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 PDF

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Publication number
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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WIPO (PCT)
Prior art keywords
recording medium
compound
color
recording
recording layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2022/012809
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English (en)
French (fr)
Japanese (ja)
Inventor
諒太 山野
由利子 貝野
麻由美 甲斐
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Sony Group Corp
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Sony Group Corp
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Publication date
Application filed by Sony Group Corp filed Critical Sony Group Corp
Priority to EP22837265.2A priority Critical patent/EP4368407B1/en
Priority to JP2023533090A priority patent/JP7823661B2/ja
Publication of WO2023281843A1 publication Critical patent/WO2023281843A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
PCT/JP2022/012809 2021-07-09 2022-03-18 記録媒体、カードおよび冊子 Ceased WO2023281843A1 (ja)

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EP22837265.2A EP4368407B1 (en) 2021-07-09 2022-03-18 Recording medium, card, and booklet
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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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Publication number Priority date Publication date Assignee Title
JP3509082B2 (ja) * 1994-06-23 2004-03-22 日本製紙株式会社 感熱記録体
JP2002331760A (ja) * 2001-03-09 2002-11-19 Ricoh Co Ltd 感熱記録材料
JP2002331762A (ja) * 2001-03-09 2002-11-19 Ricoh Co Ltd 感熱記録材料
JP2003094832A (ja) * 2001-09-21 2003-04-03 Ricoh Co Ltd 感熱記録材料

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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Title
See also references of EP4368407A4

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EP4368407A1 (en) 2024-05-15
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JPWO2023281843A1 (https=) 2023-01-12
EP4368407A4 (en) 2024-10-09

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