量部以下である(1)から(6)のいずれかに記載の記録媒体。
(8)
前記記録層が、複数備えられ、
複数の前記記録層にそれぞれ含まれる前記呈色性化合物は、発色状態において互いに異なる色相を呈することが可能である(1)から(7)のいずれかに記載の記録媒体。
(9)
複数の前記記録層が、光熱変換剤を含み、
複数の前記記録層それぞれに含まれる前記光熱変換剤は、互いに異なる吸収波長ピークを有する(8)に記載の記録媒体。
(10)
前記記録層は、複数種類のカプセルを含み、
複数種類の前記カプセルは、前記呈色性化合物と、前記顕色剤と、前記アミン系化合物と、前記少なくとも1種の化合物と、前記ポリカーボネート系樹脂とを含み、
複数種類の前記カプセルにそれぞれ含まれる前記呈色性化合物は、発色状態において互いに異なる色相を呈することが可能である(1)から(7)のいずれかに記載の記録媒体。
(11)
複数種類の前記カプセルが、光熱変換剤を含み、
複数種類の前記カプセルそれぞれに含まれる前記光熱変換剤は、互いに異なる吸収波長ピークを有する(10)に記載の記録媒体。
(12)
基材をさらに備え、
前記記録層は、前記基材上に設けられている(1)から(11)のいずれかに記載の記録媒体。
(13)
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色剤と、アミン系化合物と、エポキシ系化合物およびカルボジイミド系化合物のうちの少なくとも1種の化合物と、マトリックス樹脂とを含む記録層を備え、
前記顕色剤は、下記の式(1A)および式(1B)で表される化合物のうちの少なくとも1種を含む記録媒体。
(14)
(1)から(13)のいずれかに記載の記録媒体を備えるカード。
(15)
(1)から(13)のいずれかに記載の記録媒体を備える冊子。
次に、上記第1、第2、第3の実施形態および変形例に係る記録媒体10、10A、10Bの適用例について説明する。但し、以下で説明する電子機器等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。上記記録媒体10、10A、10Bは、各種の電子機器および服飾品の一部に適用可能であり、その電子機器および服飾品の種類は特に限定されない。具体的には例えば、ウェアラブル端末として、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に可能である。また、電子機器や服飾品に限らず、例えば、建造物の内壁または外壁の外装部材、および机等の家具の外装部材等にも適用することができる。
図4Aは、カード型の身分証明書の外観を表したものである。図4Bは、図4AのIVB-IVB線に沿った断面図である。カード型の身分証明書は、カードまたは身分証明書の一例である。カード型の身分証明書は、基材21と、貼合層22と、記録媒体23と、貼合層24と、オーバーレイ層25とを順次備える。ここでは、記録媒体23が基材21の一方の面に設けられている例について説明するが、記録媒体23が基材21の両面に設けられていてもよい。
図5は、冊子型の身分証明書の外観を表したものである。冊子型の身分証明書は、冊子の一例である。冊子型の身分証明書は、複数のシート31を備えている。複数のシート31は、中綴じされている。シート31の少なくとも一方の面には、記録媒体10が設けられる。記録媒体10には、文字、数値および顔写真等が描画されている。冊子型の身分証明書の具体例としては、例えば、パスポート等が挙げられる。
図6Aおよび図6B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、印字面110にはシート状の記録媒体10が設けられている。ICカードの印字面110に記録媒体10が設けられていることで、図6Aおよび図6Bに示したように、所望の画像等を印字面110に描画することが可能となる。
図7Aおよび図7Bは、ICチップ付きのクレジットカードの外観を表したものである。ICチップ付きのクレジットカードは、ICカードの他の例である。クレジットカードは、表面(第1の面)120BにICチップ121を有し、裏面(第2の面)120Aに顔写真122を有する。クレジットカードの表面120Bおよび裏面120Aに記録媒体10を配置することで、図7Aおよび図7Bに示したように、クレジットカードの表面120Bおよび裏面120Aに描画が可能となる。
図8Aは、スマートフォンの前面の外観構成を表したものである。図8Bは、図8A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、例えば記録媒体10が設けられており、これにより、図8B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9Aおよび図9B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、収納部310に記録媒体10が設けられている。これにより、収納部310に様々な文字や図柄等を表示することが可能である。また、持ち手320部分に記録媒体10が取り付けることで、様々な色柄を表示することができる。図9A、図9B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10Aは自動車の上面の外観を、図10Bは自動車の側面の外観を表したものである。記録媒体10は、例えば、ボンネット411、バンパー412、ルーフ413、トランクカバー414、フロントドア415、リアドア416およびリアバンパー417等の車体に設けることで各部に様々な情報や色柄を表示することができる。また、記録媒体10は、自動車の内装、例えば、ハンドルやダッシュボード等に設けることで様々な色柄を表示することができる。
図11は、化粧容器の外観を表したものである。この化粧容器は、収容部510と収容部510を覆う蓋520を有しており、蓋520に記録媒体10が設けられている。蓋520は、この記録媒体10により、例えば図11に示したような図柄や色柄あるいは文字等で加飾される。この蓋520の図柄や色柄あるいは文字等は、所定の描画装置で書き込むことが可能である。なお、記録媒体10は、化粧容器の表面(蓋520)だけでなく、裏面(収容部510)等に添付することができる。
図12は、ネイルチップの外観を表したものである。ネイルチップは、外装部材の一例である。ネイルチップは、表面に記録媒体10を備える。このようにネイルチップが表面に記録媒体10を備えることで、様々な色柄を表示することができる。なお、上記の例では、ネイルチップが表面に記録媒体10を備える構成について説明したが、ネイルチップの構成はこれに限られるものではなく、記録媒体10自体がネイルチップであってもよい。この場合、基材11が爪状の形状とされる。
図13Aは、ネイルシールの外観を表したものである。図13Bは、図13AのXIIIB-XIIIB線に沿った断面を表したものである。ネイルシールは、外装部材の一例である。ネイルシールは、粘着層付き記録媒体610と、剥離シート620とを備える。粘着層付き記録媒体610は、記録媒体10と、粘着層611とを備える。このように粘着層付き記録媒体610が記録媒体10を備えることで、様々な色柄を表示することができる。粘着層611は、記録媒体10の基材11側の面に設けられている。記録媒体10は、記録層12上に保護層13をさらに備えていてもよい。
以下、実施例により本開示を具体的に説明するが、本開示はこれらの実施例に限定されるものではない。
[実施例1~7]
(記録層形成用塗料の調製工程)
まず、メチルエチルケトン(MEK)にポリカーボネート(PC)を溶解し、さらに顕色剤を加え、ロッキングミルを用いて分散させ溶液を得た。顕色剤としては上記式(1A)で表される化合物を用いた。次に、溶液にロイコ色素を追加し、最終的にロイコ色素:顕色剤:ポリカーボネート=1:2:4という比率(質量比)になるように溶液を調製した。さらに、フタロシアニン骨格を有する光熱変換剤を溶液に追加した。なお、光熱変換剤の配合量は、塗膜時における吸光度が0.2になる程度とした。さらにアミン系化合物とエポキシ系化合物とを溶液に追加し、記録層形成用塗料を調製した。
(ロイコ色素)
マゼンタ色を呈することが可能なロイコ色素
(アミン系化合物)
くし形の分子構造を有するアミン系化合物:SOLSPERSE 24000GR(実施例1)、SOLSPERSE 35000(実施例2)、SOLSPERSE 71000(実施例3)、SOLSPERSE 72700(実施例4)、SOLSPERSE 76700(実施例5)、SOLSPERSE M387(実施例6)、SOLSPERSE X300(実施例7、16、18)(いずれもルーブリゾール株式会社製)
(エポキシ系化合物)
エポキシ樹脂:EHPE3150(2,2-ビス(ヒドロキシメチル)-1-ブタノールの1,2-エポキシ-4-(2-オキシラニル)シクロヘキサン付加物)(株式会社ダイセル製、エポキシ当量170~190g/mol)
次に、50μm厚のPETフィルム(支持基材)上にワイヤーバーを用いて記録層形成用塗料を5μm厚に塗膜し、110℃で5分乾燥させ、記録層を得た。次に、レーザー光を記録層に照射することにより発色部と未発色部(地肌)を形成した。レーザー光の出力は、発色時のOD(Optical Density)が1.1になるようにした。以上により、目的とする記録媒体が得られた。
アミン系化合物として以下のものを用いたこと以外は実施例1と同様にして記録媒体を得た。
(アミン系化合物)
DISPERBYK-145(実施例8)、DISPERBYK-161(実施例9)、DISPERBYK-166(実施例10)、DISPERBYK-2155(実施例11)、BYK-9076(実施例12)(いずれもビックケミー・ジャパン株式会社製)
アミン系化合物として以下のものを用いたこと以外は実施例1と同様にして記録媒体を得た。
(アミン系化合物)
くし形の分子構造を有するアミン系化合物:ヒノアクトT9100(川研ファインケミカル株式会社製)
アミン系化合物として以下のものを用いたこと以外は実施例1と同様にして記録媒体を得た。
(アミン系化合物)
ヒンダードアミン系化合物:Hostavin N 30(クラリアントケミカルズ株式会社製)
エポキシ系化合物に代えて以下のカルボジイミド系化合物を用いたこと以外は実施例7と同様にして記録媒体を得た。なお、カルボジイミド系化合物の配合量は、完成した記録媒体の記録層中におけるカルボジイミド系化合物の含有量が顕色剤100質量部に対して100質量部となるように調整された。
(カルボジイミド系化合物)
カルボジイミドオリゴマー(日清紡ケミカル株式会社製、カルボジライト V-09GB、カルボジイミド当量200g/mol)
ロイコ色素として以下のものを用いたこと以外は実施例7と同様にして記録媒体を得た。
(ロイコ色素)
シアン色を呈することが可能なロイコ色素
エポキシ系化合物に代えて以下のカルボジイミド系化合物を用いたこと以外は実施例16と同様にして記録媒体を得た。
(カルボジイミド系化合物)
カルボジイミドオリゴマー(日清紡ケミカル株式会社製、カルボジライト V-09GB、カルボジイミド当量200g/mol)
ロイコ色素として以下のものを用いたこと以外は実施例7と同様にして記録媒体を得た。
(ロイコ色素)
イエロー色を呈することが可能なロイコ色素
エポキシ系化合物に代えて以下のカルボジイミド系化合物を用いたこと以外は実施例18と同様にして記録媒体を得た。
(カルボジイミド系化合物)
カルボジイミドオリゴマー(日清紡ケミカル株式会社製、カルボジライト V-09GB、カルボジイミド当量200g/mol)
記録層形成用塗料の調製工程において、エポキシ系化合物を加えずに記録層形成用塗料を調製したこと以外は実施例7と同様にして記録媒体を得た。
記録層形成用塗料の調製工程において、アミン系化合物を加えずに記録層形成用塗料を調製したこと以外は実施例7と同様にして記録媒体を得た。
記録層形成用塗料の調製工程において、アミン系化合物およびエポキシ系化合物を加えずに記録層形成用塗料を調製したこと以外は実施例7と同様にして記録媒体を得た。
記録層形成用塗料の調製工程において、アミン系化合物およびエポキシ系化合物を加えずに記録層形成用塗料を調製したこと以外は実施例16と同様にして記録媒体を得た。
記録層形成用塗料の調製工程において、アミン系化合物およびエポキシ系化合物を加えずに記録層形成用塗料を調製したこと以外は実施例18と同様にして記録媒体を得た。
上記のようにして得られた記録媒体の未発色部のODを測定した。未発色部のODが0.25以下であるサンプルを“良好”とし、保管試験前後のOD変化率が0.25%を超えているサンプルを“不良”とした。ODが0.25を超えると、一般的に誰がみても呈色性色素の発色が認識できるレベルになると言われるため、0.25を良好/不良の判定の基準値とした。未発色部の評価結果を表1に示す。
まず、上記のようにして得られた記録媒体の発色部のODを測定した。次に、記録媒体を80℃、60%RHの高温高湿条件に24時間保管することにより、保管試験を行った。保管試験の温度80℃という条件はあらゆる部品の保管試験において最高温度であり、この温度の保管試験で良好な結果が得られれば、様々な環境下での保管に記録媒体が耐え得ると考えられる。次に、発色部に関して、以下の式により、保管試験前後のOD変化率を求めた。
(保管試験前後のOD変化率)[%]=100-(((保管試験後のOD)/(保管試験前のOD))×100)
記録層がアミン系化合物とエポキシ系化合物またはカルボジイミド系化合物とを含むことで、地肌の着色を抑制することができ、かつ、高温高湿保管時の発色部の信頼性の低下を抑制することができる(実施例1~19参照)。
記録層がアミン系化合物を含むが、エポキシ系化合物またはカルボジイミド系化合物を含まない場合には、地肌の着色を抑制することはできるが、高温高湿保管時の発色部の信頼性が低下する(比較例1参照)。
記録層がアミン系化合物を含まないが、エポキシ系化合物を含む場合には、高温高湿保管時の発色部の信頼性は低下しないが、地肌が着色する(比較例2参照)。
記録層がアミン系化合物も、エポキシ系化合物またはカルボジイミド系化合物も含まない場合には、高温高湿保管時の発色部の信頼性は低下しないか、もしくは殆ど低下しないが、地肌が着色する(比較例3~5参照)。
[実施例20~22]
表2に示すように、完成した記録媒体の記録層中におけるアミン系化合物の含有量が顕色剤100質量部に対して5質量部、20質量部、30質量部となるように、アミン系化合物の配合量を調整したこと以外は実施例7と同様にして記録媒体を得た。
上記のようにして得られた記録媒体について、上記の未発色部の評価と同様にして未発色部の評価を行った。その結果を表2に示す。
上記のようにして得られた記録媒体について、上記の保管安定性の評価と同様にして保管安定性の評価を行った。その結果を表2に示す。
記録層中にけるアミン系化合物の含有量が多いほど、地肌の着色がより抑制される傾向があるが、記録層中におけるアミン系化合物の含有量が多くなるほど、高温高湿保管時の発色部の信頼性は低下する傾向がある。
記録層中におけるアミン系化合物の含有量は、地肌の着色の抑制と高温高湿保管時の発色部の信頼性低下の抑制との両立の観点から、好ましくは顕色剤100質量部に対して3質量部以上25質量部以下、より好ましくは顕色剤100質量部に対して5質量部以上20質量部以下、さらにより好ましくは顕色剤100質量部に対して8質量部以上15質量部以下である。
[実施例23、24]
表3に示すように、完成した記録媒体の記録層中におけるエポキシ系化合物の含有量が顕色剤100質量部に対して50質量部、150質量部となるように、エポキシ系化合物の配合量を調整したこと以外は実施例7と同様にして記録媒体を得た。
上記のようにして得られた記録媒体について、上記の未発色部の評価と同様にして未発色部の評価を行った。その結果を表3に示す。
上記のようにして得られた記録媒体について、上記の保管安定性の評価と同様にして保管安定性の評価を行った。その結果を表3に示す。
記録層がエポキシ系化合物を含むと、高温高湿保管時の発色部の信頼性の低下を抑制することができる。
記録層中におけるエポキシ系化合物の含有量は、高温高湿保管時の発色部の信頼性低下の抑制の観点から、好ましくは顕色剤100質量部に対して10質量部以上、より好ましくは顕色剤100質量部に対して50質量部以上である。
11、21 基材
12、12A、12B、12C、15 記録層
13 保護層
14A、14B 断熱層
15A、15B、15C マイクロカプセル
22、24 貼合層
25 オーバーレイ層
31 シート
110 印字面
120A 裏面
120B 表面
121 ICチップ
122 顔写真
210 表示部
220 非表示部
230 筐体
310 収納部
320 持ち手
411 ボンネット
412 バンパー
413 ルーフ
414 トランクカバー
415 フロントドア
416 リアドア
417 リアバンパー
510 収容部
520 蓋
610 粘着層付き記録媒体
620 剥離シート
611 粘着層
612 ネイルシール部
Claims (15)
- 前記アミン系化合物は、分枝構造を有する請求項1に記載の記録媒体。
- 前記アミン系化合物は、アミノ基を有するくし形分子である請求項1に記載の記録媒体。
- 前記アミン系化合物は、ヒンダードアミン系化合物である請求項1に記載の記録媒体。
- 前記エポキシ系化合物は、エポキシ樹脂である請求項1に記載の記録媒体。
- 前記記録層中における前記アミン系化合物の含有量は、前記顕色剤100質量部に対して3質量部以上25質量部以下である請求項1に記載の記録媒体。
- 前記記録層中における前記少なくとも1種の化合物の含有量は、前記顕色剤100質量部に対して10質量部以上150質量部以下である請求項1に記載の記録媒体。
- 前記記録層が、複数備えられ、
複数の前記記録層にそれぞれ含まれる前記呈色性化合物は、発色状態において互いに異なる色相を呈することが可能である請求項1に記載の記録媒体。 - 複数の前記記録層が、光熱変換剤を含み、
複数の前記記録層それぞれに含まれる前記光熱変換剤は、互いに異なる吸収波長ピークを有する請求項8に記載の記録媒体。 - 前記記録層は、複数種類のカプセルを含み、
複数種類の前記カプセルは、前記呈色性化合物と、前記顕色剤と、前記アミン系化合物と、前記少なくとも1種の化合物と、前記ポリカーボネート系樹脂とを含み、
複数種類の前記カプセルにそれぞれ含まれる前記呈色性化合物は、発色状態において互いに異なる色相を呈することが可能である請求項1に記載の記録媒体。 - 複数種類の前記カプセルが、光熱変換剤を含み、
複数種類の前記カプセルそれぞれに含まれる前記光熱変換剤は、互いに異なる吸収波長ピークを有する請求項10に記載の記録媒体。 - 基材をさらに備え、
前記記録層は、前記基材上に設けられている請求項1に記載の記録媒体。 - 請求項1に記載の記録媒体を備えるカード。
- 請求項1に記載の記録媒体を備える冊子。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS6313778A (ja) * | 1986-07-04 | 1988-01-21 | Fuji Photo Film Co Ltd | 記録材料 |
JPH02292086A (ja) * | 1989-05-02 | 1990-12-03 | Kanzaki Paper Mfg Co Ltd | 記録材料 |
JPH08244355A (ja) | 1995-03-15 | 1996-09-24 | Nippon Paper Ind Co Ltd | 感熱記録体 |
WO2020003868A1 (ja) * | 2018-06-29 | 2020-01-02 | ソニー株式会社 | 可逆性記録媒体および外装部材 |
WO2021187385A1 (ja) * | 2020-03-16 | 2021-09-23 | ソニーグループ株式会社 | 記録媒体および外装部材 |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPS6313778A (ja) * | 1986-07-04 | 1988-01-21 | Fuji Photo Film Co Ltd | 記録材料 |
JPH02292086A (ja) * | 1989-05-02 | 1990-12-03 | Kanzaki Paper Mfg Co Ltd | 記録材料 |
JPH08244355A (ja) | 1995-03-15 | 1996-09-24 | Nippon Paper Ind Co Ltd | 感熱記録体 |
WO2020003868A1 (ja) * | 2018-06-29 | 2020-01-02 | ソニー株式会社 | 可逆性記録媒体および外装部材 |
WO2021187385A1 (ja) * | 2020-03-16 | 2021-09-23 | ソニーグループ株式会社 | 記録媒体および外装部材 |
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