WO2023002719A1 - Optical recording medium, identification card, card and booklet - Google Patents

Optical recording medium, identification card, card and booklet Download PDF

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Publication number
WO2023002719A1
WO2023002719A1 PCT/JP2022/016141 JP2022016141W WO2023002719A1 WO 2023002719 A1 WO2023002719 A1 WO 2023002719A1 JP 2022016141 W JP2022016141 W JP 2022016141W WO 2023002719 A1 WO2023002719 A1 WO 2023002719A1
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WO
WIPO (PCT)
Prior art keywords
recording medium
optical recording
thermal
base
generator
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Application number
PCT/JP2022/016141
Other languages
French (fr)
Japanese (ja)
Inventor
武久 石田
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ソニーグループ株式会社
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Publication of WO2023002719A1 publication Critical patent/WO2023002719A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • 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
    • B42D25/40—Manufacture
    • B42D25/405—Marking
    • B42D25/41—Marking using electromagnetic radiation

Definitions

  • This disclosure relates to an optical recording medium, an identification card, a card, and a booklet comprising the same.
  • thermal acid-generating compounds generally have the property of gradually generating acid when heated for a long period of time, even at temperatures below the activation temperature. Therefore, when the optical recording medium is stored in a high-temperature (for example, 80° C.) environment, there is a problem that the hue of the background changes.
  • background means an unrecorded portion where recording is not performed by irradiation with laser light.
  • An object of the present disclosure is to provide an optical recording medium capable of suppressing color change of the background during high-temperature storage, and an identification card, card, and booklet including the same.
  • the first disclosure is a recording layer containing a matrix resin, an electron-donating dye in a decolorized state, a thermal acid generator and a photothermal conversion agent; an auxiliary layer comprising a matrix resin and a thermal base generator;
  • the electron-donating dye is capable of exhibiting a reversible hue change under the action of acids and bases
  • the optical recording medium includes a thermal acid generator containing at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
  • the second disclosure is a recording layer containing a matrix resin, an electron-donating dye in a colored state, a thermal base generator and a photothermal conversion agent; an auxiliary layer comprising a matrix resin and a thermal acid generator;
  • the optical recording medium includes a thermal acid generator containing at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
  • a third disclosure is: a recording layer containing a matrix resin, an electron-donating dye in a decolorized state, and a thermal base generator; an auxiliary layer comprising a matrix resin, a thermal acid generator and a photothermal conversion agent;
  • the optical recording medium includes a thermal acid generator containing at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
  • a fourth disclosure is: a recording layer containing a matrix resin, an electron-donating dye in a colored state and a thermal acid generator; an auxiliary layer containing a matrix resin, a thermal base generator and a photothermal conversion agent;
  • the optical recording medium includes a thermal acid generator containing at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
  • a fifth disclosure is an identification card comprising the optical recording medium of any one of the first to fourth disclosures.
  • a sixth disclosure is a booklet comprising the optical recording medium of any one of the first to fourth disclosures.
  • a seventh disclosure is a card comprising the optical recording medium of any one of the first to fourth disclosures.
  • FIG. 1 is a cross-sectional view showing an example of the configuration of an optical recording medium according to the first embodiment.
  • FIG. 2 is a graph for explaining how to determine the acid generation temperature T A of the thermal acid generator and the base generation temperature T B of the thermal base generator.
  • FIG. 3 is a cross-sectional view showing an example of the states of the electron-donating dye, the thermal acid generator, and the thermal base generator in the optical recording medium before drawing.
  • FIG. 4 is a cross-sectional view showing an example of the states of the electron-donating dye, the thermal acid generator, and the thermal base generator in the optical recording medium after drawing.
  • FIG. 1 is a cross-sectional view showing an example of the configuration of an optical recording medium according to the first embodiment.
  • FIG. 2 is a graph for explaining how to determine the acid generation temperature T A of the thermal acid generator and the base generation temperature T B of the thermal base generator.
  • FIG. 3 is a cross-sectional view showing an example of the states of the electron-donating dye, the thermal acid generator, and
  • FIG. 5 is a cross-sectional view showing an example of the states of the electron-donating dye, the thermal acid generator, and the thermal base generator in the optical recording medium during high-temperature storage.
  • FIG. 6 is a cross-sectional view showing an example of the configuration of an optical recording medium according to the second embodiment.
  • FIG. 7 is a cross-sectional view showing an example of the configuration of an optical recording medium according to the third embodiment.
  • 8 is a cross-sectional view showing an example of the configuration of an optical recording medium according to Modification 1.
  • FIG. FIG. 9 is a cross-sectional view showing an example of the configuration of an optical recording medium according to Modification 2.
  • FIG. 10A is a plan view showing an example of the appearance of Application Example 1.
  • FIG. FIG. 10A is a plan view showing an example of the appearance of Application Example 1.
  • FIG. FIG. 10A is a plan view showing an example of the appearance of Application Example 1.
  • FIG. FIG. 10A is a plan view showing an example of the appearance of Application Example 1.
  • FIG. 10B is a cross-sectional view along line XB-XB of FIG. 10A.
  • FIG. 11 is a perspective view showing an example of the appearance of Application Example 2.
  • FIG. 12A is a plan view showing an example of the appearance (surface side) of Application Example 3.
  • FIG. 12B is a plan view showing an example of the appearance (rear side) of Application Example 3.
  • FIG. 13A is a plan view showing an example of the appearance (surface side) of Application Example 4.
  • FIG. 13B is a plan view showing an example of the appearance (rear side) of Application Example 4.
  • FIG. 14A is a perspective view showing an example of the appearance (front side) of Application Example 5.
  • FIG. 14B is a perspective view showing an example of the appearance (rear side) of Application Example 5.
  • FIG. 14A is a perspective view showing an example of the appearance (front side) of Application Example 5.
  • FIG. 15A is a perspective view showing an example of the appearance (first surface side) of Application Example 6.
  • FIG. 15B is a perspective view showing an example of the appearance (second surface side) of Application Example 6.
  • FIG. 16A is a plan view showing an example of the appearance (upper surface side) of Application Example 7.
  • FIG. 16B is a plan view showing an example of the appearance (side surface side) of Application Example 7.
  • FIG. 17 is a plan view showing an example of the appearance of Application Example 8.
  • FIG. 18 is a perspective view showing an example of the appearance of Application Example 9.
  • FIG. 19A is a plan view showing an example of the appearance of Application Example 10.
  • FIG. 19B is a cross-sectional view along line XIXB-XIXB of FIG. 19A.
  • FIG. 20 is a graph showing changes in optical density with respect to high temperature storage time.
  • FIG. 1 is a cross-sectional view showing an example of the configuration of an optical recording medium 10 according to the first embodiment.
  • the optical recording medium 10 is configured to be able to change its coloring state by an external stimulus.
  • an image or the like can be drawn on the optical 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 external stimulus is laser light.
  • 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 optical recording medium 10 may be rewritable in which an image or the like can be rewritten, or may be write-once 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 optical recording medium 10 includes a substrate 11 , an auxiliary layer 12 provided on the substrate 11 , and a recording layer 13 provided on the auxiliary layer 12 .
  • the optical recording medium 10 may further have a protective layer on the recording layer 13 .
  • the substrate 11, the recording layer 13, and the auxiliary layer 12 will be described in order below.
  • the base material 11 is a support for supporting the auxiliary layer 12 and the recording layer 13 .
  • 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 substrate 11 may be, for example, a rigid substrate such as a wafer, or a flexible thin-layer glass, film, paper, or the like. By using a flexible substrate as the base material 11, a flexible (bendable) recording medium can be realized.
  • 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 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 13 in an unrecorded state is in an erased state.
  • the recording layer 13 can change from a decolored state to a colored state by laser light (external stimulus).
  • the recording layer 13 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 13 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 layer 13 is 1 ⁇ m or more, the color density can be improved.
  • the thickness of the recording layer 13 is 20 ⁇ m or less, it is possible to prevent the heat utilization amount of the recording layer 13 from becoming too large. Therefore, it is possible to suppress the deterioration of color developability.
  • the recording layer 13 contains a matrix resin, a decolorized electron-donating dye, a thermal acid generator, and a photothermal conversion agent.
  • the recording layer 13 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 matrix resin preferably functions as a binder.
  • the matrix resin is preferably one in which the electron-donating dye, the thermal acid generator and the photothermal conversion agent are easily dispersed homogeneously.
  • the matrix resin include at least one selected from the group consisting of thermosetting resins and thermoplastic resins.
  • Specific examples of the matrix resin include polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethyl cellulose, polystyrene, styrenic copolymer, phenoxy resin, polyester, aromatic polyester, polyurethane, and polycarbonate.
  • polyacrylic acid ester polymethacrylic acid ester, acrylic acid-based copolymer, maleic acid-based polymer, polyvinyl alcohol, modified polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose and at least one selected from the group consisting of starch, etc. mentioned.
  • Electron-donating dyes are compounds capable of exhibiting reversible hue changes under the action of acids and bases. That is, the decolorized electron-donating dye can change its structure and develop color by the action of an acid, and the electron-donating dye in the colored state can change its structure and decolor by the action of a base. It is possible.
  • Electron-donating dyes are, for example, leuco dyes.
  • Leuco dyes can be, for example, existing thermal paper dyes.
  • a specific example is a compound containing an electron-donating group in the molecule represented by the following formula (1).
  • the electron-donating dye is not particularly limited and can be appropriately selected according to the purpose.
  • Specific electron-donating dyes include, in addition to the compounds represented by the above formula (1), fluoran-based compounds, triphenylmethanephthalide-based compounds, azaphthalide-based compounds, phenothiazine-based compounds, and 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-
  • thermal acid generator is a so-called color developer that generates an acid at a predetermined temperature or higher. When the generated acid acts on the decolorized electron-donating dye, the structure of the electron-donating dye changes to develop color.
  • Thermal acid generators are, for example, onium salts.
  • the onium salt preferably contains at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
  • the ammonium salt, sulfonium salt and iodonium salt all have an acid generation temperature within the range of 150°C or higher and lower than 280°C. The reason why the acid generation temperature is preferably 150° C. or more and less than 280° C. will be described later.
  • Anions of ammonium, sulfonium and iodonium salts include, for example, compounds containing sulfur, phosphorus, boron or antimony.
  • Ammonium salts are, for example, quaternary ammonium salts.
  • Quaternary ammonium salts include, for example, salts of quaternary ammonium cations and sulfur compound anions.
  • Salts of quaternary ammonium cations and sulfur compound anions include, for example, salts represented by the following formula (2).
  • the sulfonium salt includes, for example, at least one selected from the group consisting of salts of sulfonium cations and antimony compound anions and salts of sulfonium cations and boron compound anions.
  • Salts of sulfonium cations and antimony compound anions include, for example, salts represented by the following formula (3).
  • the salt of the sulfonium cation and the boron compound anion includes, for example, at least one salt selected from the group consisting of salts represented by the following formula (4) and formula (5).
  • Iodonium salts are, for example, salts of iodonium cations and boron compounds.
  • Salts of iodonium cations and boron compounds include, for example, salts represented by the following formula (6).
  • the lower limit of the acid generating temperature TA of the thermal acid generator is preferably 150°C or higher.
  • the acid generating temperature TA of the thermal acid generator is 150° C. or higher, recording on the optical recording medium 10 is possible even when the optical recording medium 10 is left in a high-temperature environment (for example, in a car under the hot sun reaching 80° C.). It is possible to suppress a change in hue of a portion (colored portion) and an unrecorded portion (uncolored portion), and maintain the original recording state.
  • the acid generation temperature TA of the thermal acid generator is Even higher temperatures above 180°C are desirable.
  • the upper limit of the acid generation temperature TA of the thermal acid generator is preferably lower than the thermal decomposition temperature of the matrix resin contained in the recording layer 13, for example, lower than 280.degree.
  • the thermal decomposition temperature of the matrix resin is measured by thermogravimetric analysis (TGA).
  • the acid generation temperature TA of the thermal acid generator is determined as follows. First, a sample 1 is obtained by removing the recording layer 13 from the optical recording medium 10 and bonding it onto a PET substrate. Next, sample 1 is set in a thermal gradient tester (heat seal tester HG-3) manufactured by Toyo Seiki Seisakusho Co., Ltd., and a contact kept at a specified temperature is applied to the unrecorded part of sample 1 at a pressure of 0.1 MPa. for 5 seconds to develop a color, and the optical density (hereinafter referred to as "OD") at that time is measured. The temperature of the contact is changed from 40° C. to 280° C.
  • a thermal gradient tester heat seal tester HG-3 manufactured by Toyo Seiki Seisakusho Co., Ltd.
  • a graph showing the relationship between contactor temperature and OD is obtained (see FIG. 2). If one sample 1 does not have enough measurement positions, one or two or more samples 1 are prepared separately and the same measurement as above is performed.
  • the temperature of the contactor is the temperature of the contactor displayed on the thermal gradient tester.
  • a spectrophotometer X-Rite eXact manufactured by Videojet X-Rite Co., Ltd. is used for the measurement of OD.
  • the photothermal conversion agent for example, absorbs light in a predetermined wavelength range and generates heat.
  • the predetermined wavelength range is preferably in 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.
  • Specific examples thereof include at least one selected from the group consisting of compounds having a phthalocyanine skeleton (phthalocyanine dyes), compounds having a squarylium skeleton (squarylium dyes), and inorganic compounds.
  • 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 optical recording medium 10 in the first embodiment has both the counter ion and a cyclic structure such as a 5-membered ring or a 6-membered ring in the methine chain. However, if at least one of them is provided, sufficient light resistance and heat resistance are ensured.
  • the auxiliary layer 12 is capable of generating a base and diffusing it into the recording layer 13 during high-temperature storage.
  • the auxiliary layer 12 is provided adjacent to the recording layer 13 . Since the auxiliary layer 12 is provided adjacent to the recording layer 13, when the optical recording medium 10 is stored in a high-temperature environment, the thermal acid generator generates acid and the thermal base generator generates acid. Generates a base. As a result, the generated acid and base can undergo a neutralization reaction, so that the amount of acid acting on the electron-donating dye can be reduced. Therefore, it is possible to suppress the hue change of the background during high-temperature storage.
  • the background refers to an erased portion (unrecorded portion) of the recording layer 13 .
  • the thickness of the auxiliary layer 12 is preferably 1 ⁇ m or more and 20 ⁇ m or less, more preferably 2 ⁇ m or more and 15 ⁇ m or less.
  • the auxiliary layer 12 contains a matrix resin and a thermal base generator. If necessary, the recording layer 13 may contain additives such as ultraviolet absorbers in addition to the above materials.
  • the matrix resin preferably functions as a binder.
  • the matrix resin is preferably one in which the thermal base generator can easily be uniformly dispersed.
  • the matrix resin include at least one selected from the group consisting of thermosetting resins and thermoplastic resins.
  • Specific examples of the matrix resin include materials similar to those of the matrix resin of the recording layer 13 .
  • Thermal base generator A thermal base generator generates a base at a predetermined temperature or higher. The generated base diffuses into the recording layer 13 .
  • the thermal base generator includes, for example, at least one salt selected from the group consisting of diazabicycloundecene (DBU (registered trademark)) salts and DBU derivative salts.
  • DBU diazabicycloundecene
  • Anions of diazabicycloundecene salts and diazabicycloundecene derivative salts are, for example, phenol, octylic acid or boric acid.
  • DBU salts include, for example, salts represented by the following formula (7).
  • X in Formula (7) is a compound represented by Formula (8) below.
  • DBU derivative salts include, for example, salts represented by the following formula (9).
  • the base generation temperature of the thermal base generator is preferably approximately the same as the acid generation temperature of the thermal acid generator. If the base generation temperature of the thermal base generator substantially coincides with the acid generation temperature of the thermal acid generator, when the optical recording medium 10 is stored at a high temperature, the thermal base is generated at substantially the same time as the thermal acid generator generates acid. A generator generates and diffuses a base. Therefore, the amount of acid generated by the thermal acid generator and the amount of base generated by the thermal base generator can be balanced. Therefore, it is possible to counteract the color development and the color decoloration, and to suppress the progress of either color development or color decoloration.
  • the lower limit of the base generation temperature T B of the thermal base generator is preferably 150° C. or higher.
  • the base generation temperature T B of the thermal base generator is 150° C. or higher, even when the optical recording medium 10 after recording is left in a high-temperature environment (for example, in a car under the hot sun reaching 80° C.), The change in hue of the 10 printed portions (colored portions) can be suppressed, and the original printed state can be maintained.
  • the upper limit of the base generation temperature T B of the thermal base generator is preferably less than the thermal decomposition temperature of the matrix resin contained in the auxiliary layer 12, for example less than 280°C.
  • the base generation temperature T B of the thermal base generator is lower than the thermal decomposition temperature of the matrix resin contained in the auxiliary layer 12, the disappearance of the auxiliary layer 12 is suppressed before the thermal base generator generates a base. can do.
  • the base generation temperature T B of the thermal base generator is obtained as follows. First, the auxiliary layer 12 and the recording layer 13 are taken out from the optical recording medium 10, respectively. Next, the taken-out recording layer 13 is pasted on the PET substrate. Next, the PET substrate is heated in an oven at 150° C. for 30 minutes so that the recording layer 13 is sufficiently colored. Sample 2 is thus obtained.
  • a graph f B (T) showing the relationship between contactor temperature T and OD is created in the same manner as the method for determining the acid generation temperature T A of the thermal acid generator except that sample 2 is used.
  • the maximum OD max maximum value of f B (T)
  • minimum OD min minimum value of f B (T)
  • these maximum OD max and minimum OD midpoint OD mid is obtained.
  • the temperature at which the midpoint OD mid is obtained is obtained by interpolation of the graph, and this temperature is defined as the base generation temperature T B of the base generation temperature.
  • T B the base generation temperature
  • R is a parameter representing the gradual rise of the graph.
  • the acid generation temperature T A of the thermal acid generator and the base generation temperature T B of the thermal base generator preferably satisfy the following relational expression (A).
  • the methods for obtaining the acid generation temperature T A of the thermal acid generator and the base generation temperature T B of the thermal base generator are as described above.
  • FIG. 1 An example of a drawing method for the optical recording medium 10 according to the first embodiment will be described below with reference to FIGS. 3 and 4.
  • FIG. 1 An example of a drawing method for the optical recording medium 10 according to the first embodiment will be described below with reference to FIGS. 3 and 4.
  • FIG. 1 An example of a drawing method for the optical recording medium 10 according to the first embodiment will be described below with reference to FIGS. 3 and 4.
  • FIG. 1 An example of a drawing method for the optical recording medium 10 according to the first embodiment will be described below with reference to FIGS. 3 and 4.
  • the electron-donating dye and the thermal acid generator contained in the recording layer 13 are in a decolored state and a neutral state, respectively.
  • the thermal base generator contained in the auxiliary layer 12 is in a neutral state.
  • the photothermal conversion agent contained in the laser beam-irradiated portion of the recording layer 13 absorbs the laser beam L. Absorption generates heat, which activates the thermal acid generator to generate acid.
  • the thermal acid generator to generate acid.
  • the generated acid diffuses in the recording layer 13 and acts on the decolorized electron-donating dye, the electron-donating dye undergoes a hue change and becomes colored. A desired image is thus drawn on the recording layer 13 .
  • the thermal base generator contained in the auxiliary layer 12 does not receive sufficient heat to activate the thermal base generator even when irradiated with the laser beam. can't Therefore, the thermal base generator remains neutral and does not generate base. Therefore, during writing, the base will not diffuse from the auxiliary layer 12 to the recording layer 13 .
  • the recording layer may be damaged by long-term heating.
  • the thermal acid generator contained in 13 generates an acid
  • the thermal base generator contained in the auxiliary layer 12 generates a base.
  • the generated acid and base diffuse and react to neutralize.
  • the coloring of the drawing portion (recording portion) of the recording layer is maintained as it is.
  • FIG. 5 shows the state of the optical recording medium 10 after drawing, but the effect of suppressing background coloring is not limited to the optical recording medium 10 after drawing. A medium 10 is similarly obtained.
  • a solvent eg, pure water
  • a thermal base generator is added to this solution and dispersed.
  • an auxiliary layer-forming coating material is obtained.
  • the auxiliary layer 12 is formed by coating the auxiliary layer forming coating material on the substrate 11 and drying it.
  • the matrix polymer dissolves in a solvent (eg, methyl ethyl ketone).
  • a solvent eg, methyl ethyl ketone.
  • the decolorized electron-donating dye, the thermal acid generator and the photothermal conversion material are added to the solution and dispersed.
  • a coating material for forming a recording layer is obtained.
  • the recording layer 13 is formed by coating the recording layer forming coating material on the auxiliary layer 12 and drying it.
  • the optical recording medium 10 shown in FIG. 1 is obtained.
  • the optical recording medium 10 includes a recording layer containing a matrix resin, a decolorized electron-donating dye, a thermal acid generator, and a photothermal conversion agent. Electron-donating dyes are capable of exhibiting reversible hue changes under the action of acids and bases.
  • a laser beam L such as a near-infrared laser beam
  • the photothermal conversion agent contained in the irradiated portion of the recording layer 13 absorbs the laser beam and generates heat. This heat generation causes the thermal acid generator to generate acid.
  • the generated acid acts on the electron-donating dye, the electron-donating dye undergoes a reversible hue change and becomes colored. Therefore, a desired image can be drawn on the optical recording medium 10 .
  • the auxiliary layer 12 containing the thermal base generator is provided adjacent to the recording layer 13 containing the thermal acid generator.
  • a crystalline acidic substance is generally used as a color developer at room temperature.
  • an acidic substance that is crystalline at room temperature is irradiated with a laser beam and melted, the molten acidic substance acts on the electron-donating dye, causing the electron-donating dye to develop a color.
  • substances having long-chain alkyl groups are often used as such crystalline acidic substances (color developers), and the raw materials thereof are generally expensive. For this reason, the conventional optical recording medium has a problem that the manufacturing cost rises significantly.
  • the optical recording medium 10 according to the first embodiment a less expensive thermal acid generator (which generates acid at a temperature equal to or higher than the activation temperature) is used as the color developer instead of the crystalline acidic substance. substances) are used. Therefore, the manufacturing cost of the optical recording medium 10 according to the first embodiment can be reduced.
  • the optical recording medium has one recording layer.
  • the optical recording medium contains color formers having different coloring hues. An example with three recording layers will be described.
  • FIG. 6 is a cross-sectional view showing an example of the configuration of an optical recording medium 10A according to the second embodiment.
  • the optical recording medium 10A comprises a substrate 11, three recording layers 13A, 13B, 13C and three auxiliary layers 12A, 12B, 12C.
  • the recording layers 13A, 13B, and 13C are collectively referred to as the recording layer 13 without any particular distinction.
  • the auxiliary layers 12A, 12B, and 12C are collectively referred to as the auxiliary layer 12 without any particular distinction.
  • symbol is attached
  • a laminate is composed of three recording layers 13 and three auxiliary layers 12 .
  • the recording layers 13 and the auxiliary layers 12 are alternately provided on the substrate 11 .
  • the recording layer 13 and the auxiliary layer 12 are adjacent to each other.
  • the bottom layer of the laminate may be either the auxiliary layer 12 or the recording layer 13 .
  • the bottom layer of the laminate is on the substrate 11 side.
  • the optical recording medium 10A may further include a protective layer on the laminate.
  • the recording layers 13A, 13B, and 13C can change the coloring state by laser light (external stimulus).
  • the recording layers 13A, 13B, and 13C can exhibit hues different from each other in the colored state.
  • the recording layer 13A can exhibit a magenta color in a colored state.
  • the recording layer 13B can exhibit a cyan color in a colored state.
  • the recording layer 13C 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 recording layer 13A contains a first matrix resin, a decolorized first electron-donating dye, a first thermal acid generator, and a first photothermal conversion agent.
  • the recording layer 13B contains a second matrix resin, a decolorized second electron-donating dye, a second thermal acid generator, and a second photothermal conversion agent.
  • the recording layer 13B contains a third matrix resin, a third electron-donating dye in a decolorized state, a third thermal acid generator, and a third photothermal conversion agent.
  • the recording layers 13A, 13B, and 13C, like the recording layer 13, 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 matrix resins are the same as the matrix resins contained in the recording layer 13 of the first embodiment.
  • the first, second, and third electron-donating dyes can exhibit different hues in the developed state. Specifically, the first electron-donating dye can exhibit a magenta color in the developed state. The second electron-donating dye is capable of exhibiting a cyan color in the developed state. The third electron-donating dye can exhibit a yellow color in the developed state.
  • the first, second and third thermal acid generators are the same as the thermal acid generators contained in the recording layer 13 of the first embodiment.
  • the acid generation temperatures of the first, second and third thermal acid generators may all be different, or the acid generation temperatures of the first, second and third thermal acid generators may all be the same.
  • 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 13A, 13B, and 13C is selectively colored by irradiation with a laser beam.
  • each of the recording layers 13A, 13B, and 13C is preferably, for example, 1 ⁇ m or more and 20 ⁇ m or less, and more preferably, for example, 2 ⁇ m or more and 15 ⁇ m or less.
  • the thickness of the recording layers 13A, 13B, and 13C is 1 ⁇ m or more, the color density can be improved.
  • the thickness of the recording layers 13A, 13B, and 13C is 20 ⁇ m or less, it is possible to suppress an increase in the amount of heat utilization of the recording layers 13A, 13B, and 13C, and to suppress deterioration of color developability.
  • the auxiliary layer 12A is a base layer capable of generating a base during storage at high temperature and diffusing it into the recording layer 13A.
  • the auxiliary layer 12A is provided adjacent to the recording layer 13A.
  • the auxiliary layer 12A contains a fourth matrix resin and a first thermal base generator. If necessary, the auxiliary layer 12A may contain additives such as ultraviolet absorbers in addition to the above materials.
  • the auxiliary layer 12B is a base layer that can generate a base during high-temperature storage and diffuse into the recording layer 13B.
  • the auxiliary layer 12B may be capable of diffusing the generated base into the recording layer 13A as well.
  • the auxiliary layer 12B is provided adjacent to the recording layer 13B.
  • the auxiliary layer 12B contains a fifth matrix resin and a second thermal base generator. If necessary, the auxiliary layer 12B may contain additives such as ultraviolet absorbers in addition to the above materials.
  • the auxiliary layer 12C is a base layer that can generate a base during high-temperature storage and diffuse into the recording layer 13C.
  • the auxiliary layer 12C may be capable of diffusing the generated base into the recording layer 13B as well.
  • the auxiliary layer 12C is provided adjacent to the recording layer 13C.
  • Auxiliary layer 12C contains a sixth matrix resin and a third thermal base generator. 12 C of auxiliary
  • the first, second and third matrix resins are the same as the matrix resins contained in the auxiliary layer 12 of the first embodiment.
  • first, second, and third thermal base generators As the first, second, and third thermal base generators, the same materials as the thermal base generators contained in the auxiliary layer 12 of the first embodiment can be exemplified.
  • the base generation temperatures of the first, second and third thermal base generators may all be different, or the base generation temperatures of the first, second and third thermal base generators may all be the same.
  • the base generation temperature of the first thermal base generator is preferably approximately the same as the acid generation temperature of the first thermal acid generator.
  • the base generation temperature of the first thermal base generator substantially matches the acid generation temperature of the first thermal acid generator, when the optical recording medium 10A is stored at a high temperature, the first thermal acid generator generates an acid, the first thermal base generator generates and diffuses a base substantially at the same time.
  • the base generation temperature of the second thermal base generator substantially coincides with the acid generation temperature of the second thermal acid generator or lower. It is preferable that the base generation temperature of the third thermal base generator substantially coincides with the acid generation temperature of the third thermal acid generator or lower.
  • the effect obtained by defining the base generation temperatures of the second thermal base generator and the third thermal base generator as described above can be obtained by defining the base generation temperature of the first thermal base generator. Since it is the same as the effect obtained, the explanation is omitted.
  • the acid generation temperature T A1 of the first thermal acid generator and the first thermal base generation preferably satisfies the following relational expression (A1).
  • the acid generation temperature TA2 of the second thermal acid generator and the second thermal base generation preferably satisfies the following relational expression (A2).
  • the acid generation temperature TA3 of the third thermal acid generator and the third thermal base generation preferably satisfies the following relational expression (A3).
  • the recording layer 13A is colored magenta as follows.
  • a predetermined position of the recording layer 13A is irradiated with a near - infrared laser beam having a wavelength of ⁇ 1.
  • the photothermal conversion agent contained in the irradiated portion of the laser beam absorbs the near-infrared laser beam and generates heat, and the heat generation causes the thermal acid generator to generate acid.
  • the generated acid acts on the electron-donating dye
  • the electron-donating dye changes its hue and develops a magenta color.
  • the portion irradiated with the laser light develops a magenta color.
  • the recording layer 13B is colored cyan in the following manner.
  • a predetermined position of the recording layer 13B is irradiated with a near - infrared laser beam having a wavelength of ⁇ 2. Due to the reaction similar to that of the recording layer 13A, the portion irradiated with the laser light develops a cyan color.
  • the recording layer 13C is colored yellow in the following manner.
  • a predetermined position of the recording layer 13C is irradiated with a near - infrared laser beam having a wavelength of ⁇ 3. Due to the reaction similar to that of the recording layer 13A, the portion irradiated with the laser light develops a yellow color.
  • predetermined positions of the recording layers 13A, 13B, and 13C are colored magenta, cyan, and yellow, respectively, so that a desired full-color image is drawn on the optical recording medium 10 .
  • the auxiliary layer 12A is provided adjacent to the recording layer 13A
  • the auxiliary layer 12B is provided adjacent to the recording layer 13B
  • the auxiliary layer 12C is provided adjacent to the recording layer 13C.
  • the recording layers 13A, 13B, and 13C are capable of exhibiting magenta, cyan, and yellow, respectively, in the colored state. Therefore, a desired image can be drawn in full color.
  • the optical recording medium has three recording layers and is capable of drawing a full-color image.
  • An example in which a recording layer containing microcapsules is provided and a full-color image can be drawn will be described.
  • FIG. 7 is a cross-sectional view showing an example of the configuration of an optical recording medium 10B according to the third embodiment.
  • the optical recording medium 10B includes a substrate 11 , an auxiliary layer 12 provided on the substrate 11 , and a recording layer 15 provided on the auxiliary layer 12 .
  • 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 the coloring state by laser light (external stimulus).
  • 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 microcapsule 15A contains a decolorized first electron-donating dye, a first thermal acid generator and a first photothermal conversion agent in the microcapsule wall.
  • the microcapsule 15B contains a second electron-donating dye in a decolorized state, a second thermal acid generator and a second photothermal conversion agent within the microcapsule wall.
  • the microcapsule 15C contains a third electron-donating dye in a decolorized state, a third thermal acid generator and a third photothermal conversion agent within the microcapsule wall.
  • Each of the microcapsules 15A, 15B, and 15C contains, in addition to the above materials, at least one additive selected from the group consisting of matrix resins, sensitizers, ultraviolet absorbers, etc., in the microcapsule walls. You can stay.
  • microcapsule wall The microcapsule walls of the microcapsules 15A, 15B, and 15C can be dissolved by the heat generation of the photothermal conversion agent due to absorption of laser light.
  • the microcapsule walls of microcapsules 15A, 15B, 15C may be permeable to the base generated from the base generator.
  • the microcapsule wall is 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, methyl cellulose, polystyrene, styrenic copolymer, phenoxy resin, polyester, and aromatic polyester.
  • the first, second and third electron-donating dyes are the same as in the second embodiment.
  • the first, second and third thermal acid generators 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 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 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 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 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 optical recording medium 10B by developing magenta, cyan, and yellow colors at predetermined positions on the recording layer 15, respectively.
  • the optical recording medium 10B when the recording layer 15 is colored by laser light irradiation, the microcapsules 15A, 15B, and 15C contained in the laser light irradiated portion (color-developed portion) are dissolved. do.
  • the optical recording medium 10B after drawing is stored in a high-temperature environment, the acid generated from the thermal acid generator and the base generated from the thermal base generator are mixed in the irradiated portion (portion in the colored state). Because of the sum reaction, the amount of acid acting on the electron-donating dye can be reduced. Therefore, it is possible to suppress the change in hue of the colored portion (recording portion) during high-temperature storage.
  • the base generated by the thermal base generator when the optical recording medium 10B is stored in a high-temperature environment can diffuse from the auxiliary layer 12 to the recording layer 15 and penetrate the capsule walls of the microcapsules 15A, 15B, 15C.
  • the base that has permeated the capsule wall can neutralize with the acid generated in the microcapsules 15A, 15B, and 15C. can be suppressed.
  • the recording layer contains a thermal acid generator and the auxiliary layer contains a thermal base generator.
  • a thermal base generator is included instead and the auxiliary layer includes a thermal acid generator instead of the thermal base generator will be described.
  • the optical recording medium 10 according to the fourth embodiment has the same layer structure as the optical recording medium 10 according to the first embodiment. Therefore, the configuration of the optical recording medium 10 according to the fourth embodiment will be described below with reference to FIG.
  • the recording layer 13 contains a matrix resin, an electron-donating dye in a colored state, a thermal base generator and a photothermal conversion agent, and the auxiliary layer 12 contains a matrix resin and a thermal acid generator. is different from the optical recording medium 10 according to the first embodiment.
  • the recording layer 13 in an unrecorded state is in a colored state.
  • the recording layer 13 can change from a colored state to a decolored state by laser light (external stimulus).
  • the recording layer 13 can exhibit a predetermined color in a colored state.
  • the auxiliary layer 12 is capable of generating acid and diffusing it into the recording layer 13 during high-temperature storage.
  • the acid generation temperature of the thermal acid generator is preferably approximately the same as the base generation temperature of the thermal base generator. If the acid generation temperature of the thermal acid generator substantially coincides with the base generation temperature of the thermal base generator, when the optical recording medium 10 is stored at a high temperature, thermal acid is generated substantially at the same time as the thermal base generator generates a base.
  • a generator generates and diffuses acid.
  • the background refers to a colored portion of the recording layer 13 .
  • the electron-donating dye and thermal base generator contained in the recording layer 13 are in a colored state and a neutral state, respectively. Also, the thermal acid generator contained in the auxiliary layer 12 is in a neutral state.
  • the photothermal conversion agent contained in the irradiated portion of the recording layer 13 absorbs the laser beam and generates heat.
  • a generator is activated to generate a base.
  • the generated base diffuses in the recording layer 13 and acts on the electron-donating dye in the colored state, the electron-donating dye changes its hue and becomes decolored. A desired image is thus drawn on the recording layer 13 .
  • the thermal acid generator contained in the auxiliary layer 12 does not receive sufficient heat to activate the thermal acid generator even when irradiated with the laser beam. can't Therefore, the thermal acid generator remains neutral and does not generate acid. Therefore, acid is not diffused from the auxiliary layer 12 to the recording layer 13 during writing.
  • the thermal base generator contained in the recording layer 13 when the temperature of the entire optical recording medium 10 is raised due to high-temperature storage, the thermal base generator contained in the recording layer 13 generates a base, and the auxiliary layer 12 The included thermal acid generator generates a base. The generated base and acid diffuse and react to neutralize. As a result, it is possible to suppress the action of the generated base on the electron-donating dye, thereby suppressing the background color development during high-temperature storage.
  • the effect of suppressing background coloring may be obtained in the optical recording medium 10 after drawing, or may be obtained in the optical recording medium 10 before drawing (initial state).
  • the recording layer contains a thermal acid generator and a photothermal conversion agent
  • the auxiliary layer contains a thermal base generator.
  • a thermal base generator is included in place of the acid generator and the photothermal conversion agent and the auxiliary layer includes the thermal acid generator and the photothermal conversion agent in place of the thermal base generator will be described.
  • the optical recording medium 10 according to the fifth embodiment has the same layer structure as the optical recording medium 10 according to the first embodiment. Therefore, the configuration of the optical recording medium 10 according to the fifth embodiment will be described below with reference to FIG.
  • the recording layer 13 contains a matrix resin, a decolorized electron-donating dye and a thermal base generator
  • the auxiliary layer 12 contains a matrix resin, a thermal acid generator and a photothermal converter. It differs from the optical recording medium 10 according to the first embodiment in that it contains an agent.
  • the base generation temperature of the thermal base generator substantially coincides with the acid generation temperature of the thermal acid generator.
  • the electron-donating dye and thermal base generator contained in the recording layer 13 are in a decolored state and a neutral state, respectively.
  • each of the thermal acid generators contained in the auxiliary layer 12 is in a neutral state.
  • the photothermal conversion agent contained in the irradiated portion of the auxiliary layer 12 absorbs the laser beam and generates heat.
  • the generator is activated to generate acid.
  • the generated acid diffuses from the auxiliary layer 12 to the recording layer 13 and acts on the decolorized electron-donating dye, the electron-donating dye exhibits a hue change and becomes colored. A desired image is thus drawn on the recording layer 13 .
  • the thermal base generator contained in the recording layer 13 is not given sufficient heat to activate the thermal base generator even by the laser light irradiation. Absent. Therefore, the thermal base generator remains neutral and does not generate base. Therefore, the base is not diffused into the recording layer 13 during writing.
  • the thermal acid generator contained in the auxiliary layer 12 when the temperature of the entire optical recording medium 10 is raised due to high-temperature storage, the thermal acid generator contained in the auxiliary layer 12 generates a base, and the recording layer 13 The included thermal base generator generates a base. The generated base and acid diffuse and react to neutralize. As a result, it is possible to suppress the action of the generated acid on the electron-donating dye, thereby suppressing the coloring of the background during high-temperature storage.
  • the effect of suppressing background coloring may be obtained in the optical recording medium 10 after drawing, or may be obtained in the optical recording medium 10 before drawing (initial state).
  • the optical recording medium 10 according to the sixth embodiment has the same layer structure as the optical recording medium 10 according to the first embodiment. Therefore, the configuration of the optical recording medium 10 according to the sixth embodiment will be described below with reference to FIG.
  • the recording layer 13 contains a matrix resin, an electron-donating dye in a colored state, and a thermal acid generator
  • the auxiliary layer 12 contains a matrix resin, a thermal base generator, and a photothermal conversion agent. is different from the optical recording medium 10 according to the first embodiment.
  • the recording layer 13 in an unrecorded state is in a colored state.
  • the recording layer 13 can change from a colored state to a decolored state by laser light (external stimulus).
  • the recording layer 13 can exhibit a predetermined color in a colored state.
  • the acid generation temperature of the thermal acid generator is preferably approximately the same as the base generation temperature of the thermal base generator. If the acid generation temperature of the thermal acid generator substantially coincides with the base generation temperature of the thermal base generator, when the optical recording medium 10 is stored at a high temperature, thermal acid is generated substantially at the same time as the thermal base generator generates a base. A generator generates and diffuses acid.
  • the background refers to a colored portion of the recording layer 13 .
  • auxiliary layer 12 When the auxiliary layer 12 is irradiated with a laser beam, a base can be generated from the irradiated portion of the laser beam and diffused into the recording layer 13 .
  • the electron-donating dye and the thermal acid generator contained in the recording layer 13 are in a colored state and a neutral state, respectively.
  • the thermal base generator contained in the auxiliary layer 12 is in a neutral state.
  • the photothermal conversion agent contained in the irradiated portion of the auxiliary layer 12 absorbs the laser beam and generates heat.
  • a generator is activated to generate a base.
  • the generated base diffuses from the auxiliary layer 12 to the recording layer 13 and acts on the electron-donating dye in the colored state, the electron-donating dye changes its hue and becomes decolored. A desired image is thus drawn on the recording layer 13 .
  • the thermal acid generator contained in the recording layer 13 does not receive enough heat to activate the thermal acid generator even when irradiated with the laser beam. can't Therefore, the thermal acid generator remains neutral and does not generate acid. Therefore, the acid does not diffuse into the recording layer 13 during writing.
  • the thermal base generator contained in the auxiliary layer 12 when the temperature of the entire optical recording medium 10 is raised by high-temperature storage, the thermal base generator contained in the auxiliary layer 12 generates a base, and the recording layer 13 The included thermal acid generator generates acid. The generated base and acid diffuse and react to neutralize. As a result, it is possible to suppress the action of the generated base on the electron-donating dye, thereby suppressing the background color development during high-temperature storage.
  • the effect of suppressing background coloring may be obtained in the optical recording medium 10 after drawing, or may be obtained in the optical recording medium 10 before drawing (initial state).
  • Modification 1 Modification 1
  • Modification 2 In the third embodiment, the example in which the recording layer 13A and the auxiliary layer 12B are adjacent and the recording layer 13B and the auxiliary layer 12C are adjacent (see FIG. 6) has been described.
  • a heat insulating layer 14A may be provided between the recording layer 13A and the auxiliary layer 12B, and a heat insulating layer 14B may be provided between the recording layer 13B and the auxiliary layer 12C.
  • the heat insulating 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 heat insulating layers 14A and 14B may contain various additives such as ultraviolet absorbers.
  • the heat insulating 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 heat insulating layers 14A, 14B can be formed by, for example, a sol-gel method.
  • the thickness of the heat insulating layers 14A and 14B is preferably, for example, 3 ⁇ m or more and 100 ⁇ m or less, and more preferably, for example, 5 ⁇ m or more and 50 ⁇ m or less. If the heat insulating layers 14A and 14B are too thin, there is a possibility that a sufficient heat insulating effect cannot be obtained. On the other hand, if the heat insulating layers 14A and 14B are too thick, there is a possibility that the translucency will be lowered. In addition, the bending resistance of the optical recording medium 10B is lowered, and defects such as cracks are likely to occur.
  • the electron-donating dye is capable of exhibiting a reversible hue change under the action of an acid and a base. It may be possible to exhibit an irreversible hue change upon action.
  • the base generation temperature of the thermal base generator may be lower than the acid generation temperature of the thermal acid generator.
  • the image can be fixed by heating the optical recording media 10, 10A, and 10B to the base-generating temperature after the laser drawing to create an excess base state.
  • auxiliary layer 12 is adjacent to the recording layer 13
  • the layer 13 may be configured to allow the base to diffuse.
  • an intermediate layer may be provided between the auxiliary layer 12A and the recording layer 13A, and the intermediate layer may be configured to allow the base to diffuse from the auxiliary layer 12A to the recording layer 13A.
  • an intermediate layer may be provided between the auxiliary layer 12B and the recording layer 13B, and the intermediate layer may be configured to allow the base to diffuse from the auxiliary layer 12B to the recording layer 13B.
  • an intermediate layer may be provided between the auxiliary layer 12C and the recording layer 13C, and the intermediate layer may be configured to allow the base to diffuse from the auxiliary layer 12C to the recording layer 13C.
  • an intermediate layer may be provided between the auxiliary layer 12 and the recording layer 15 so that the intermediate layer can diffuse the base from the auxiliary layer 12 to the recording layer 15 .
  • the optical recording medium 10 may be manufactured using other methods. That is, the auxiliary layer 12 may be formed using a method other than coating, and the recording layer 13 may be formed using a method other than coating.
  • the auxiliary layer 12 may be formed as follows.
  • the auxiliary layer 12 that is formed by coating another base material in advance may be attached onto the base material 11 via an adhesive layer, for example.
  • the auxiliary layer 12 may be formed by immersing the substrate 11 in the auxiliary layer forming coating material.
  • the recording layer 13 may be formed as follows.
  • the recording layer 13 formed by coating another base material in advance may be attached onto the auxiliary layer 12 via an adhesive layer, for example.
  • the recording layer 13 may be formed by immersing the substrate 11 with the auxiliary layer 12 formed thereon in a recording layer forming coating material.
  • the optical recording medium 10A includes three recording layers 13A, 13B, 13C and three auxiliary layers 12A, 12B, 12C.
  • a plurality of recording layers other than three and a plurality of auxiliary layers other than three may be provided.
  • the plurality of recording layers and the plurality of auxiliary layers may be laminated such that the recording layers and the auxiliary layers are alternately positioned.
  • Each of the plurality of recording layers may be capable of exhibiting different hues in a colored state.
  • the photothermal conversion agents contained in each of the plurality of recording layers may have absorption wavelength peaks different from each other.
  • the recording layer 15 may contain more than three types of microcapsules.
  • Each of the plurality of types of microcapsules may be capable of exhibiting different hues in a colored state.
  • the photothermal conversion agents contained in the plurality of types of microcapsules may have absorption wavelength peaks different from each other.
  • the structure of the recording layer 13 in the fourth embodiment is applied to the recording layers 13A, 13B, and 13C in the second embodiment, and the auxiliary layers 12A, 12B, and 12C in the second embodiment are applied to the recording layers 13A, 13B, and 13C of the fourth embodiment.
  • the photothermal conversion agents contained in the recording layers 13A, 13B, and 13C have different absorption wavelength peaks.
  • the structure of the recording layer 13 in the fifth embodiment is applied to the recording layers 13A, 13B, and 13C in the second embodiment, and the auxiliary layers 12A, 12B, and 12C in the second embodiment are applied to the recording layers 13A, 13B, and 13C of the fifth embodiment.
  • the photothermal conversion agents contained in the auxiliary layers 12A, 12B, and 12C have different absorption wavelength peaks.
  • the structure of the recording layer 13 in the sixth embodiment is applied to the recording layers 13A, 13B, and 13C in the second embodiment, and the auxiliary layers 12A, 12B, and 12C in the second embodiment are applied to the recording layers 13A, 13B, and 13C of the sixth embodiment.
  • the photothermal conversion agents contained in the auxiliary layers 12A, 12B, and 12C have different absorption wavelength peaks.
  • the microcapsules 15A in the third embodiment contain the first electron-donating dye in the coloring state, the first thermal base generator and the first photothermal conversion agent, and the microcapsules 15B and 15B are color-developing a second electron-donating dye, a second thermal base generator, and a second photothermal conversion agent in a state of and a third photothermal conversion agent.
  • the auxiliary layer 12 may contain a matrix resin and a thermal acid generator.
  • the first, second and third photothermal conversion agents may have different absorption wavelength peaks.
  • the temperature of the thermal acid generator determined as follows: The acid generation temperature T C and the base generation temperature T D of the thermal base generator may be used.
  • the acid generation temperature TC of the thermal acid generator and the base generation temperature TD of the thermal base generator obtained as described above may satisfy the following relational expression ( B ).
  • the acid generation temperature TC of the thermal acid generator and the base generation temperature TD of the thermal base generator satisfy the above relational expression ( B )
  • the amount of acid generated by the thermal acid generator and the thermal base generator can be antagonized with the amount of base generated. Therefore, it is possible to antagonize coloring and decoloring, and to suppress progress of either coloring or decoloring.
  • the acid generation temperature T C1 of the first thermal acid generator and the first thermal base generation preferably satisfies the following relational expression (B1).
  • the acid generation temperature TC2 of the second thermal acid generator and the second thermal base generation preferably satisfies the following relational expression (B2).
  • the acid generation temperature TC3 of the third thermal acid generator and the third thermal base generation preferably satisfies the following relational expression (B3).
  • 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 present disclosure can also employ the following configuration.
  • a recording layer containing a matrix resin, an electron-donating dye in a decolorized state, a thermal acid generator and a photothermal conversion agent; an auxiliary layer comprising a matrix resin and a thermal base generator;
  • the optical recording medium wherein the thermal acid generator contains at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
  • the electron-donating dye is capable of exhibiting a reversible hue change under the action of acid and base.
  • the electron-donating dye is capable of exhibiting an irreversible hue change under the action of an acid.
  • a plurality of the recording layers are provided, A plurality of the auxiliary layers are provided, The recording layers and the auxiliary layers are alternately provided, The electron-donating dyes contained in each of the plurality of recording layers are capable of exhibiting different hues in a colored state,
  • the optical recording medium according to any one of (1) to (3), wherein the photothermal conversion agents contained in the plurality of recording layers have different absorption wavelength peaks.
  • the recording layer contains a plurality of types of capsules,
  • the plurality of types of capsules contain the electron-donating dye, the thermal acid generator and the photothermal conversion agent,
  • the electron-donating dyes contained in each of the plurality of types of capsules are capable of exhibiting different hues in a colored state
  • the optical recording medium according to any one of (1) to (3), wherein the photothermal conversion agents contained in each of the plurality of types of capsules have absorption wavelength peaks different from each other.
  • the light according to any one of (1) to (5), wherein the acid generation temperature T A of the thermal acid generator and the base generation temperature T B of the thermal base generator satisfy the following relational expression (A): recoding media.
  • the thermal acid generator contains at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
  • thermo acid generator contains at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
  • An identification card comprising the optical recording medium according to any one of (1) to (12).
  • a booklet comprising the optical recording medium according to any one of (1) to (12).
  • a card comprising the optical recording medium according to any one of (1) to (12).
  • optical recording media 10, 10A, and 10B are used as a part of various electronic devices or accessories, such as so-called wearable terminals, such as watches (watches), bags, clothes, hats, glasses, and shoes. It can be applied to some, and the type of the electronic equipment is not particularly limited. Moreover, it can be applied not only to electronic devices and furnishings, but also to interiors and exteriors such as walls of buildings as exterior members, exteriors of furniture such as desks, and the like.
  • optical recording medium 10 is applied to an identification card, a card, an electronic device, etc.
  • a card a card, an electronic device, etc.
  • two or more of the optical recording media 10, 10A, 10B can be combined and applied to identification cards, cards, electronic devices, etc. It is possible.
  • FIG. 10A shows the appearance of a card-type identification card.
  • FIG. 10B is a cross-sectional view along line XB-XB of FIG. 10A.
  • a card-type identification card is an example of a card, and includes a substrate 21, an adhesive layer 22, an optical recording medium 23, an adhesive layer 24, and an overlay layer 25 in sequence.
  • the optical recording medium 23 is provided on one side of the base material 21 will be described, but the optical recording medium 23 may be provided on both sides of the base material 21 .
  • the base material 21 is a supporting base material that supports the optical recording medium 23 .
  • the base material 21 is, for example, a plastic substrate.
  • the optical recording medium 23 is the optical recording medium 10 .
  • the adhesive layer 22 bonds the base material 21 and the optical recording medium 23 together.
  • the adhesive layer 24 bonds the optical recording medium 23 and the overlay layer 25 together.
  • Overlay layer 25 protects optical recording medium 23 .
  • An overlay layer 25 covers one side of the optical 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. 11 shows the appearance of a booklet-type identification card.
  • a booklet-type identification card is an example of a booklet, and includes a plurality of sheets 31 . The plurality of sheets 31 are saddle-stitched.
  • An optical recording medium 10 is provided on at least one surface of the sheet 31 . On the optical recording medium 10, characters, numerical values, facial photographs, etc. are drawn.
  • a specific example of a booklet-type identification card is, for example, a passport.
  • FIGS. 12A and 12B show the appearance of an integrated circuit (IC) card with a rewrite function.
  • This IC card has a printed surface 110 on the front side of the card, to which, for example, a sheet-like optical recording medium 10 is attached.
  • IC integrated circuit
  • 13A and 13B 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. 14A shows the external configuration of the front surface of the smartphone.
  • FIG. 14B shows the external configuration of the back surface of the smartphone shown in FIG. 14A.
  • This smartphone includes, for example, a display section 210 , a non-display section 220 , and a housing 230 .
  • An optical recording medium 10, for example is provided as an exterior member of the housing 230 on, for example, one surface of the housing 230 on the back side, thereby displaying various colors and patterns as shown in FIG. 14B. can be done.
  • 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
  • FIG. 15A and 15B show the appearance of the bag.
  • This bag has, for example, a storage section 310 and a handle 320.
  • the optical recording medium 10 is attached to the storage section 310, for example.
  • Various characters and patterns are displayed on the storage unit 310 by the optical recording medium 10, for example.
  • various colored patterns can be displayed, and the design of the storage portion 310 can be changed from the example in FIG. 15A to the example in FIG. 15B. can. It becomes possible to realize an electronic device that is also useful for fashion applications.
  • FIG. 16A shows the appearance of the top surface of the automobile
  • FIG. 16B shows the appearance of the side surface of the automobile.
  • the optical recording medium 10 of the present disclosure can be used in various parts of the vehicle body such as the bonnet 411, bumper 412, roof 413, trunk cover 414, front door 415, rear door 416 and rear bumper 417. Information and colors can be displayed. Also, the optical 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. 17 shows the appearance of the cosmetic container.
  • This cosmetic container has, for example, a storage portion 510 and a lid 520 covering the storage portion 510.
  • the optical recording medium 10 is attached to the lid 520, for example.
  • the cover 520 is decorated by the optical recording medium 10, for example, with patterns, colors, or characters as shown in FIG.
  • the pattern, color pattern, characters, etc. of the lid 520 can be written by a predetermined drawing device.
  • the optical recording medium 10 can be attached not only to the front surface (cover 520) of the cosmetic container, but also to the back surface (accommodating portion 510) or the like.
  • FIG. 18 shows the appearance of the nail tip.
  • a nail tip is an example of an exterior member.
  • the nail tip has an optical recording medium 10 on its surface.
  • the optical recording medium 10 By providing the optical recording medium 10 on the surface of the nail tip in this way, various colors and patterns can be displayed.
  • the configuration in which the nail tip has the optical recording medium 10 on its surface has been described, but the configuration of the nail tip is not limited to this, and the optical recording medium 10 itself may be the nail tip.
  • the substrate 11 has a nail-like shape.
  • FIG. 19A shows the appearance of the nail seal.
  • FIG. 19B shows a cross section along line XIXB-XIXB in FIG. 19A.
  • 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 an optical recording medium 10 and an adhesive layer 611 .
  • the adhesive layer 611 is provided on the surface of the optical recording medium 10 on the substrate 11 side.
  • the optical recording medium 10 may further include a protective layer 16 on the recording layer 13 .
  • the optical recording medium 10 and the like have a plurality of nail seal portions 612 that are 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 auxiliary layer 12 and the recording layer 13 may be directly laminated on a natural nail (human nail) as a supporting substrate.
  • the auxiliary layer 12 and the recording layer 13 may be formed by applying a paint to the base nail and curing it, or a laminated sheet composed of the auxiliary layer 12 and the recording layer 13 may be separately formed and attached to the base nail. good.
  • Example 1 (Preparation step of coating material for forming recording layer) A coating material for forming a recording layer was prepared by blending the following materials.
  • Matrix resin manufactured by Mitsubishi Gas Chemical Company, Inc., FPC0330
  • Leuco dye manufactured by Yamamoto Kasei Co., Ltd., RED-3
  • TAG-2689 2% by mass Thermal acid generator (TAG-2689, manufactured by King Industries Inc.)
  • Photothermal conversion agent manufactured by Yamada Chemical Co., Ltd., FDN-005
  • Solvent manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., methyl ethyl ketone (MEK)
  • the thermal acid generator and the thermal base generator were selected such that the acid generation temperature T A of the thermal acid generator and the base generation temperature T B of the thermal base generator satisfy the above relational expression (A).
  • the acid generation temperature T A of the thermal acid generator and the base generation temperature T B of the thermal base generator are each determined by the method for obtaining the acid generation temperature T A of the thermal acid generator described in the first embodiment. , is a value obtained by the method for obtaining the base generation temperature T B of the thermal base generator.
  • a base layer (auxiliary layer) having a thickness of 5 ⁇ m was formed by applying the base layer-forming coating composition onto a PET substrate and drying it.
  • the above recording layer forming coating material was applied onto the base layer and dried to form a recording layer having a thickness of 5 ⁇ m.
  • an intended optical recording medium was obtained.
  • FIG. 20 shows changes in OD with respect to high temperature storage time.
  • the following can be understood from FIG.
  • the increase in OD during high temperature storage is suppressed. Therefore, the hue change of the background is suppressed.
  • the optical recording medium of Comparative Example 1 in which the basic layer was not provided adjacent to the recording layer, the OD increased during high temperature storage. Therefore, the hue change of the background during high-temperature storage is not suppressed.
  • Reference Signs List 10 10A, 10B, 23 Optical recording medium 11, 21 Substrate 12, 12A, 12B, 12C Auxiliary layer 13, 13A, 13B, 13C, 15 Recording layer 14A, 14B Thermal insulation layer 15A, 15B, 15C Microcapsule 16 Protective layer 22, 24 adhesive layer 25 overlay layer 31 sheet 110 printed surface back surface 120A Surface 120B 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 part

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Abstract

The present invention provides an optical recording medium which is capable of suppressing hue change in the background when the optical recording medium is stored at high temperatures.　This optical recording medium is provided with: a recording layer that contains a matrix resin, an electron-donating dye in a color erased state, a thermal acid generator and a photothermal converter; and an auxiliary layer that contains a matrix resin and a thermal base generator. The thermal acid generator contains at least one substance that is selected from the group consisting of an ammonium salt, a sulfonium salt and an iodonium salt.

Description

光記録媒体、身分証明書、カードおよび冊子optical media, identity cards, cards and brochures
　本開示は、光記録媒体、それを備える身分証明書、カードおよび冊子に関する。 This disclosure relates to an optical recording medium, an identification card, a card, and a booklet comprising the same.
　近年、レーザー光照射により画像を描画が可能な光記録媒体の開発が進められている。このような光記録媒体としては、電子供与性色素と顕色剤を用いるものが知られている。顕色剤として熱酸発生化合物を用いることが提案されている（例えば特許文献１参照）。 In recent years, the development of optical recording media on which images can be drawn by laser light irradiation is underway. As such an optical recording medium, one using an electron-donating dye and a developer is known. It has been proposed to use a thermal acid generating compound as a color developer (see, for example, Patent Document 1).
国際公開第２０１６／１３５４６８号パンフレットInternational Publication No. 2016/135468 pamphlet
　しかしながら、熱酸発生化合物（熱酸発生剤）は、一般に活性化温度未満の温度であっても、長時間の加温によって徐々に酸を発生してしまうという性質を有している。このため、光記録媒体を高温（例えば８０℃）の環境に保存すると、地肌の色相が変化するという問題がある。本明細書において、地肌とは、レーザー光の照射により記録が行われていない未記録部を意味する。 However, thermal acid-generating compounds (thermal acid generators) generally have the property of gradually generating acid when heated for a long period of time, even at temperatures below the activation temperature. Therefore, when the optical recording medium is stored in a high-temperature (for example, 80° C.) environment, there is a problem that the hue of the background changes. As used herein, the term "background" means an unrecorded portion where recording is not performed by irradiation with laser light.
　本開示の目的は、高温保存時における地肌の色相変化を抑制することができる光記録媒体、それを備える身分証明書、カードおよび冊子を提供することにある。 An object of the present disclosure is to provide an optical recording medium capable of suppressing color change of the background during high-temperature storage, and an identification card, card, and booklet including the same.
　上記の課題を解決するために、第１の開示は、
　マトリクス樹脂、消色状態の電子供与性色素、熱酸発生剤および光熱変換剤を含む記録層と、
　マトリクス樹脂および熱塩基発生剤を含む補助層と
　を備え、
　電子供与性色素は、酸および塩基の作用により可逆的色相変化を呈することが可能であり、
　熱酸発生剤が、アンモニウム塩、スルホニウム塩およびヨードニウム塩からなる群より選ばれた少なくとも１種を含む光記録媒体である。 In order to solve the above problems, the first disclosure is
a recording layer containing a matrix resin, an electron-donating dye in a decolorized state, a thermal acid generator and a photothermal conversion agent;
an auxiliary layer comprising a matrix resin and a thermal base generator;
The electron-donating dye is capable of exhibiting a reversible hue change under the action of acids and bases,
The optical recording medium includes a thermal acid generator containing at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
　第２の開示は、
　マトリクス樹脂、発色状態の電子供与性色素、熱塩基発生剤および光熱変換剤を含む記録層と、
　マトリクス樹脂および熱酸発生剤を含む補助層と
　を備え、
　熱酸発生剤が、アンモニウム塩、スルホニウム塩およびヨードニウム塩からなる群より選ばれた少なくとも１種を含む光記録媒体である。 The second disclosure is
a recording layer containing a matrix resin, an electron-donating dye in a colored state, a thermal base generator and a photothermal conversion agent;
an auxiliary layer comprising a matrix resin and a thermal acid generator;
The optical recording medium includes a thermal acid generator containing at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
　第３の開示は、
　マトリクス樹脂、消色状態の電子供与性色素および熱塩基発生剤を含む記録層と、
　マトリクス樹脂、熱酸発生剤および光熱変換剤を含む補助層と
　を備え、
　熱酸発生剤が、アンモニウム塩、スルホニウム塩およびヨードニウム塩からなる群より選ばれた少なくとも１種を含む光記録媒体である。 A third disclosure is:
a recording layer containing a matrix resin, an electron-donating dye in a decolorized state, and a thermal base generator;
an auxiliary layer comprising a matrix resin, a thermal acid generator and a photothermal conversion agent;
The optical recording medium includes a thermal acid generator containing at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
　第４の開示は、
　マトリクス樹脂、発色状態の電子供与性色素および熱酸発生剤を含む記録層と、
　マトリクス樹脂、熱塩基発生剤および光熱変換剤を含む補助層と
　を備え、
　熱酸発生剤が、アンモニウム塩、スルホニウム塩およびヨードニウム塩からなる群より選ばれた少なくとも１種を含む光記録媒体である。 A fourth disclosure is:
a recording layer containing a matrix resin, an electron-donating dye in a colored state and a thermal acid generator;
an auxiliary layer containing a matrix resin, a thermal base generator and a photothermal conversion agent;
The optical recording medium includes a thermal acid generator containing at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
　第５の開示は、第１から第４の開示のいずれかの光記録媒体を備える身分証明書である。 A fifth disclosure is an identification card comprising the optical recording medium of any one of the first to fourth disclosures.
　第６の開示は、第１から第４の開示のいずれかの光記録媒体を備える冊子である。 A sixth disclosure is a booklet comprising the optical recording medium of any one of the first to fourth disclosures.
　第７の開示は、第１から第４の開示のいずれかの光記録媒体を備えるカードである。 A seventh disclosure is a card comprising the optical recording medium of any one of the first to fourth disclosures.
図１は、第１の実施形態に係る光記録媒体の構成の一例を示す断面図である。FIG. 1 is a cross-sectional view showing an example of the configuration of an optical recording medium according to the first embodiment. 図２は、熱酸発生剤の酸発生温度ＴＡと熱塩基発生剤の塩基発生温度ＴＢの求め方を説明するためのグラフである。FIG. 2 is a graph for explaining how to determine the acid generation temperature T A of the thermal acid generator and the base generation temperature T B of the thermal base generator. 図３は、描画前の光記録媒体における電子供与性色素、熱酸発生剤および熱塩基発生剤の状態の一例を示す断面図である。FIG. 3 is a cross-sectional view showing an example of the states of the electron-donating dye, the thermal acid generator, and the thermal base generator in the optical recording medium before drawing. 図４は、描画後の光記録媒体における電子供与性色素、熱酸発生剤および熱塩基発生剤の状態の一例を示す断面図である。FIG. 4 is a cross-sectional view showing an example of the states of the electron-donating dye, the thermal acid generator, and the thermal base generator in the optical recording medium after drawing. 図５は、高温保存時の光記録媒体における電子供与性色素、熱酸発生剤および熱塩基発生剤の状態の一例を示す断面図である。FIG. 5 is a cross-sectional view showing an example of the states of the electron-donating dye, the thermal acid generator, and the thermal base generator in the optical recording medium during high-temperature storage. 図６は、第２の実施形態に係る光記録媒体の構成の一例を示す断面図である。FIG. 6 is a cross-sectional view showing an example of the configuration of an optical recording medium according to the second embodiment. 図７は、第３の実施形態に係る光記録媒体の構成の一例を示す断面図である。FIG. 7 is a cross-sectional view showing an example of the configuration of an optical recording medium according to the third embodiment. 図８は、変形例１に係る光記録媒体の構成の一例を示す断面図である。8 is a cross-sectional view showing an example of the configuration of an optical recording medium according to Modification 1. FIG. 図９は、変形例２に係る光記録媒体の構成の一例を示す断面図である。FIG. 9 is a cross-sectional view showing an example of the configuration of an optical recording medium according to Modification 2. As shown in FIG. 図１０Ａは、適用例１の外観の一例を示す平面図である。図１０Ｂは、図１０ＡのＸＢ－ＸＢ線に沿った断面図である。10A is a plan view showing an example of the appearance of Application Example 1. FIG. FIG. 10B is a cross-sectional view along line XB-XB of FIG. 10A. 図１１は、適用例２の外観の一例を示す斜視図である。FIG. 11 is a perspective view showing an example of the appearance of Application Example 2. FIG. 図１２Ａは、適用例３の外観（表面側）の一例を表す平面図である。図１２Ｂは、適用例３の外観（裏面側）の一例を表す平面図である。12A is a plan view showing an example of the appearance (surface side) of Application Example 3. FIG. 12B is a plan view showing an example of the appearance (rear side) of Application Example 3. FIG. 図１３Ａは、適用例４の外観（表面側）の一例を表す平面図である。図１３Ｂは、適用例４の外観（裏面側）の一例を表す平面図である。13A is a plan view showing an example of the appearance (surface side) of Application Example 4. FIG. 13B is a plan view showing an example of the appearance (rear side) of Application Example 4. FIG. 図１４Ａは、適用例５の外観（前面側）の一例を表す斜視図である。図１４Ｂは、適用例５の外観（背面側）の一例を表す斜視図である。14A is a perspective view showing an example of the appearance (front side) of Application Example 5. FIG. 14B is a perspective view showing an example of the appearance (rear side) of Application Example 5. FIG. 図１５Ａは、適用例６の外観（第１の面側）の一例を表す斜視図である。図１５Ｂは、適用例６の外観（第２の面側）の一例を表す斜視図である。15A is a perspective view showing an example of the appearance (first surface side) of Application Example 6. FIG. 15B is a perspective view showing an example of the appearance (second surface side) of Application Example 6. FIG. 図１６Ａは、適用例７の外観（上面側）の一例を表す平面図である。図１６Ｂは、適用例７の外観（側面側）の一例を表す平面図である。16A is a plan view showing an example of the appearance (upper surface side) of Application Example 7. FIG. 16B is a plan view showing an example of the appearance (side surface side) of Application Example 7. FIG. 図１７は、適用例８の外観の一例を表す平面図である。FIG. 17 is a plan view showing an example of the appearance of Application Example 8. FIG. 図１８は、適用例９の外観の一例を表す斜視図である。18 is a perspective view showing an example of the appearance of Application Example 9. FIG. 図１９Ａは、適用例１０の外観の一例を表す平面図である。図１９Ｂは、図１９ＡのＸＩＸＢ－ＸＩＸＢ線に沿った断面図である。19A is a plan view showing an example of the appearance of Application Example 10. FIG. FIG. 19B is a cross-sectional view along line XIXB-XIXB of FIG. 19A. 図２０は、高温保存時間に対する光学濃度の変化を示すグラフである。FIG. 20 is a graph showing changes in optical density with respect to high temperature storage time.
　本開示の実施形態について以下の順序で説明する。なお、以下の実施形態の全図においては、同一または対応する部分には同一の符号を付す。
１　第１の実施形態（光記録媒体の例）
　１．１　光記録媒体の構成
　１．２　光記録媒体の描画方法
　１．３　高温保存時の光記録媒体の状態
　１．４　光記録媒体の製造方法
　１．５　作用効果
２　第２の実施形態（光記録媒体の例）
　２．１　光記録媒体の構成
　２．２　光記録媒体の描画方法
　２．３　作用効果
３　第３の実施形態（光記録媒体の例）
　３．１　光記録媒体の構成
　３．２　光記録媒体の描画方法
　３．３　作用効果
４　第４の実施形態（光記録媒体の例）
　４．１　光記録媒体の構成
　４．２　光記録媒体の描画方法
　４．３　作用効果
５　第５の実施形態（光記録媒体の例）
　５．１　光記録媒体の構成
　５．２　光記録媒体の描画方法
　５．３　作用効果
６　第６の実施形態（光記録媒体の例）
　６．１　光記録媒体の構成
　６．２　光記録媒体の描画方法
　６．３　作用効果
７　変形例
８　適用例
９　実施例 Embodiments of the present disclosure will be described in the following order. In addition, in all the drawings of the following embodiments, the same reference numerals are given to the same or corresponding parts.
1 First Embodiment (Example of Optical Recording Medium)
1.1 Configuration of optical recording medium 1.2 Drawing method of optical recording medium 1.3 State of optical recording medium during high temperature storage 1.4 Manufacturing method of optical recording medium 1.5 Effect 2 Second embodiment ( Example of optical recording media)
2.1 Configuration of optical recording medium 2.2 Drawing method for optical recording medium 2.3 Effect 3 Third embodiment (example of optical recording medium)
3.1 Structure of optical recording medium 3.2 Drawing method of optical recording medium 3.3 Effects 4 Fourth embodiment (example of optical recording medium)
4.1 Configuration of optical recording medium 4.2 Drawing method for optical recording medium 4.3 Effect 5 Fifth embodiment (example of optical recording medium)
5.1 Structure of Optical Recording Medium 5.2 Drawing Method of Optical Recording Medium 5.3 Effects 6 Sixth Embodiment (Example of Optical Recording Medium)
6.1 Configuration of optical recording medium 6.2 Drawing method for optical recording medium 6.3 Effect 7 Modification 8 Application 9 Example
＜１　第１の実施形態＞
［１．１　光記録媒体の構成］
　図１は、第１の実施形態に係る光記録媒体１０の構成の一例を示す断面図である。光記録媒体１０は、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、画像等を光記録媒体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。 <1 First Embodiment>
[1.1 Structure of optical recording medium]
FIG. 1 is a cross-sectional view showing an example of the configuration of an optical recording medium 10 according to the first embodiment. The optical recording medium 10 is configured to be able to change its coloring state by an external stimulus. For example, an image or the like can be drawn on the optical recording medium 10 by changing the coloring state. Here, the image includes not only images such as patterns, colors, and photographs, but also text such as characters and symbols.
　外部刺激は、レーザー光である。レーザー光は、近赤外レーザー光であることが好ましい。着色状態の変化は、可逆変化であってもよいし、不可逆変化であってもよい。すなわち、光記録媒体１０の方式は、画像等を書換可能なリライタブルであってもよいし、画像等を一度だけ書き込むことが可能なライトワンスであってもよい。偽造防止性の観点からすると、着色状態の変化は、不可逆変化であることが好ましい。 The external stimulus is laser light. 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 optical recording medium 10 may be rewritable in which an image or the like can be rewritten, or may be write-once 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.
　光記録媒体１０は、基材１１と、基材１１上に設けられた補助層１２と、補助層１２上に設けられた記録層１３とを備える。光記録媒体１０は、記録層１３上に保護層をさらに備えていてもよい。以下、基材１１、記録層１３、補助層１２について順次説明する。 The optical recording medium 10 includes a substrate 11 , an auxiliary layer 12 provided on the substrate 11 , and a recording layer 13 provided on the auxiliary layer 12 . The optical recording medium 10 may further have a protective layer on the recording layer 13 . The substrate 11, the recording layer 13, and the auxiliary layer 12 will be described in order below.
(基材)
　基材１１は、補助層１２および記録層１３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、例えば、ウェハ等の剛性を有する基板でもよいし、可撓性を有する薄層ガラス、フィルムあるいは紙等でもよい。基材１１として可撓性基板を用いることにより、フレキシブル（折り曲げ可能）な記録媒体を実現することができる。 (Base material)
The base material 11 is a support for supporting the auxiliary layer 12 and the recording layer 13 . 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 substrate 11 may be, for example, a rigid substrate such as a wafer, or a flexible thin-layer glass, film, paper, or the like. By using a flexible substrate as the base material 11, a flexible (bendable) recording medium can be realized.
　基材１１の構成材料としては、例えば、無機材料、金属材料または高分子材料等が挙げられる。無機材料は、例えば、ケイ素（Ｓｉ）、酸化ケイ素（ＳｉＯＸ）、窒化ケイ素（ＳｉＮＸ）および酸化アルミニウム（ＡｌＯＸ）等からなる群より選ばれた少なくとも１種を含む。酸化ケイ素には、ガラスおよびスピンオングラス（ＳＯＧ）等が含まれる。金属材料は、例えば、アルミニウム（Ａｌ）、ニッケル（Ｎｉ）およびステンレス等からなる群より選ばれた少なくとも１種を含む。高分子材料は、例えば、ポリカーボネート（ＰＣ）、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート（ＰＥＮ）、ポリエチルエーテルケトン（ＰＥＥＫ）およびポリ塩化ビニル（ＰＶＣ）等からなる群より選ばれた少なくとも１種を含む。 Examples of 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 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.
　なお、基材１１の少なくとも一方の主面には、反射層（図示せず）が設けられていてもよいし、基材１１自体が反射層としての機能を兼ね備えていてもよい。基材１１がこのような構成を有していることで、より鮮明な色表示が可能となる。 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.
（記録層）
　未記録状態（初期状態）の記録層１３は、消色状態にある。記録層１３は、レーザー光（外部刺激）により消色状態から発色状態に変化可能である。記録層１３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。 (Recording layer)
The recording layer 13 in an unrecorded state (initial state) is in an erased state. The recording layer 13 can change from a decolored state to a colored state by laser light (external stimulus). The recording layer 13 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.
　記録層１３の厚みは、好ましくは１μｍ以上２０μｍ以下、より好ましくは２μｍ以上１５μｍ以下である。記録層１３の厚みが１μｍ以上であると、発色濃度を向上させることができる。一方、記録層１３の厚みが２０μｍ以下であると、記録層１３の熱利用量が大きくなり過ぎることを抑制することができる。したがって、発色性が劣化することを抑制することができる。 The thickness of the recording layer 13 is preferably 1 μm or more and 20 μm or less, more preferably 2 μm or more and 15 μm or less. When the thickness of the recording layer 13 is 1 μm or more, the color density can be improved. On the other hand, when the thickness of the recording layer 13 is 20 μm or less, it is possible to prevent the heat utilization amount of the recording layer 13 from becoming too large. Therefore, it is possible to suppress the deterioration of color developability.
　記録層１３は、マトリックス樹脂、消色状態の電子供与性色素、熱酸発生剤および光熱変換剤を含む。記録層１３は、必要に応じて、上記材料の他に、例えば、増感剤および紫外線吸収材等からなる群より選ばれた少なくとも１種の添加剤を含んでいてもよい。記録層１３に含まれる材料の種類を選択することで、光記録媒体１０の方式（すなわち、リライタブル方式およびライトワンス方式）を作り分けることができる。 The recording layer 13 contains a matrix resin, a decolorized electron-donating dye, a thermal acid generator, and a photothermal conversion agent. The recording layer 13 may contain, if necessary, at least one additive selected from the group consisting of sensitizers, ultraviolet absorbers, etc., in addition to the above materials. By selecting the type of material contained in the recording layer 13, the method of the optical recording medium 10 (that is, the rewritable method and the write-once method) can be produced separately.
（マトリックス樹脂）
　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、電子供与性色素、熱酸発生剤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。マトリックス樹脂としては、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種が挙げられる。マトリックス樹脂としては、具体的には例えば、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。 (matrix resin)
The matrix resin preferably functions as a binder. The matrix resin is preferably one in which the electron-donating dye, the thermal acid generator and the photothermal conversion agent are easily dispersed homogeneously. Examples of the matrix resin include at least one selected from the group consisting of thermosetting resins and thermoplastic resins. Specific examples of the matrix resin include polyvinyl chloride, polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, ethyl cellulose, polystyrene, styrenic copolymer, phenoxy resin, polyester, aromatic polyester, polyurethane, and polycarbonate. , polyacrylic acid ester, polymethacrylic acid ester, acrylic acid-based copolymer, maleic acid-based polymer, polyvinyl alcohol, modified polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose and at least one selected from the group consisting of starch, etc. mentioned.
（電子供与性色素）
　電子供与性色素は、酸および塩基の作用により可逆的色相変化を呈することが可能な化合物である。すなわち、消色状態の電子供与性色素は、酸の作用により構造を変化し発色することが可能であり、また、発色状態の電子供与性色素は、塩基の作用により構造を変化し消色することが可能である。 (Electron donating dye)
Electron-donating dyes are compounds capable of exhibiting reversible hue changes under the action of acids and bases. That is, the decolorized electron-donating dye can change its structure and develop color by the action of an acid, and the electron-donating dye in the colored state can change its structure and decolor by the action of a base. It is possible.
　電子供与性色素は、例えば、ロイコ色素である。ロイコ色素は、当該色素内に含まれ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し、開環状態となったラクトン環が塩基と反応すると、ラクトン環が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。具体例として、下記の式（１）で表される、分子内に電子供与性を有する基を含む化合物が挙げられる。
Figure JPOXMLDOC01-appb-C000001
 Electron-donating dyes are, for example, leuco dyes. When the lactone ring contained in the dye reacts with an acid, the lactone ring in the leuco dye reacts with an acid to open the lactone ring and develop a color. do. Leuco dyes can be, for example, existing thermal paper dyes. A specific example is a compound containing an electron-donating group in the molecule represented by the following formula (1).
Figure JPOXMLDOC01-appb-C000001
　電子供与性色素は、特に制限はなく、目的に応じて適宜選択することができる。具体的な電子供与性色素としては、上記式（１）に示した化合物の他に、例えば、フルオラン系化合物、トリフェニルメタンフタリド系化合物、アザフタリド系化合物、フェノチアジン系化合物、ロイコオーラミン系化合物およびインドリノフタリド系化合物等が挙げられる。この他、例えば、２－アニリノ－３－メチル－６－ジエチルアミノフルオラン、２－アニリノ－３－メチル－６－ジ（ｎ－ブチルアミノ）フルオラン、２－アニリノ－３－メチル－６－（Ｎ－ｎ－プロピル－Ｎ－メチルアミノ）フルオラン、２－アニリノ－３－メチル－６－（Ｎ－イソプロピル－Ｎ－メチルアミノ）フルオラン、２－アニリノ－３－メチル－６－（Ｎ－イソブチル－Ｎ－メチルアミノ）フルオラン、２－アニリノ－３－メチル－６－（Ｎ－ｎ－アミル－Ｎ－メチルアミノ）フルオラン、２－アニリノ－３－メチル－６－（Ｎ－ｓｅｃ－ブチル－Ｎ－メチルアミノ）フルオラン、２－アニリノ－３－メチル－６－（Ｎ－ｎ－アミル－Ｎ－エチルアミノ）フルオラン、２－アニリノ－３－メチル－６－（Ｎ－ｉｓｏ－アミル－Ｎ－エチルアミノ）フルオラン、２－アニリノ－３－メチル－６－（Ｎ－ｎ－プロピル－Ｎ－イソプロピルアミノ）フルオラン、２－アニリノ－３－メチル－６－（Ｎ－シクロヘキシル－Ｎ－メチルアミノ）フルオラン、２－アニリノ－３－メチル－６－（Ｎ－エチル－ｐ－トルイジノ）フルオラン、２－アニリノ－３－メチル－６－（Ｎ－メチル－ｐ－トルイジノ）フルオラン、２－（ｍ－トリクロロメチルアニリノ）－３－メチル－６－ジエチルアミノフルオラン、２－（ｍ－トリフルロロメチルアニリノ）－３－メチル－６－ジエチルアミノフルオラン、２－（ｍ－トリクロロメチルアニリノ）－３－メチル－６－（Ｎ－シクロヘキシル－Ｎ－メチルアミノ）フルオラン、２－（２，４－ジメチルアニリノ）－３－メチル－６－ジエチルアミノフルオラン、２－（Ｎ－エチル－ｐ－トルイジノ）－３－メチル－６－（Ｎ－エチルアニリノ）フルオラン、２－（Ｎ－エチル－ｐ－トルイジノ）－３－メチル－６－（Ｎ－プロピル－ｐ－トルイジノ）フルオラン、２－アニリノ－６－（Ｎ－ｎ－ヘキシル－Ｎ－エチルアミノ）フルオラン、２－（ｏ－クロロアニリノ）－６－ジエチルアミノフルオラン、２－（ｏ－クロロアニリノ）－６－ジブチルアミノフルオラン、２－（ｍ－トリフロロメチルアニリノ）－６－ジエチルアミノフルオラン、２，３－ジメチル－６－ジメチルアミノフルオラン、３－メチル－６－（Ｎ－エチル－ｐ－トルイジノ）フルオラン、２－クロロ－６－ジエチルアミノフルオラン、２－ブロモ－６－ジエチルアミノフルオラン、２－クロロ－６－ジプロピルアミノフルオラン、３－クロロ－６－シクロヘキシルアミノフルオラン、３－ブロモ－６－シクロヘキシルアミノフルオラン、２－クロロ－６－（Ｎ－エチル－Ｎ－イソアミルアミノ）フルオラン、２－クロロ－３－メチル－６－ジエチルアミノフルオラン、２－アニリノ－３－クロロ－６－ジエチルアミノフルオラン、２－（ｏ－クロロアニリノ）－３－クロロ－６－シクロヘキシルアミノフルオラン、２－（ｍ－トリフロロメチルアニリノ）－３－クロロ－６－ジエチルアミノフルオラン、２－（２，３－ジクロロアニリノ）－３－クロロ－６－ジエチルアミノフルオラン、１，２－ベンゾ－６－ジエチルアミノフルオラン、３－ジエチルアミノ－６－（ｍ－トリフロロメチルアニリノ）フルオラン、３－（１－エチル－２－メチルインドール－３－イル）－３－（２－エトキシ－４－ジエチルアミノフェニル）－４－アザフタリド、３－（１－エチル－２－メチルインドール－３－イル）－３－（２－エトキシ－４－ジエチルアミノフェニル）－７－アザフタリド、３－（１－オクチル－２－メチルインドール－３－イル）－３－（２－エトキシ－４－ジエチルアミノフェニル）－４－アザフタリド、３－（１－エチル－２－メチルインドール－３－イル）－３－（２－メチル－４－ジエチルアミノフェニル）－４－アザフタリド、３－（１－エチル－２－メチルインドール－３－イル）－３－（２－メチル－４－ジエチルアミノフェニル）－７－アザフタリド、３－（１－エチル－２－メチルインドール－３－イル）－３－（４－ジエチルアミノフェニル）－４－アザフタリド、３－（１－エチル－２－メチルインドール－３－イル）－３－（４－Ｎ－ｎ－アミル－Ｎ－メチルアミノフェニル）－４－アザフタリド、３－（１－メチル－２－メチルインドール－３－イル）－３－（２－ヘキシルオキシ－４－ジエチルアミノフェニル）－４－アザフタリド、３，３－ビス（２－エトキシ－４－ジエチルアミノフェニル）－４－アザフタリド、３，３－ビス（２－エトキシ－４－ジエチルアミノフェニル）－７－アザフタリド、２－（ｐ－アセチルアニリノ）－６－（Ｎ－ｎ－アミル－Ｎ－ｎ－ブチルアミノ）フルオラン、２－ベンジルアミノ－６－（Ｎ－エチル－ｐ－トルイジノ）フルオラン、２－ベンジルアミノ－６－（Ｎ－メチル－２，４－ジメチルアニリノ）フルオラン、２－ベンジルアミノ－６－（Ｎ－エチル－２，４－ジメチルアニリノ）フルオラン、２－ベンジルアミノ－６－（Ｎ－メチル－ｐ－トルイジノ）フルオラン、２－ベンジルアミノ－６－（Ｎ－エチル－ｐ－トルイジノ）フルオラン、２－（ジ－ｐ－メチルベンジルアミノ）－６－（Ｎ－エチル－ｐ－トルイジノ）フルオラン、２－（α－フェニルエチルアミノ）－６－（Ｎ－エチル－ｐ－トルイジノ）フルオラン、２－メチルアミノ－６－（Ｎ－メチルアニリノ）フルオラン、２－メチルアミノ－６－（Ｎ－エチルアニリノ）フルオラン、２－メチルアミノ－６－（Ｎ－プロピルアニリノ）フルオラン、２－エチルアミノ－６－（Ｎ－メチル－ｐ－トルイジノ）フルオラン、２－メチルアミノ－６－（Ｎ－メチル－２，４－ジメチルアニリノ）フルオラン、２－エチルアミノ－６－（Ｎ－エチル－２，４－ジメチルアニリノ）フルオラン、２－ジメチルアミノ－６－（Ｎ－メチルアニリノ）フルオラン、２－ジメチルアミノ－６－（Ｎ－エチルアニリノ）フルオラン、２－ジエチルアミノ－６－（Ｎ－メチル－ｐ－トルイジノ）フルオラン、２－ジエチルアミノ－６－（Ｎ－エチル－ｐ－トルイジノ）フルオラン、２－ジプロピルアミノ－６－（Ｎ－メチルアニリノ）フルオラン、２－ジプロピルアミノ－６－（Ｎ－エチルアニリノ）フルオラン、２－アミノ－６－（Ｎ－メチルアニリノ）フルオラン、２－アミノ－６－（Ｎ－エチルアニリノ）フルオラン、２－アミノ－６－（Ｎ－プロピルアニリノ）フルオラン、２－アミノ－６－（Ｎ－メチル－ｐ－トルイジノ）フルオラン、２－アミノ－６－（Ｎ－エチル－ｐ－トルイジノ）フルオラン、２－アミノ－６－（Ｎ－プロピル－ｐ－トルイジノ）フルオラン、２－アミノ－６－（Ｎ－メチル－ｐ－エチルアニリノ）フルオラン、２－アミノ－６－（Ｎ－エチル－ｐ－エチルアニリノ）フルオラン、２－アミノ－６－（Ｎ－プロピル－ｐ－エチルアニリノ）フルオラン、２－アミノ－６－（Ｎ－メチル－２，４－ジメチルアニリノ）フルオラン、２－アミノ－６－（Ｎ－エチル－２，４－ジメチルアニリノ）フルオラン、２－アミノ－６－（Ｎ－プロピル－２，４－ジメチルアニリノ）フルオラン、２－アミノ－６－（Ｎ－メチル－ｐ－クロロアニリノ）フルオラン、２－アミノ－６－（Ｎ－エチル－ｐ－クロロアニリノ）フルオラン、２－アミノ－６－（Ｎ－プロピル－ｐ－クロロアニリノ）フルオラン、１，２－ベンゾ－６－（Ｎ－エチル－Ｎ－イソアミルアミノ）フルオラン、１，２－ベンゾ－６－ジブチルアミノフルオラン、１，２－ベンゾ－６－（Ｎ－メチル－Ｎ－シクロヘキシルアミノ）フルオランおよび１，２－ベンゾ－６－（Ｎ－エチル－Ｎ－トルイジノ）フルオラン等が挙げられる。記録層１３は、上記電子供与性色素のうちの１種を単独で含んでいてもよいし、２種以上を含んでいてもよい。 The electron-donating dye is not particularly limited and can be appropriately selected according to the purpose. Specific electron-donating dyes include, in addition to the compounds represented by the above formula (1), fluoran-based compounds, triphenylmethanephthalide-based compounds, azaphthalide-based compounds, phenothiazine-based compounds, and leuco auramine-based compounds. and indolinophthalide-based compounds. In addition, for example, 2-anilino-3-methyl-6-diethylaminofluorane, 2-anilino-3-methyl-6-di(n-butylamino)fluorane, 2-anilino-3-methyl-6-(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-amyl-N-ethylamino) Fluorane, 2-anilino-3-methyl-6-(Nn-propyl-N-isopropylamino)fluorane, 2-anilino-3-methyl-6-(N-cyclohexyl-N-methylamino)fluorane, 2- Anilino-3-methyl-6-(N-ethyl-p-toluidino)fluorane, 2-anilino-3-methyl-6-(N-methyl-p-toluidino)fluorane, 2-(m-trichloromethylanilino) -3-methyl-6-diethylaminofluorane, 2-(m-trifluoromethylanilino)-3-methyl-6-diethylaminofluorane, 2-(m-trichloromethylanilino)-3-methyl-6- (N-cyclohexyl-N-methylamino)fluorane, 2-(2,4-dimethylanilino)-3-methyl-6-diethylaminofluorane, 2-(N-ethyl-p-toluidino)-3-methyl- 6-(N-ethylanilino)fluorane, 2-(N-ethyl-p-toluidino)-3-methyl-6-(N-propyl-p-toluidino)fluorane, 2-anilino-6-(Nn-hexyl -N-ethylamino)fluorane, 2-(o-chloroanilino)-6-diethylaminofluorane, 2-(o-chloroanilino)-6-dibutylaminofluorane, 2-(m-trifluoromethylanilino)-6 -diethylaminofluorane, 2,3-dimethyl-6-dimethylaminofluorane, 3-methyl-6-(N-ethyl-p-toluidino)fluorane, 2-chloro-6-diethylaminofluorane, 2-bromo-6 -diethylaminofluorane, 2-chloro-6-dipropyl Aminofluorane, 3-chloro-6-cyclohexylaminofluorane, 3-bromo-6-cyclohexylaminofluorane, 2-chloro-6-(N-ethyl-N-isoamylamino)fluorane, 2-chloro-3- methyl-6-diethylaminofluorane, 2-anilino-3-chloro-6-diethylaminofluorane, 2-(o-chloroanilino)-3-chloro-6-cyclohexylaminofluorane, 2-(m-trifluoromethylani Lino)-3-chloro-6-diethylaminofluorane, 2-(2,3-dichloroanilino)-3-chloro-6-diethylaminofluorane, 1,2-benzo-6-diethylaminofluorane, 3-diethylamino -6-(m-trifluoromethylanilino)fluorane, 3-(1-ethyl-2-methylindol-3-yl)-3-(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide, 3- (1-ethyl-2-methylindol-3-yl)-3-(2-ethoxy-4-diethylaminophenyl)-7-azaphthalide, 3-(1-octyl-2-methylindol-3-yl)-3 -(2-ethoxy-4-diethylaminophenyl)-4-azaphthalide, 3-(1-ethyl-2-methylindol-3-yl)-3-(2-methyl-4-diethylaminophenyl)-4-azaphthalide, 3-(1-ethyl-2-methylindol-3-yl)-3-(2-methyl-4-diethylaminophenyl)-7-azaphthalide, 3-(1-ethyl-2-methylindol-3-yl) -3-(4-diethylaminophenyl)-4-azaphthalide, 3-(1-ethyl-2-methylindol-3-yl)-3-(4-Nn-amyl-N-methylaminophenyl)-4 -azaphthalide, 3-(1-methyl-2-methylindol-3-yl)-3-(2-hexyloxy-4-diethylaminophenyl)-4-azaphthalide, 3,3-bis(2-ethoxy-4- diethylaminophenyl)-4-azaphthalide, 3,3-bis(2-ethoxy-4-diethylaminophenyl)-7-azaphthalide, 2-(p-acetylanilino)-6-(Nn-amyl-Nn -butylamino)fluorane, 2-benzylamino-6-(N-ethyl-p-toluidino)fluorane, 2-benzylamino-6-(N-methyl-2,4-dimethylanilino)fluorane, 2-benzylamino -6-(N-E ethyl-2,4-dimethylanilino)fluorane, 2-benzylamino-6-(N-methyl-p-toluidino)fluorane, 2-benzylamino-6-(N-ethyl-p-toluidino)fluorane, 2- (Di-p-methylbenzylamino)-6-(N-ethyl-p-toluidino)fluorane, 2-(α-phenylethylamino)-6-(N-ethyl-p-toluidino)fluorane, 2-methylamino -6-(N-methylanilino)fluorane, 2-methylamino-6-(N-ethylanilino)fluorane, 2-methylamino-6-(N-propylanilino)fluorane, 2-ethylamino-6-(N- methyl-p-toluidino)fluorane, 2-methylamino-6-(N-methyl-2,4-dimethylanilino)fluorane, 2-ethylamino-6-(N-ethyl-2,4-dimethylanilino) Fluorane, 2-dimethylamino-6-(N-methylanilino)fluorane, 2-dimethylamino-6-(N-ethylanilino)fluorane, 2-diethylamino-6-(N-methyl-p-toluidino)fluorane, 2-diethylamino -6-(N-ethyl-p-toluidino)fluorane, 2-dipropylamino-6-(N-methylanilino)fluorane, 2-dipropylamino-6-(N-ethylanilino)fluorane, 2-amino-6- (N-methylanilino)fluorane, 2-amino-6-(N-ethylanilino)fluorane, 2-amino-6-(N-propylanilino)fluorane, 2-amino-6-(N-methyl-p-toluidino) Fluorane, 2-amino-6-(N-ethyl-p-toluidino)fluorane, 2-amino-6-(N-propyl-p-toluidino)fluorane, 2-amino-6-(N-methyl-p-ethylanilino ) fluoran, 2-amino-6-(N-ethyl-p-ethylanilino)fluorane, 2-amino-6-(N-propyl-p-ethylanilino)fluorane, 2-amino-6-(N-methyl-2, 4-dimethylanilino)fluorane, 2-amino-6-(N-ethyl-2,4-dimethylanilino)fluorane, 2-amino-6-(N-propyl-2,4-dimethylanilino)fluorane, 2-amino-6-(N-methyl-p-chloroanilino)fluorane, 2-amino-6-(N-ethyl-p-chloroanilino)fluorane, 2-amino-6-(N-propyl-p-chloroanilino)fluorane , 1,2-benzo-6-(N-ethyl-N-isoamylamino)fluorane, 1,2-benzo-6-dibutylaminofluorane, 1,2-benzo-6-(N-methyl-N-cyclohexylamino ) fluorane and 1,2-benzo-6-(N-ethyl-N-toluidino)fluorane. The recording layer 13 may contain one of the above electron-donating dyes alone, or may contain two or more thereof.
（熱酸発生剤）
　熱酸発生剤は、いわゆる顕色剤であり、所定の温度以上で酸を発生する。発生した酸が消色状態の電子供与性色素に作用すると、電子供与性色素の構造が変化し発色する。熱酸発生剤は、例えば、オニウム塩である。オニウム塩は、アンモニウム塩、スルホニウム塩およびヨードニウム塩からなる群より選ばれた少なくとも１種を含むことが好ましい。アンモニウム塩、スルホニウム塩およびヨードニウム塩の酸発生温度はいずれも、１５０℃以上２８０℃未満の範囲内にある。酸発生温度が１５０℃以上２８０℃未満であることが好ましい理由については後述する。アンモニウム塩、スルホニウム塩およびヨードニウム塩のアニオンは、例えば、硫黄、リン、ホウ素またはアンチモンを含む化合物を含む。 (Thermal acid generator)
A thermal acid generator is a so-called color developer that generates an acid at a predetermined temperature or higher. When the generated acid acts on the decolorized electron-donating dye, the structure of the electron-donating dye changes to develop color. Thermal acid generators are, for example, onium salts. The onium salt preferably contains at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts. The ammonium salt, sulfonium salt and iodonium salt all have an acid generation temperature within the range of 150°C or higher and lower than 280°C. The reason why the acid generation temperature is preferably 150° C. or more and less than 280° C. will be described later. Anions of ammonium, sulfonium and iodonium salts include, for example, compounds containing sulfur, phosphorus, boron or antimony.
　アンモニウム塩は、例えば、第四級アンモニウム塩である。第四級アンモニウム塩は、例えば、第四級アンモニウムカチオンと硫黄化合物アニオンとの塩を含む。第四級アンモニウムカチオンと硫黄化合物アニオンとの塩は、例えば、下記の式（２）で表される塩を含む。
Figure JPOXMLDOC01-appb-C000002
 Ammonium salts are, for example, quaternary ammonium salts. Quaternary ammonium salts include, for example, salts of quaternary ammonium cations and sulfur compound anions. Salts of quaternary ammonium cations and sulfur compound anions include, for example, salts represented by the following formula (2).
Figure JPOXMLDOC01-appb-C000002
　スルホニウム塩は、例えば、スルホニウムカチオンとアンチモン化合物アニオンとの塩、およびスルホニウムカチオンとホウ素化合物アニオンとの塩からなる群より選ばれた少なくとも１種を含む。スルホニウムカチオンとアンチモン化合物アニオンとの塩は、例えば、下記の式（３）で表される塩を含む。
Figure JPOXMLDOC01-appb-C000003
 The sulfonium salt includes, for example, at least one selected from the group consisting of salts of sulfonium cations and antimony compound anions and salts of sulfonium cations and boron compound anions. Salts of sulfonium cations and antimony compound anions include, for example, salts represented by the following formula (3).
Figure JPOXMLDOC01-appb-C000003
　スルホニウムカチオンとホウ素化合物アニオンとの塩は、例えば、下記の式（４）で表される塩および式（５）で表される塩からなる群より選ばれた少なくとも１種の塩を含む。
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
 The salt of the sulfonium cation and the boron compound anion includes, for example, at least one salt selected from the group consisting of salts represented by the following formula (4) and formula (5).
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000005
　ヨードニウム塩は、例えば、ヨードニウムカチオンとホウ素化合物との塩である。ヨードニウムカチオンとホウ素化合物との塩は、例えば、下記の式（６）で表される塩を含む。
Figure JPOXMLDOC01-appb-C000006
 Iodonium salts are, for example, salts of iodonium cations and boron compounds. Salts of iodonium cations and boron compounds include, for example, salts represented by the following formula (6).
Figure JPOXMLDOC01-appb-C000006
（熱酸発生剤の酸発生温度ＴＡ）
　熱酸発生剤の酸発生温度ＴＡの下限値が、好ましくは１５０℃以上である。熱酸発生剤の酸発生温度ＴＡが１５０℃以上であると、光記録媒体１０が高温の環境（例えば８０℃に達する炎天下の車中）に放置された場合においても光記録媒体１０の記録部（着色部）および未記録部（未着色部）の色相の変化を抑制することができ、元の記録状態を維持することができる。また、光記録媒体１０を備えたカードまたは冊子などを製造する工程で熱プレス（例えば１１０℃でカバーフィルムなどを積層する工程）を採用する場合には熱酸発生剤の酸発生温度ＴＡは更に高い１８０℃を超える温度が望ましい。 (Acid Generation Temperature T A of Thermal Acid Generator)
The lower limit of the acid generating temperature TA of the thermal acid generator is preferably 150°C or higher. When the acid generating temperature TA of the thermal acid generator is 150° C. or higher, recording on the optical recording medium 10 is possible even when the optical recording medium 10 is left in a high-temperature environment (for example, in a car under the hot sun reaching 80° C.). It is possible to suppress a change in hue of a portion (colored portion) and an unrecorded portion (uncolored portion), and maintain the original recording state. Further, when a heat press (for example, a process of laminating a cover film or the like at 110° C.) is employed in the process of manufacturing a card or booklet equipped with the optical recording medium 10, the acid generation temperature TA of the thermal acid generator is Even higher temperatures above 180°C are desirable.
　熱酸発生剤の酸発生温度ＴＡの上限値が、好ましくは、記録層１３中に含まれるマトリクス樹脂の熱分解温度未満、例えば２８０℃未満である。熱酸発生剤の酸発生温度ＴＡが、記録層１３中に含まれるマトリクス樹脂の熱分解温度未満であると、記録層１３に含まれるマトリクス樹脂を熱分解させずに、記録層１３に呈色反応を誘起させることができる。マトリクス樹脂の熱分解温度は、熱重量分析（Thermogravimetric analysis:ＴＧＡ）により測定される。 The upper limit of the acid generation temperature TA of the thermal acid generator is preferably lower than the thermal decomposition temperature of the matrix resin contained in the recording layer 13, for example, lower than 280.degree. When the acid generation temperature TA of the thermal acid generator is lower than the thermal decomposition temperature of the matrix resin contained in the recording layer 13, the matrix resin contained in the recording layer 13 is not thermally decomposed, and is exposed to the recording layer 13. A color reaction can be induced. The thermal decomposition temperature of the matrix resin is measured by thermogravimetric analysis (TGA).
（熱酸発生剤の酸発生温度ＴＡの求め方）
　熱酸発生剤の酸発生温度ＴＡは次のようにして求められる。まず、光記録媒体１０から記録層１３を取り出し、ＰＥＴ基板上に貼り合わせることにより、サンプル１を得る。次に、サンプル１を株式会社東洋精機製作所製の熱傾斜試験機（ヒートシールテスターＨＧ－３）にセットし、サンプル１の未記録部に規定温度に保温された接触子を０．１ＭＰａの圧力で５秒間押し当てて発色させ、その時の光学濃度（Optical Density、以下「ＯＤ」という。）を測定する。接触子の温度を４０℃から２８０℃まで１０℃刻みで変化させ、各温度で測定位置を変えながら、上記ＯＤの測定を行う。これにより、接触子の温度とＯＤとの関係を示すグラフが得られる（図２参照）。なお、１つのサンプル１で測定位置が不足する場合には、１枚または２枚以上のサンプル１を別途作製し、上記と同様の測定を行う。また、上記接触子の温度は、熱傾斜試験機に表示される接触子の温度である。ＯＤの測定には、ビデオジェット・エックスライト株式会社の分光測色計Ｘ－Ｒｉｔｅ　ｅＸａｃｔを用いる。 (Method for determining the acid generation temperature TA of the thermal acid generator)
The acid generation temperature TA of the thermal acid generator is determined as follows. First, a sample 1 is obtained by removing the recording layer 13 from the optical recording medium 10 and bonding it onto a PET substrate. Next, sample 1 is set in a thermal gradient tester (heat seal tester HG-3) manufactured by Toyo Seiki Seisakusho Co., Ltd., and a contact kept at a specified temperature is applied to the unrecorded part of sample 1 at a pressure of 0.1 MPa. for 5 seconds to develop a color, and the optical density (hereinafter referred to as "OD") at that time is measured. The temperature of the contact is changed from 40° C. to 280° C. in increments of 10° C., and the above OD is measured while changing the measurement position at each temperature. As a result, a graph showing the relationship between contactor temperature and OD is obtained (see FIG. 2). If one sample 1 does not have enough measurement positions, one or two or more samples 1 are prepared separately and the same measurement as above is performed. The temperature of the contactor is the temperature of the contactor displayed on the thermal gradient tester. For the measurement of OD, a spectrophotometer X-Rite eXact manufactured by Videojet X-Rite Co., Ltd. is used.
　次に、図２で得られた接触子の温度とＯＤとの関係を示すグラフから、４０℃以上２８０℃以下の範囲における最大ＯＤｍａｘ（ｆＡ（Ｔ）の最大値）と最小ＯＤｍｉｎ（ｆＡ（Ｔ）の最小値）を求め、これらの最大ＯＤｍａｘと最小ＯＤｍｉｎの中点ＯＤｍｉｄ（＝（［最大ＯＤｍｉｎ］－［最小ＯＤｍｉｎ］）／２）を求める。次に、グラフの内挿により中点ＯＤｍｉｄが得られる温度を求め、この温度を熱酸発生剤の酸発生温度ＴＡとする。一般に曲線ｆＡ（Ｔ）は式（Ａ）で近似できる。ただしＲはグラフの立ち上がりの緩急を表すパラメータである。
Figure JPOXMLDOC01-appb-M000007
 Next, from the graph showing the relationship between contact temperature and OD obtained in FIG. 2, maximum OD max (maximum value of f A (T)) and minimum OD min ( The minimum value of f A (T)) is obtained, and the midpoint OD mid (=([maximum OD min ]−[minimum OD min ])/2) between the maximum OD max and the minimum OD min is obtained. Next, the temperature at which the midpoint OD mid is obtained is obtained by interpolation of the graph, and this temperature is defined as the acid generation temperature TA of the thermal acid generator. In general, the curve f A (T) can be approximated by Equation (A). However, R is a parameter representing the gradual rise of the graph.
Figure JPOXMLDOC01-appb-M000007
（光熱変換剤）
　光熱変換剤は、例えば、所定の波長域の光を吸収して発熱するものである。所定の波長域は、近赤外線領域であることが好ましい。光熱変換剤としては、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。 (Photothermal conversion agent)
The photothermal conversion agent, for example, absorbs light in a predetermined wavelength range and generates heat. The predetermined wavelength range is preferably in the near-infrared region. As the photothermal conversion agent, it is preferable to use 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. Specific examples thereof include at least one selected from the group consisting of compounds having a phthalocyanine skeleton (phthalocyanine dyes), compounds having a squarylium skeleton (squarylium dyes), and inorganic compounds.
　無機化合物としては、例えば、ジチオ錯体等の金属錯体、ジイモニウム塩、アミニウム塩、グラファイト、カーボンブラック、金属粉末粒子、四三酸化コバルト、酸化鉄、酸化クロム、酸化銅、チタンブラック、ＩＴＯ（Indium Tin Oxide）等の金属酸化物、窒化ニオブ等の金属窒化物、炭化タンタル等の金属炭化物、金属硫化物および各種磁性粉末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。この他、優れた耐光性および耐熱性を有するシアニン骨格を有する化合物（シアニン系染料）を用いてもよい。なお、ここで、優れた耐光性とは、使用環境下で、例えば蛍光灯の光等の照射によって、分解しないことである。優れた耐熱性とは、例えば、高分子材料と共に成膜し、例えば１５０℃で３０分間保管した際に、吸収スペクトルの最大吸収ピーク値に２０％以上の変化が生じないことである。このようなシアニン骨格を有する化合物としては、例えば、分子内に、ＳｂＦ６、ＰＦ６、ＢＦ４、ＣｌＯ４、ＣＦ３ＳＯ３および（ＣＦ３ＳＯ３）２Ｎのうちのいずれかのカウンターイオンと、５員環または６員環を含むメチン鎖との少なくとも一方を有するものが挙げられる。なお、第１の実施形態において光記録媒体１０に用いられるシアニン骨格を有する化合物は、上記カウンターイオンのいずれかおよびメチン鎖内に５員環および６員環等の環状構造の両方を備えていることが好ましいが、少なくとも一方を備えていれば、十分な耐光性および耐熱性が担保される。 Examples of 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. In addition, a compound having a cyanine skeleton (cyanine dye) having excellent light resistance and heat resistance may be used. Here, the term "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. In addition, the compound having a cyanine skeleton used in the optical recording medium 10 in the first embodiment has both the counter ion and a cyclic structure such as a 5-membered ring or a 6-membered ring in the methine chain. However, if at least one of them is provided, sufficient light resistance and heat resistance are ensured.
（補助層）
　補助層１２は、高温保存時に塩基を発生し記録層１３に拡散することが可能である。補助層１２は、記録層１３に隣接して設けられていている。補助層１２が記録層１３に隣接して設けられていていることで、光記録媒体１０が高温の環境に保存された際に、熱酸発生剤が酸を発生する共に、熱塩基発生剤が塩基を発生する。これにより、発生した酸と塩基を中和反応させることができるので、電子供与性色素に作用する酸の量を低減することができる。よって、高温保存時における地肌の色相変化を抑制することができる。第１の実施形態では、地肌とは、記録層１３の消色状態の部分（未記録部）をいう。補助層１２の厚みは、好ましくは１μｍ以上２０μｍ以下、より好ましくは２μｍ以上１５μｍ以下である。 (auxiliary layer)
The auxiliary layer 12 is capable of generating a base and diffusing it into the recording layer 13 during high-temperature storage. The auxiliary layer 12 is provided adjacent to the recording layer 13 . Since the auxiliary layer 12 is provided adjacent to the recording layer 13, when the optical recording medium 10 is stored in a high-temperature environment, the thermal acid generator generates acid and the thermal base generator generates acid. Generates a base. As a result, the generated acid and base can undergo a neutralization reaction, so that the amount of acid acting on the electron-donating dye can be reduced. Therefore, it is possible to suppress the hue change of the background during high-temperature storage. In the first embodiment, the background refers to an erased portion (unrecorded portion) of the recording layer 13 . The thickness of the auxiliary layer 12 is preferably 1 μm or more and 20 μm or less, more preferably 2 μm or more and 15 μm or less.
　補助層１２は、マトリクス樹脂および熱塩基発生剤を含む。記録層１３は、必要に応じて、上記材料の他に、例えば、紫外線吸収材等の添加剤を含んでいてもよい。 The auxiliary layer 12 contains a matrix resin and a thermal base generator. If necessary, the recording layer 13 may contain additives such as ultraviolet absorbers in addition to the above materials.
（マトリックス樹脂）
　マトリクス樹脂は、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、熱塩基発生剤が均質に分散しやすいものが好ましい。マトリックス樹脂としては、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種が挙げられる。マトリックス樹脂の具体例としては、記録層１３のマトリックス樹脂と同様の材料を挙げることができる。 (matrix resin)
The matrix resin preferably functions as a binder. The matrix resin is preferably one in which the thermal base generator can easily be uniformly dispersed. Examples of the matrix resin include at least one selected from the group consisting of thermosetting resins and thermoplastic resins. Specific examples of the matrix resin include materials similar to those of the matrix resin of the recording layer 13 .
（熱塩基発生剤）
　熱塩基発生剤は、所定の温度以上で塩基を発生する。発生した塩基は、記録層１３に拡散される。熱塩基発生剤は、例えば、ジアザビシクロウンデセン（ＤＢＵ（登録商標））塩およびＤＢＵ誘導体塩からなる群より選ばれた少なくとも１種の塩を含む。ジアザビシクロウンデセン塩およびジアザビシクロウンデセン誘導体塩のアニオンは、例えば、フェノール、オクチル酸またはホウ酸である。 (Thermal base generator)
A thermal base generator generates a base at a predetermined temperature or higher. The generated base diffuses into the recording layer 13 . The thermal base generator includes, for example, at least one salt selected from the group consisting of diazabicycloundecene (DBU (registered trademark)) salts and DBU derivative salts. Anions of diazabicycloundecene salts and diazabicycloundecene derivative salts are, for example, phenol, octylic acid or boric acid.
　ＤＢＵ塩は、例えば、下記の式（７）で表される塩を含む。
Figure JPOXMLDOC01-appb-C000008
 　式（７）中のＸは、下記の式（８）で表される化合物である。
Figure JPOXMLDOC01-appb-C000009
 DBU salts include, for example, salts represented by the following formula (7).
Figure JPOXMLDOC01-appb-C000008
 X in Formula (7) is a compound represented by Formula (8) below.
Figure JPOXMLDOC01-appb-C000009
　ＤＢＵ誘導体塩は、例えば、下記の式（９）で表される塩を含む。
Figure JPOXMLDOC01-appb-C000010
 DBU derivative salts include, for example, salts represented by the following formula (9).
Figure JPOXMLDOC01-appb-C000010
　熱塩基発生剤の塩基発生温度は、熱酸発生剤の酸発生温度と略一致することが好ましい。熱塩基発生剤の塩基発生温度が熱酸発生剤の酸発生温度と略一致していると、光記録媒体１０が高温保存された際に、熱酸発生剤が酸を発生すると略同時に熱塩基発生剤が塩基を発生し拡散する。したがって、熱酸発生剤が発生する酸の量と、熱塩基発生剤が発生する塩基の量とを拮抗させることができる。よって、発色と消色とを拮抗させ、発色および消色のいずれか一方が進行することを抑制することができる。 The base generation temperature of the thermal base generator is preferably approximately the same as the acid generation temperature of the thermal acid generator. If the base generation temperature of the thermal base generator substantially coincides with the acid generation temperature of the thermal acid generator, when the optical recording medium 10 is stored at a high temperature, the thermal base is generated at substantially the same time as the thermal acid generator generates acid. A generator generates and diffuses a base. Therefore, the amount of acid generated by the thermal acid generator and the amount of base generated by the thermal base generator can be balanced. Therefore, it is possible to counteract the color development and the color decoloration, and to suppress the progress of either color development or color decoloration.
（熱塩基発生剤の塩基発生温度ＴＢ）
　熱塩基発生剤の塩基発生温度ＴＢの下限値が、好ましくは１５０℃以上である。熱塩基発生剤の塩基発生温度ＴＢが１５０℃以上であると、記録後の光記録媒体１０が高温の環境（例えば８０℃に達する炎天下の車中）に放置された場合においても光記録媒体１０の記録部（着色部）の色相の変化を抑制することができ、元の記録状態を維持することができる。 (Base generation temperature T B of thermal base generator)
The lower limit of the base generation temperature T B of the thermal base generator is preferably 150° C. or higher. When the base generation temperature T B of the thermal base generator is 150° C. or higher, even when the optical recording medium 10 after recording is left in a high-temperature environment (for example, in a car under the hot sun reaching 80° C.), The change in hue of the 10 printed portions (colored portions) can be suppressed, and the original printed state can be maintained.
　熱塩基発生剤の塩基発生温度ＴＢの上限値が、好ましくは、補助層１２に含まれるマトリクス樹脂の熱分解温度未満、例えば２８０℃未満である。熱塩基発生剤の塩基発生温度ＴＢが、補助層１２に含まれるマトリクス樹脂の熱分解温度未満であると、熱塩基発生剤が塩基を発生する前に、補助層１２が消失することを抑制することができる。 The upper limit of the base generation temperature T B of the thermal base generator is preferably less than the thermal decomposition temperature of the matrix resin contained in the auxiliary layer 12, for example less than 280°C. When the base generation temperature T B of the thermal base generator is lower than the thermal decomposition temperature of the matrix resin contained in the auxiliary layer 12, the disappearance of the auxiliary layer 12 is suppressed before the thermal base generator generates a base. can do.
（熱塩基発生剤の塩基発生温度ＴＢの求め方）
　熱塩基発生剤の塩基発生温度ＴＢは次のようにして求められる。まず、光記録媒体１０から補助層１２および記録層１３をそれぞれ取り出す。次に、取り出された記録層１３をＰＥＴ基板上に貼り合わせる。次に、ＰＥＴ基板を１５０℃のオーブンで３０分間加熱して充分に記録層１３を発色させた後、取り出された補助層１２を記録層１３上に貼り合わせる。これにより、サンプル２が得られる。 (Method for obtaining the base generation temperature T B of the thermal base generator)
The base generation temperature T B of the thermal base generator is obtained as follows. First, the auxiliary layer 12 and the recording layer 13 are taken out from the optical recording medium 10, respectively. Next, the taken-out recording layer 13 is pasted on the PET substrate. Next, the PET substrate is heated in an oven at 150° C. for 30 minutes so that the recording layer 13 is sufficiently colored. Sample 2 is thus obtained.
　次に、サンプル２を用いること以外は上記の熱酸発生剤の酸発生温度ＴＡの求め方と同様にして、接触子の温度ＴとＯＤの関係を示すグラフｆＢ（Ｔ）を作成する。次に４０℃以上２８０℃以下の範囲における最大ＯＤｍａｘ（ｆＢ（Ｔ）の最大値）と最小ＯＤｍｉｎ（ｆＢ（Ｔ）の最小値）を求めた後、これらの最大ＯＤｍａｘと最小ＯＤの中点ＯＤｍｉｄ（＝（［最大ＯＤｍａｘ］－［最小ＯＤｍｉｎ］）／２）を求める。さらに、グラフの内挿により中点ＯＤｍｉｄが得られる温度を求め、この温度を塩基発生温度の塩基発生温度ＴＢとする。一般に曲線ｆＢ（Ｔ）は式（Ｂ）で近似できる。ただしＲはグラフの立ち上がりの緩急を表すパラメータである。
Figure JPOXMLDOC01-appb-M000011
 Next, a graph f B (T) showing the relationship between contactor temperature T and OD is created in the same manner as the method for determining the acid generation temperature T A of the thermal acid generator except that sample 2 is used. . Next, after obtaining the maximum OD max (maximum value of f B (T)) and minimum OD min (minimum value of f B (T)) in the range of 40 ° C to 280 ° C, these maximum OD max and minimum OD midpoint OD mid (=([maximum OD max ]−[minimum OD min ])/2) is obtained. Further, the temperature at which the midpoint OD mid is obtained is obtained by interpolation of the graph, and this temperature is defined as the base generation temperature T B of the base generation temperature. In general, the curve f B (T) can be approximated by Equation (B). However, R is a parameter representing the gradual rise of the graph.
Figure JPOXMLDOC01-appb-M000011
（熱酸発生剤の酸発生温度ＴＡと熱塩基発生剤の塩基発生温度ＴＢの関係）
　熱酸発生剤の酸発生温度ＴＡおよび熱塩基発生剤の塩基発生温度ＴＢが、以下の関係式（Ａ）を満たすことが好ましい。
　｜ＴＡ－ＴＢ｜≦２０［Ｋ］　・・・（Ａ）
　熱酸発生剤の酸発生温度ＴＡおよび熱塩基発生剤の塩基発生温度ＴＢが上記の関係式（Ａ）を満たすことで、光記録媒体１０が高温の環境に保存された際に、熱酸発生剤が発生する酸の量と、熱塩基発生剤が発生する塩基の量とを拮抗させることができる。したがって、発色と消色とを拮抗させ、発色および消色のいずれか一方が進行することを抑制することができる。 (Relationship between acid generation temperature T A of thermal acid generator and base generation temperature T B of thermal base generator)
The acid generation temperature T A of the thermal acid generator and the base generation temperature T B of the thermal base generator preferably satisfy the following relational expression (A).
|T A −T B |≦20 [K] (A)
Since the acid generation temperature T A of the thermal acid generator and the base generation temperature T B of the thermal base generator satisfy the above relational expression (A), when the optical recording medium 10 is stored in a high-temperature environment, heat It is possible to balance the amount of acid generated by the acid generator with the amount of base generated by the thermal base generator. Therefore, it is possible to antagonize coloring and decoloring, and to suppress progress of either coloring or decoloring.
　熱酸発生剤の酸発生温度ＴＡおよび熱塩基発生剤の塩基発生温度ＴＢの求め方は、前述したとおりである。 The methods for obtaining the acid generation temperature T A of the thermal acid generator and the base generation temperature T B of the thermal base generator are as described above.
［１．２　光記録媒体の描画方法］
　以下、図３および図４を参照して、第１の実施形態に係る光記録媒体１０の描画方法の一例について説明する。 [1.2 Drawing method for optical recording medium]
An example of a drawing method for the optical recording medium 10 according to the first embodiment will be described below with reference to FIGS. 3 and 4. FIG.
　図３に示すように、描画前（すなわち初期状態）の光記録媒体１０では、記録層１３に含まれる電子供与性色素、熱酸発生剤はそれぞれ、消色状態、中性状態にある。また、補助層１２に含まれる熱塩基発生剤は、中性状態にある。 As shown in FIG. 3, in the optical recording medium 10 before drawing (that is, in the initial state), the electron-donating dye and the thermal acid generator contained in the recording layer 13 are in a decolored state and a neutral state, respectively. Moreover, the thermal base generator contained in the auxiliary layer 12 is in a neutral state.
　図４に示すように、近赤外レーザー光等のレーザー光Ｌが記録層１３の所定の位置に照射されると、記録層１３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Ｌを吸収して発熱し、この発熱により熱酸発生剤が活性化し酸を発生する。発生した酸が記録層１３内を拡散し消色状態の電子供与性色素に作用すると、電子供与性色素は色相変化を呈し、発色状態となる。これにより、記録層１３に所望の画像が描画される。 As shown in FIG. 4, when a predetermined position of the recording layer 13 is irradiated with a laser beam L such as a near-infrared laser beam, the photothermal conversion agent contained in the laser beam-irradiated portion of the recording layer 13 absorbs the laser beam L. Absorption generates heat, which activates the thermal acid generator to generate acid. When the generated acid diffuses in the recording layer 13 and acts on the decolorized electron-donating dye, the electron-donating dye undergoes a hue change and becomes colored. A desired image is thus drawn on the recording layer 13 .
　補助層１２は光熱変換剤を含んでいないため、上記レーザー光の照射によっても、補助層１２に含まれる熱塩基発生剤には、当該熱塩基発生剤が活性化するのに十分な熱は与えられない。したがって、熱塩基発生剤は中性状態を維持し、塩基を発生しない。よって、描画時には、補助層１２から記録層１３に塩基が拡散されることはない。 Since the auxiliary layer 12 does not contain a photothermal conversion agent, the thermal base generator contained in the auxiliary layer 12 does not receive sufficient heat to activate the thermal base generator even when irradiated with the laser beam. can't Therefore, the thermal base generator remains neutral and does not generate base. Therefore, during writing, the base will not diffuse from the auxiliary layer 12 to the recording layer 13 .
［１．３　高温保存時の光記録媒体の状態］
　以下、図５を参照して、高温保存時の光記録媒体の状態について説明する。 [1.3 State of Optical Recording Medium During High-Temperature Storage]
The state of the optical recording medium during high-temperature storage will be described below with reference to FIG.
　光記録媒体１０が高温保存されると、熱酸生成剤および熱塩基発生剤の活性化温度（酸発生温度および塩基発生温度）未満の温度であっても、長時間の加温によって、記録層１３に含まれる熱酸発生剤が酸を発生すると共に、補助層１２に含まれる熱塩基発生剤が塩基を発生する。発生した酸および塩基が拡散し反応することで、中和される。これにより、発生した酸が電子供与性色素に作用することを抑制することができるので、高温保存時の地肌発色が抑制される。なお、記録層の描画部（記録部）の発色はそのまま維持される。 When the optical recording medium 10 is stored at a high temperature, even if the temperature is lower than the activation temperature (acid generation temperature and base generation temperature) of the thermal acid generator and the thermal base generator, the recording layer may be damaged by long-term heating. The thermal acid generator contained in 13 generates an acid, and the thermal base generator contained in the auxiliary layer 12 generates a base. The generated acid and base diffuse and react to neutralize. As a result, it is possible to suppress the action of the generated acid on the electron-donating dye, thereby suppressing the coloring of the background during high-temperature storage. The coloring of the drawing portion (recording portion) of the recording layer is maintained as it is.
　図５では、描画後の光記録媒体１０の状態を示しているが、地肌発色の抑制効果は、描画後の光記録媒体１０に限定されるものではなく、描画前（初期状態）の光記録媒体１０でも同様に得られる。 FIG. 5 shows the state of the optical recording medium 10 after drawing, but the effect of suppressing background coloring is not limited to the optical recording medium 10 after drawing. A medium 10 is similarly obtained.
［１．４　光記録媒体の製造方法］
　以下、第１の実施形態に係る光記録媒体１０の製造方法の一例について説明する。ここでは、塗布法を用いて光記録媒体１０を製造する例について説明する。 [1.4 Manufacturing method of optical recording medium]
An example of a method for manufacturing the optical recording medium 10 according to the first embodiment will be described below. Here, an example of manufacturing the optical recording medium 10 using the coating method will be described.
　まず、溶媒（例えば、純水）に、マトリックスポリマーを溶解させる。次に、この溶液に、熱塩基発生剤を添加し、分散させる。これにより、補助層形成用塗料が得られる。続いて、この補助層形成用塗料を、基材１１上に塗布し乾燥させることにより、補助層１２を形成する。 First, dissolve the matrix polymer in a solvent (eg, pure water). Next, a thermal base generator is added to this solution and dispersed. As a result, an auxiliary layer-forming coating material is obtained. Subsequently, the auxiliary layer 12 is formed by coating the auxiliary layer forming coating material on the substrate 11 and drying it.
　次に、溶媒（例えば、メチルエチルケトン）に、マトリックスポリマーを溶解させる。次に、この溶液に、消色状態の電子供与性色素、熱酸発生剤および光熱変換材料を添加し、分散させる。これにより、記録層形成用塗料が得られる。続いて、この記録層形成用塗料を、補助層１２上に塗布し乾燥させることにより、記録層１３を形成する。以上により、図１に示される光記録媒体１０が得られる。 Next, dissolve the matrix polymer in a solvent (eg, methyl ethyl ketone). Next, the decolorized electron-donating dye, the thermal acid generator and the photothermal conversion material are added to the solution and dispersed. Thereby, a coating material for forming a recording layer is obtained. Subsequently, the recording layer 13 is formed by coating the recording layer forming coating material on the auxiliary layer 12 and drying it. As described above, the optical recording medium 10 shown in FIG. 1 is obtained.
［１．５　作用効果］
　第１の実施形態に係る光記録媒体１０は、マトリクス樹脂、消色状態の電子供与性色素、熱酸発生剤および光熱変換剤を含む記録層を備える。電子供与性色素は、酸および塩基の作用により可逆的色相変化を呈することが可能である。これにより、図４に示すように、近赤外レーザー光等のレーザー光Ｌが記録層１３に照射されると、記録層１３の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し、この発熱により熱酸発生剤が酸を発生する。発生した酸が電子供与性色素に作用すると、電子供与性色素は可逆的色相変化を呈し、発色状態となる。したがって、光記録媒体１０に所望の画像を描画することができる。 [1.5 Effects]
The optical recording medium 10 according to the first embodiment includes a recording layer containing a matrix resin, a decolorized electron-donating dye, a thermal acid generator, and a photothermal conversion agent. Electron-donating dyes are capable of exhibiting reversible hue changes under the action of acids and bases. As a result, as shown in FIG. 4, when the recording layer 13 is irradiated with a laser beam L such as a near-infrared laser beam, the photothermal conversion agent contained in the irradiated portion of the recording layer 13 absorbs the laser beam and generates heat. This heat generation causes the thermal acid generator to generate acid. When the generated acid acts on the electron-donating dye, the electron-donating dye undergoes a reversible hue change and becomes colored. Therefore, a desired image can be drawn on the optical recording medium 10 .
　第１の実施形態に係る光記録媒体１０では、熱酸発生剤を含む記録層１３に隣接して、熱塩基発生剤を含む補助層１２が備えられている。これにより、光記録媒体１０が高温に保存された際に、熱酸発生剤が酸を発生すると共に、熱塩基発生剤が塩基を発生する。これにより、発生した酸と塩基を中和反応させることができるので、電子供与性色素に作用する酸の量を低減することができる。よって、高温保存時における地肌の色相変化を抑制することができる。 In the optical recording medium 10 according to the first embodiment, the auxiliary layer 12 containing the thermal base generator is provided adjacent to the recording layer 13 containing the thermal acid generator. As a result, when the optical recording medium 10 is stored at a high temperature, the thermal acid generator generates an acid and the thermal base generator generates a base. As a result, the generated acid and base can undergo a neutralization reaction, so that the amount of acid acting on the electron-donating dye can be reduced. Therefore, it is possible to suppress the hue change of the background during high-temperature storage.
　従来の光記録媒体では、顕色剤として常温では結晶状の酸性物質が一般的に用いられている。常温では結晶状の酸性物質にレーザー光が照射され溶融されると、溶融された酸性物質が、電子供与性色素に作用し電子供与性色素が発色する。しかしながら、このような結晶状の酸性物質（顕色剤）としては長鎖型アルキル基を持つ物質を使用されることが多く、その原料は一般的に高価である。このため、従来の光記録媒体には、製造コストが著しく上昇するという問題があった。
　これに対して、第１の実施形態に係る光記録媒体１０では、顕色剤として、結晶状酸性物質に代えて、より安価な熱酸発生剤（活性化温度以上の温度で酸を発生させる物質）が用いられている。このため、第１の実施形態に係る光記録媒体１０では、製造コストを低減することができる。 In conventional optical recording media, a crystalline acidic substance is generally used as a color developer at room temperature. When an acidic substance that is crystalline at room temperature is irradiated with a laser beam and melted, the molten acidic substance acts on the electron-donating dye, causing the electron-donating dye to develop a color. However, substances having long-chain alkyl groups are often used as such crystalline acidic substances (color developers), and the raw materials thereof are generally expensive. For this reason, the conventional optical recording medium has a problem that the manufacturing cost rises significantly.
On the other hand, in the optical recording medium 10 according to the first embodiment, a less expensive thermal acid generator (which generates acid at a temperature equal to or higher than the activation temperature) is used as the color developer instead of the crystalline acidic substance. substances) are used. Therefore, the manufacturing cost of the optical recording medium 10 according to the first embodiment can be reduced.
＜２　第２の実施形態＞
　上記第１の実施形態では、光記録媒体が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、光記録媒体が互いに発色色相の異なる呈色性化合物をそれぞれ含む３つの記録層を備える例について説明する。 <2 Second Embodiment>
In the first embodiment, the optical recording medium has one recording layer. In the second embodiment, the optical recording medium contains color formers having different coloring hues. An example with three recording layers will be described.
［２．１　光記録媒体の構成］
　図６は、第２の実施形態に係る光記録媒体１０Ａの構成の一例を示す断面図である。光記録媒体１０Ａは、基材１１と、３つの記録層１３Ａ、１３Ｂ、１３Ｃと、３つの補助層１２Ａ、１２Ｂ、１２Ｃとを備える。記録層１３Ａ、１３Ｂ、１３Ｃを特に区別せず総称する場合には、記録層１３という。また、補助層１２Ａ、１２Ｂ、１２Ｃを特に区別せず総称する場合には、補助層１２という。なお、第２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。 [2.1 Structure of optical recording medium]
FIG. 6 is a cross-sectional view showing an example of the configuration of an optical recording medium 10A according to the second embodiment. The optical recording medium 10A comprises a substrate 11, three recording layers 13A, 13B, 13C and three auxiliary layers 12A, 12B, 12C. The recording layers 13A, 13B, and 13C are collectively referred to as the recording layer 13 without any particular distinction. Further, the auxiliary layers 12A, 12B, and 12C are collectively referred to as the auxiliary layer 12 without any particular distinction. In addition, in 2nd Embodiment, the same code|symbol is attached|subjected to the same location as 1st Embodiment, and description is abbreviate|omitted.
　３層の記録層１３と３層の補助層１２とにより積層体が構成されている。記録層１３と補助層１２とは、基材１１上に交互に設けられている。記録層１３と補助層１２とは隣接している。積層体の最下層は、補助層１２および記録層１３のいずれであってもよい。積層体の最下層が、基材１１側となる。光記録媒体１０Ａは、積層体上に保護層をさらに備えていてもよい。 A laminate is composed of three recording layers 13 and three auxiliary layers 12 . The recording layers 13 and the auxiliary layers 12 are alternately provided on the substrate 11 . The recording layer 13 and the auxiliary layer 12 are adjacent to each other. The bottom layer of the laminate may be either the auxiliary layer 12 or the recording layer 13 . The bottom layer of the laminate is on the substrate 11 side. The optical recording medium 10A may further include a protective layer on the laminate.
（記録層）
　記録層１３Ａ、１３Ｂ、１３Ｃは、レーザー光（外部刺激）により着色状態を変化させることが可能である。記録層１３Ａ、１３Ｂ、１３Ｃ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１３Ａ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１３Ｂ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１３Ｃ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。 (Recording layer)
The recording layers 13A, 13B, and 13C can change the coloring state by laser light (external stimulus). The recording layers 13A, 13B, and 13C can exhibit hues different from each other in the colored state. Specifically, the recording layer 13A can exhibit a magenta color in a colored state. The recording layer 13B can exhibit a cyan color in a colored state. The recording layer 13C 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.
　記録層１３Ａは、第１のマトリクス樹脂、消色状態の第１の電子供与性色素、第１の熱酸発生剤および第１の光熱変換剤を含む。記録層１３Ｂは、第２のマトリクス樹脂、消色状態の第２の電子供与性色素、第２の熱酸発生剤および第２の光熱変換剤を含む。記録層１３Ｂは、第３のマトリクス樹脂、消色状態の第３の電子供与性色素、第３の熱酸発生剤および第３の光熱変換剤を含む。記録層１３Ａ、１３Ｂ、１３Ｃは、上記記録層１３と同様に、上記材料の他に、例えば、増感剤および紫外線吸収材等からなる群より選ばれた少なくとも１種の添加剤を含んでいてもよい。 The recording layer 13A contains a first matrix resin, a decolorized first electron-donating dye, a first thermal acid generator, and a first photothermal conversion agent. The recording layer 13B contains a second matrix resin, a decolorized second electron-donating dye, a second thermal acid generator, and a second photothermal conversion agent. The recording layer 13B contains a third matrix resin, a third electron-donating dye in a decolorized state, a third thermal acid generator, and a third photothermal conversion agent. The recording layers 13A, 13B, and 13C, like the recording layer 13, 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.
（第１、第２、第３のマトリクス樹脂）
　第１、第２、第３のマトリクス樹脂は、第１の実施形態の記録層１３に含まれるマトリックス樹脂と同様である。 (First, second and third matrix resins)
The first, second, and third matrix resins are the same as the matrix resins contained in the recording layer 13 of the first embodiment.
（第１、第２、第３の電子供与性色素）
　第１、第２、第３の電子供与性色素は、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の電子供与性色素は、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の電子供与性色素は、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の電子供与性色素は、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。 (First, second and third electron-donating dyes)
The first, second, and third electron-donating dyes can exhibit different hues in the developed state. Specifically, the first electron-donating dye can exhibit a magenta color in the developed state. The second electron-donating dye is capable of exhibiting a cyan color in the developed state. The third electron-donating dye can exhibit a yellow color in the developed state.
（第１、第２、第３の熱酸発生剤）
　第１、第２、第３の熱酸発生剤は、第１の実施形態の記録層１３に含まれる熱酸発生剤と同様である。なお、第１、第２および第３の熱酸発生剤の酸発生温度がすべて異なっていてもよいし、第１、第２および第３の熱酸発生剤の酸発生温度がすべて同一であってもよい。 (First, second and third thermal acid generators)
The first, second and third thermal acid generators are the same as the thermal acid generators contained in the recording layer 13 of the first embodiment. The acid generation temperatures of the first, second and third thermal acid generators may all be different, or the acid generation temperatures of the first, second and third thermal acid generators may all be the same. may
（第１、第２、第３の光熱変換剤）
　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１３Ａ、１３Ｂ、１３Ｃのうち所望の層を選択的に発色させることができる。 (First, Second, and Third Photothermal Conversion Agents)
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 λ1. The second photothermal conversion agent has an absorption wavelength peak at wavelength λ2. The third photothermal conversion agent has an absorption wavelength peak at wavelength λ3. The wavelengths λ 1 , λ 2 and λ 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.
As described above, 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 13A, 13B, and 13C is selectively colored by irradiation with a laser beam. can be made
　記録層１３Ａ、１３Ｂ、１３Ｃの厚みはそれぞれ、例えば、１μｍ以上２０μｍ以下であることが好ましく、より好ましくは、例えば２μｍ以上１５μｍ以下である。記録層１３Ａ、１３Ｂ、１３Ｃの厚みが１μｍ以上であると、発色濃度を向上させることができる。一方、記録層１３Ａ、１３Ｂ、１３Ｃの厚みが２０μｍ以下であると、記録層１３Ａ、１３Ｂ、１３Ｃの熱利用量の増大を抑制し、発色性の劣化を抑制することができる。 The thickness of each of the recording layers 13A, 13B, and 13C is preferably, for example, 1 μm or more and 20 μm or less, and more preferably, for example, 2 μm or more and 15 μm or less. When the thickness of the recording layers 13A, 13B, and 13C is 1 μm or more, the color density can be improved. On the other hand, when the thickness of the recording layers 13A, 13B, and 13C is 20 μm or less, it is possible to suppress an increase in the amount of heat utilization of the recording layers 13A, 13B, and 13C, and to suppress deterioration of color developability.
（補助層）
　補助層１２Ａは、高温保存時に塩基を発生し記録層１３Ａに拡散することが可能な塩基層である。補助層１２Ａは、記録層１３Ａに隣接して設けられていている。補助層１２Ａは、第４のマトリクス樹脂および第１の熱塩基発生剤を含む。補助層１２Ａは、必要に応じて、上記材料の他に、例えば、紫外線吸収材等の添加剤を含んでいてもよい。 (auxiliary layer)
The auxiliary layer 12A is a base layer capable of generating a base during storage at high temperature and diffusing it into the recording layer 13A. The auxiliary layer 12A is provided adjacent to the recording layer 13A. The auxiliary layer 12A contains a fourth matrix resin and a first thermal base generator. If necessary, the auxiliary layer 12A may contain additives such as ultraviolet absorbers in addition to the above materials.
　補助層１２Ｂは、高温保存時に塩基を発生し記録層１３Ｂに拡散することが可能な塩基層である。補助層１２Ｂは、発生した塩基を記録層１３Ａにも拡散することが可能であってもよい。補助層１２Ｂは、記録層１３Ｂに隣接して設けられていている。補助層１２Ｂは、第５のマトリクス樹脂および第２の熱塩基発生剤を含む。補助層１２Ｂは、必要に応じて、上記材料の他に、例えば、紫外線吸収材等の添加剤を含んでいてもよい。 The auxiliary layer 12B is a base layer that can generate a base during high-temperature storage and diffuse into the recording layer 13B. The auxiliary layer 12B may be capable of diffusing the generated base into the recording layer 13A as well. The auxiliary layer 12B is provided adjacent to the recording layer 13B. The auxiliary layer 12B contains a fifth matrix resin and a second thermal base generator. If necessary, the auxiliary layer 12B may contain additives such as ultraviolet absorbers in addition to the above materials.
　補助層１２Ｃは、高温保存時に塩基を発生し記録層１３Ｃに拡散することが可能な塩基層である。補助層１２Ｃは、発生した塩基を記録層１３Ｂにも拡散することが可能であってもよい。補助層１２Ｃは、記録層１３Ｃに隣接して設けられていている。補助層１２Ｃは、第６のマトリクス樹脂および第３の熱塩基発生剤を含む。補助層１２Ｃは、必要に応じて、上記材料の他に、例えば、紫外線吸収材等の添加剤を含んでいてもよい。 The auxiliary layer 12C is a base layer that can generate a base during high-temperature storage and diffuse into the recording layer 13C. The auxiliary layer 12C may be capable of diffusing the generated base into the recording layer 13B as well. The auxiliary layer 12C is provided adjacent to the recording layer 13C. Auxiliary layer 12C contains a sixth matrix resin and a third thermal base generator. 12 C of auxiliary|assistant layers may contain additives, such as an ultraviolet absorber, other than the said material as needed.
（第４、第５、第６のマトリクス樹脂）
　第１、第２、第３のマトリクス樹脂は、第１の実施形態の補助層１２に含まれるマトリックス樹脂と同様である。 (Fourth, Fifth and Sixth Matrix Resins)
The first, second and third matrix resins are the same as the matrix resins contained in the auxiliary layer 12 of the first embodiment.
（第１、第２、第３の熱塩基発生剤）
　第１、第２、第３の熱塩基発生剤としては、第１の実施形態の補助層１２に含まれる熱塩基発生剤と同様の材料を例示することができる。なお、第１、第２、第３の熱塩基発生剤の塩基発生温度がすべて異なっていてもよいし、第１、第２、第３の熱塩基発生剤の塩基発生温度がすべて同一であってもよい。 (First, second and third thermal base generators)
As the first, second, and third thermal base generators, the same materials as the thermal base generators contained in the auxiliary layer 12 of the first embodiment can be exemplified. The base generation temperatures of the first, second and third thermal base generators may all be different, or the base generation temperatures of the first, second and third thermal base generators may all be the same. may
　第１の熱塩基発生剤の塩基発生温度は、第１の熱酸発生剤の酸発生温度と略一致することが好ましい。第１の熱塩基発生剤の塩基発生温度が第１の熱酸発生剤の酸発生温度と略一致していると、光記録媒体１０Ａが高温保存された際に、第１の熱酸発生剤が酸を発生すると略同時に第１の熱塩基発生剤が塩基を発生し拡散する。 The base generation temperature of the first thermal base generator is preferably approximately the same as the acid generation temperature of the first thermal acid generator. When the base generation temperature of the first thermal base generator substantially matches the acid generation temperature of the first thermal acid generator, when the optical recording medium 10A is stored at a high temperature, the first thermal acid generator generates an acid, the first thermal base generator generates and diffuses a base substantially at the same time.
　第２の熱塩基発生剤の塩基発生温度は、第２の熱酸発生剤の酸発生温度以下と略一致することが好ましい。第３の熱塩基発生剤の塩基発生温度は、第３の熱酸発生剤の酸発生温度以下と略一致することが好ましい。第２の熱塩基発生剤および第３の熱塩基発生剤の塩基発生温度を上記のように規定することで得られる効果は、第１の熱塩基発生剤の塩基発生温度を規定することで得られる効果と同様であるので説明を省略する。 It is preferable that the base generation temperature of the second thermal base generator substantially coincides with the acid generation temperature of the second thermal acid generator or lower. It is preferable that the base generation temperature of the third thermal base generator substantially coincides with the acid generation temperature of the third thermal acid generator or lower. The effect obtained by defining the base generation temperatures of the second thermal base generator and the third thermal base generator as described above can be obtained by defining the base generation temperature of the first thermal base generator. Since it is the same as the effect obtained, the explanation is omitted.
　光記録媒体１０Ａが高温に保存された際に、記録層１３Ａにて発色と消色とを拮抗させる観点からすると、第１の熱酸発生剤の酸発生温度ＴＡ１および第１の熱塩基発生剤の塩基発生温度ＴＢ１が、以下の関係式（Ａ１）を満たすことが好ましい。
　｜ＴＡ１－ＴＢ１｜≦２０［Ｋ］　・・・（Ａ１） When the optical recording medium 10A is stored at a high temperature, from the viewpoint of balancing the color development and decoloration in the recording layer 13A, the acid generation temperature T A1 of the first thermal acid generator and the first thermal base generation The base generation temperature T B1 of the agent preferably satisfies the following relational expression (A1).
|T A1 −T B1 |≦20 [K] (A1)
　光記録媒体１０Ａが高温に保存された際に、記録層１３Ｂにて発色と消色とを拮抗させる観点からすると、第２の熱酸発生剤の酸発生温度ＴＡ２および第２の熱塩基発生剤の塩基発生温度ＴＢ２が、以下の関係式（Ａ２）を満たすことが好ましい。
　｜ＴＡ２－ＴＢ２｜≦２０［Ｋ］　・・・（Ａ２） When the optical recording medium 10A is stored at a high temperature, from the viewpoint of balancing the color development and decoloration in the recording layer 13B, the acid generation temperature TA2 of the second thermal acid generator and the second thermal base generation The base generation temperature T B2 of the agent preferably satisfies the following relational expression (A2).
|T A2 −T B2 |≦20 [K] (A2)
　光記録媒体１０Ａが高温に保存された際に、記録層１３Ｃにて発色と消色とを拮抗させる観点からすると、第３の熱酸発生剤の酸発生温度ＴＡ３および第３の熱塩基発生剤の塩基発生温度ＴＢ３が、以下の関係式（Ａ３）を満たすことが好ましい。
　｜ＴＡ３－ＴＢ３｜≦２０［Ｋ］　・・・（Ａ３） When the optical recording medium 10A is stored at a high temperature, from the viewpoint of balancing the color development and decoloration in the recording layer 13C, the acid generation temperature TA3 of the third thermal acid generator and the third thermal base generation The base generation temperature T B3 of the agent preferably satisfies the following relational expression (A3).
|T A3 −T B3 |≦20 [K] (A3)
［２．２　光記録媒体の描画方法］
　以下、第２の実施形態に係る光記録媒体１０Ａの描画方法の一例について説明する。 [2.2 Drawing method for optical recording medium]
An example of the drawing method for the optical recording medium 10A according to the second embodiment will be described below.
　記録層１３Ａは次のようにしてマゼンタ色に発色される。記録層１３Ａの所定の位置に波長λ１の近赤外レーザー光を照射する。レーザー光の照射部分に含まれる光熱変換剤が近赤外レーザー光を吸収して発熱し、この発熱により熱酸発生剤が酸を発生する。発生した酸が電子供与性色素に作用すると、電子供与性色素は色相を変化し、マゼンタ色に発色する。これにより、レーザー光の照射部分がマゼンタ色に発色する。 The recording layer 13A is colored magenta as follows. A predetermined position of the recording layer 13A is irradiated with a near - infrared laser beam having a wavelength of λ1. The photothermal conversion agent contained in the irradiated portion of the laser beam absorbs the near-infrared laser beam and generates heat, and the heat generation causes the thermal acid generator to generate acid. When the generated acid acts on the electron-donating dye, the electron-donating dye changes its hue and develops a magenta color. As a result, the portion irradiated with the laser light develops a magenta color.
　記録層１３Ｂは次のようにしてシアン色に発色される。記録層１３Ｂの所定の位置に波長λ２の近赤外レーザー光を照射する。上記の記録層１３Ａと同様の反応により、レーザー光の照射部分がシアン色に発色する。 The recording layer 13B is colored cyan in the following manner. A predetermined position of the recording layer 13B is irradiated with a near - infrared laser beam having a wavelength of λ2. Due to the reaction similar to that of the recording layer 13A, the portion irradiated with the laser light develops a cyan color.
　記録層１３Ｃは次のようにしてイエロー色に発色される。記録層１３Ｃの所定の位置に波長λ３の近赤外レーザー光を照射する。上記の記録層１３Ａと同様の反応により、レーザー光の照射部分がイエロー色に発色する。 The recording layer 13C is colored yellow in the following manner. A predetermined position of the recording layer 13C is irradiated with a near - infrared laser beam having a wavelength of λ3. Due to the reaction similar to that of the recording layer 13A, the portion irradiated with the laser light develops a yellow color.
　上記のように、記録層１３Ａ、１３Ｂ、１３Ｃの所定の位置がそれぞれマゼンタ色、シアン色、イエロー色に発色することにより、光記録媒体１０に所望のフルカラー画像が描画される。 As described above, predetermined positions of the recording layers 13A, 13B, and 13C are colored magenta, cyan, and yellow, respectively, so that a desired full-color image is drawn on the optical recording medium 10 .
［２．３　作用効果］
　第２の実施形態に係る光記録媒体１０Ａでは、補助層１２Ａが記録層１３Ａに隣接して設けられ、補助層１２Ｂが記録層１３Ｂに隣接して設けられ、補助層１２Ｃが記録層１３Ｃに隣接して設けられている。これにより、高温保存時における記録層１３Ａ、１３Ｂ、１３Ｃの地肌の色相変化を抑制することができる。 [2.3 Effects]
In the optical recording medium 10A according to the second embodiment, the auxiliary layer 12A is provided adjacent to the recording layer 13A, the auxiliary layer 12B is provided adjacent to the recording layer 13B, and the auxiliary layer 12C is provided adjacent to the recording layer 13C. is provided. As a result, it is possible to suppress the hue change of the background of the recording layers 13A, 13B, and 13C during high-temperature storage.
　第２の実施形態に係る光記録媒体１０Ａでは、記録層１３Ａ、１３Ｂ、１３Ｃはそれぞれ、発色状態においてマゼンタ色、シアン色、イエロー色を呈することが可能である。したがって、所望の画像をフルカラーで描画することができる。 In the optical recording medium 10A according to the second embodiment, the recording layers 13A, 13B, and 13C are capable of exhibiting magenta, cyan, and yellow, respectively, in the colored state. Therefore, a desired image can be drawn in full color.
＜３　第３の実施形態＞
　上記第２の実施形態では、光記録媒体が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、光記録媒体が３種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。 <3 Third Embodiment>
In the second embodiment, the optical recording medium has three recording layers and is capable of drawing a full-color image. An example in which a recording layer containing microcapsules is provided and a full-color image can be drawn will be described.
［３．１　光記録媒体の構成］
　図７は、第３の実施形態に係る光記録媒体１０Ｂの構成の一例を示す断面図である。光記録媒体１０Ｂは、基材１１、基材１１上に設けられた補助層１２と、補助層１２上に設けられた記録層１５とを備える。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。 [3.1 Structure of optical recording medium]
FIG. 7 is a cross-sectional view showing an example of the configuration of an optical recording medium 10B according to the third embodiment. The optical recording medium 10B includes a substrate 11 , an auxiliary layer 12 provided on the substrate 11 , and a recording layer 15 provided on the auxiliary layer 12 . In addition, in 3rd Embodiment, the same code|symbol is attached|subjected to the same location as 1st Embodiment, and description is abbreviate|omitted.
（記録層）
　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（外部刺激）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。 (Recording layer)
The recording layer 15 contains three types of microcapsules 15A, 15B, 15C and a matrix resin. Microcapsules 15A, 15B, and 15C can change the coloring state by laser light (external stimulus). Each of the microcapsules 15A, 15B, and 15C can present different hues in the colored state. Specifically, 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.
　マイクロカプセル１５Ａは、マイクロカプセル壁内に、消色状態の第１の電子供与性色素、第１の熱酸発生剤および第１の光熱変換剤を含む。マイクロカプセル１５Ｂは、マイクロカプセル壁内に、消色状態の第２の電子供与性色素、第２の熱酸発生剤および第２の光熱変換剤を含む。マイクロカプセル１５Ｃは、マイクロカプセル壁内に、消色状態の第３の電子供与性色素、第３の熱酸発生剤および第３の光熱変換剤を含む。マイクロカプセル１５Ａ、１５Ｂ、１５Ｃはそれぞれ、マイクロカプセル壁内に、上記材料の他に、例えば、マトリックス樹脂、増感剤および紫外線吸収材等からなる群より選ばれた少なくとも１種の添加剤を含んでいてもよい。 The microcapsule 15A contains a decolorized first electron-donating dye, a first thermal acid generator and a first photothermal conversion agent in the microcapsule wall. The microcapsule 15B contains a second electron-donating dye in a decolorized state, a second thermal acid generator and a second photothermal conversion agent within the microcapsule wall. The microcapsule 15C contains a third electron-donating dye in a decolorized state, a third thermal acid generator and a third photothermal conversion agent within the microcapsule wall. Each of the microcapsules 15A, 15B, and 15C contains, in addition to the above materials, at least one additive selected from the group consisting of matrix resins, sensitizers, ultraviolet absorbers, etc., in the microcapsule walls. You can stay.
（マイクロカプセル壁）
　マイクロカプセル１５Ａ、１５Ｂ、１５Ｃのマイクロカプセル壁は、レーザー光の吸収による光熱変換剤の発熱により溶解することが可能である。マイクロカプセル１５Ａ、１５Ｂ、１５Ｃのマイクロカプセル壁は、塩基発生剤から発生した塩基を透過することが可能であってもよい。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、メチルセルロース、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、ポリアミド、ポリウレタン、ポリウレア、ポリカーボネート、ポリアクリル酸エステル、ポリアクリル酸カルシウム、アルギン酸カルシウム、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、メラミン樹脂、エポキシ樹脂、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、カゼインナトリウム、ゼラチン、アラビアゴム、多糖類、脂肪酸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。 (microcapsule wall)
The microcapsule walls of the microcapsules 15A, 15B, and 15C can be dissolved by the heat generation of the photothermal conversion agent due to absorption of laser light. The microcapsule walls of microcapsules 15A, 15B, 15C may be permeable to the base generated from the base generator. The microcapsule wall is 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, methyl cellulose, polystyrene, styrenic copolymer, phenoxy resin, polyester, and aromatic polyester. , Polyamide, Polyurethane, Polyurea, Polycarbonate, Polyacrylate, Calcium polyacrylate, Calcium alginate, Polymethacrylate, Acrylic acid copolymer, Maleic acid polymer, Polyvinyl alcohol, Modified polyvinyl alcohol, Melamine resin, At least one selected from the group consisting of epoxy resins, hydroxyethyl cellulose, carboxymethyl cellulose, sodium caseinate, gelatin, gum arabic, polysaccharides, fatty acids, starch and the like.
（第１、第２、第３の電子供与性色素）
　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。 (First, second and third electron-donating dyes)
The first, second and third electron-donating dyes are the same as in the second embodiment.
（第１、第２、第３の熱酸発生剤）
　第１、第２、第３の熱酸発生剤は、第２の実施形態と同様である。 (First, second and third thermal acid generators)
The first, second and third thermal acid generators are the same as in the second embodiment.
（第１、第２、第３の光熱変換剤）
　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。 (First, Second, and Third Photothermal Conversion Agents)
The first, second and third photothermal conversion agents are the same as in the second embodiment.
［３．２　光記録媒体の描画方法］
　以下、第３の実施形態に係る光記録媒体１０Ｂの描画方法の一例について説明する。 [3.2 Drawing method for optical recording medium]
An example of the drawing method for the optical recording medium 10B according to the third embodiment will be described below.
　記録層１５は次のようにしてマゼンタ色に発色される。記録層１５の所定の位置に波長λ１の近赤外レーザー光を照射する。レーザー光の照射部分に含まれるマイクロカプセル１５Ａがマゼンタ色に発色する。これにより、レーザー光の照射部分がマゼンタ色に発色する。 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 wavelength of λ1. 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.
　記録層１５は次のようにしてシアン色に発色される。記録層１５の所定の位置に波長λ２の近赤外レーザー光を照射する。レーザー光の照射部分に含まれるマイクロカプセル１５Ｂがシアン色に発色する。これにより、レーザー光の照射部分がシアン色に発色する。 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 wavelength of λ2. The microcapsules 15B contained in the laser beam irradiated portion develop a cyan color. As a result, the portion irradiated with the laser light develops a cyan color.
　記録層１５は次のようにしてイエロー色に発色される。記録層１５の所定の位置に波長λ３の近赤外レーザー光を照射する。レーザー光の照射部分に含まれるマイクロカプセル１５Ｃがイエロー色に発色する。これにより、レーザー光の照射部分がイエロー色に発色する。 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 wavelength of λ3. The microcapsules 15C included in the laser light irradiated portion develop a yellow color. As a result, the portion irradiated with the laser light develops a yellow color.
　上記のように、記録層１５の所定の位置がそれぞれマゼンタ色、シアン色、イエロー色に発色することにより、光記録媒体１０Ｂに所望のフルカラー画像が描画される。 As described above, a desired full-color image is drawn on the optical recording medium 10B by developing magenta, cyan, and yellow colors at predetermined positions on the recording layer 15, respectively.
［３．３　作用効果］
　第３の実施形態に係る光記録媒体１０Ｂでは、レーザー光の照射により記録層１５が発色されると、レーザー光の照射部分（発色状態の部分）に含まれるマイクロカプセル１５Ａ、１５Ｂ、１５Ｃが溶解する。描画後の光記録媒体１０Ｂが高温の環境に保存された場合、上記の照射部分（発色状態の部分）において、熱酸発生剤から発生した酸と、熱塩基発生剤から発生した塩基とが中和反応するため、電子供与性色素に作用する酸の量を低減することができる。よって、高温保存時における発色状態の部分（記録部）の色相変化を抑制することができる。 [3.3 Effects]
In the optical recording medium 10B according to the third embodiment, when the recording layer 15 is colored by laser light irradiation, the microcapsules 15A, 15B, and 15C contained in the laser light irradiated portion (color-developed portion) are dissolved. do. When the optical recording medium 10B after drawing is stored in a high-temperature environment, the acid generated from the thermal acid generator and the base generated from the thermal base generator are mixed in the irradiated portion (portion in the colored state). Because of the sum reaction, the amount of acid acting on the electron-donating dye can be reduced. Therefore, it is possible to suppress the change in hue of the colored portion (recording portion) during high-temperature storage.
　マイクロカプセル１５Ａ、１５Ｂ、１５Ｃのマイクロカプセル壁が、塩基を透過することが可能である場合には、光記録媒体１０Ｂが高温の環境に保存された際に、熱塩基発生剤が発生した塩基は、補助層１２から記録層１５に拡散し、マイクロカプセル１５Ａ、１５Ｂ、１５Ｃのカプセル壁を透過することができる。カプセル壁を透過した塩基は、マイクロカプセル１５Ａ、１５Ｂ、１５Ｃ内で発生した酸と中和反応することができるので、高温保存時における記録層１５の地肌（消色状態の部分）の色相変化を抑制することができる。 When the microcapsule walls of the microcapsules 15A, 15B, and 15C are permeable to a base, the base generated by the thermal base generator when the optical recording medium 10B is stored in a high-temperature environment is , can diffuse from the auxiliary layer 12 to the recording layer 15 and penetrate the capsule walls of the microcapsules 15A, 15B, 15C. The base that has permeated the capsule wall can neutralize with the acid generated in the microcapsules 15A, 15B, and 15C. can be suppressed.
＜４　第４の実施形態＞
　第１の実施形態では、記録層が熱酸発生剤を含み、補助層が熱塩基発生剤を含む例について説明したのに対して、第４の実施形態では、記録層が熱酸発生剤に代えて熱塩基発生剤を含み、補助層が熱塩基発生剤に代えて熱酸発生剤を含む例について説明する。 <4 Fourth Embodiment>
In the first embodiment, the recording layer contains a thermal acid generator and the auxiliary layer contains a thermal base generator. An example in which a thermal base generator is included instead and the auxiliary layer includes a thermal acid generator instead of the thermal base generator will be described.
［４．１　光記録媒体の構成］
　第４の実施形態に係る光記録媒体１０は、第１の実施形態に係る光記録媒体１０と同一の層構成を有する。このため、以下では、図１を参照して、第４の実施形態に係る光記録媒体１０の構成について説明する。 [4.1 Configuration of Optical Recording Medium]
The optical recording medium 10 according to the fourth embodiment has the same layer structure as the optical recording medium 10 according to the first embodiment. Therefore, the configuration of the optical recording medium 10 according to the fourth embodiment will be described below with reference to FIG.
　第４の実施形態に係る光記録媒体１０は、記録層１３がマトリクス樹脂、発色状態の電子供与性色素、熱塩基発生剤および光熱変換剤を含み、補助層１２がマトリクス樹脂および熱酸発生剤を含む点において、第１の実施形態に係る光記録媒体１０とは異なっている。 In the optical recording medium 10 according to the fourth embodiment, the recording layer 13 contains a matrix resin, an electron-donating dye in a colored state, a thermal base generator and a photothermal conversion agent, and the auxiliary layer 12 contains a matrix resin and a thermal acid generator. is different from the optical recording medium 10 according to the first embodiment.
（記録層）
　未記録状態（初期状態）の記録層１３は、発色状態にある。記録層１３は、レーザー光（外部刺激）により発色状態から消色状態に変化可能である。記録層１３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。 (Recording layer)
The recording layer 13 in an unrecorded state (initial state) is in a colored state. The recording layer 13 can change from a colored state to a decolored state by laser light (external stimulus). The recording layer 13 can exhibit a predetermined color in a colored state.
（補助層）
　補助層１２は、高温保存時に酸を発生し記録層１３に拡散することが可能である。熱酸発生剤の酸発生温度は、熱塩基発生剤の塩基発生温度と略一致することが好ましい。熱酸発生剤の酸発生温度が熱塩基発生剤の塩基発生温度と略一致していると、光記録媒体１０が高温保存された際に、熱塩基発生剤が塩基を発生すると略同時に熱酸発生剤が酸を発生し拡散する。第４の実施形態では、地肌とは、記録層１３の発色状態の部分をいう。 (auxiliary layer)
The auxiliary layer 12 is capable of generating acid and diffusing it into the recording layer 13 during high-temperature storage. The acid generation temperature of the thermal acid generator is preferably approximately the same as the base generation temperature of the thermal base generator. If the acid generation temperature of the thermal acid generator substantially coincides with the base generation temperature of the thermal base generator, when the optical recording medium 10 is stored at a high temperature, thermal acid is generated substantially at the same time as the thermal base generator generates a base. A generator generates and diffuses acid. In the fourth embodiment, the background refers to a colored portion of the recording layer 13 .
［４．２　光記録媒体の描画方法］
　以下、第４の実施形態に係る光記録媒体１０の描画方法の一例について説明する。 [4.2 Drawing method for optical recording medium]
An example of a drawing method for the optical recording medium 10 according to the fourth embodiment will be described below.
　描画前（すなわち初期状態）の光記録媒体１０では、記録層１３に含まれる電子供与性色素、熱塩基発生剤はそれぞれ、発色状態、中性状態にある。また、補助層１２に含まれる熱酸発生剤は、中性状態にある。 In the optical recording medium 10 before drawing (that is, in the initial state), the electron-donating dye and thermal base generator contained in the recording layer 13 are in a colored state and a neutral state, respectively. Also, the thermal acid generator contained in the auxiliary layer 12 is in a neutral state.
　近赤外レーザー光等のレーザー光が記録層１３の所定の位置に照射されると、記録層１３の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し、この発熱により熱塩基発生剤が活性化し塩基を発生する。発生した塩基が記録層１３内を拡散し発色状態の電子供与性色素に作用すると、電子供与性色素は色相変化を呈し、消色状態となる。これにより、記録層１３に所望の画像が描画される。 When a predetermined position of the recording layer 13 is irradiated with a laser beam such as a near-infrared laser beam, the photothermal conversion agent contained in the irradiated portion of the recording layer 13 absorbs the laser beam and generates heat. A generator is activated to generate a base. When the generated base diffuses in the recording layer 13 and acts on the electron-donating dye in the colored state, the electron-donating dye changes its hue and becomes decolored. A desired image is thus drawn on the recording layer 13 .
　補助層１２は光熱変換剤を含んでいないため、上記レーザー光の照射によっても、補助層１２に含まれる熱酸発生剤には、当該熱酸発生剤が活性化するのに十分な熱は与えられない。したがって、熱酸発生剤は中性状態を維持し、酸を発生しない。よって、描画時には、補助層１２から記録層１３に酸が拡散されることはない。 Since the auxiliary layer 12 does not contain a photothermal conversion agent, the thermal acid generator contained in the auxiliary layer 12 does not receive sufficient heat to activate the thermal acid generator even when irradiated with the laser beam. can't Therefore, the thermal acid generator remains neutral and does not generate acid. Therefore, acid is not diffused from the auxiliary layer 12 to the recording layer 13 during writing.
［４．３　作用効果］
　第４の実施形態に係る光記録媒体１０では、高温保存により光記録媒体１０の全体が昇温されると、記録層１３に含まれる熱塩基発生剤が塩基を発生すると共に、補助層１２に含まれる熱酸発生剤が塩基を発生する。発生した塩基および酸が拡散し反応することで、中和される。これにより、発生した塩基が電子供与性色素に作用することを抑制することができるので、高温保存時の地肌発色が抑制される。 [4.3 Effects]
In the optical recording medium 10 according to the fourth embodiment, when the temperature of the entire optical recording medium 10 is raised due to high-temperature storage, the thermal base generator contained in the recording layer 13 generates a base, and the auxiliary layer 12 The included thermal acid generator generates a base. The generated base and acid diffuse and react to neutralize. As a result, it is possible to suppress the action of the generated base on the electron-donating dye, thereby suppressing the background color development during high-temperature storage.
　上記地肌発色の抑制効果は、描画後の光記録媒体１０において得られるものであってもよいし、描画前（初期状態）の光記録媒体１０において得られるものであってもよい。 The effect of suppressing background coloring may be obtained in the optical recording medium 10 after drawing, or may be obtained in the optical recording medium 10 before drawing (initial state).
＜５　第５の実施形態＞
　第１の実施形態では、記録層が熱酸発生剤および光熱変換剤を含み、補助層が熱塩基発生剤を含む例について説明したのに対して、第４の実施形態では、記録層が熱酸発生剤および光熱変換剤に代えて熱塩基発生剤を含み、補助層が熱塩基発生剤に代えて熱酸発生剤および光熱変換剤を含む例について説明する。 <5 Fifth Embodiment>
In the first embodiment, the recording layer contains a thermal acid generator and a photothermal conversion agent, and the auxiliary layer contains a thermal base generator. An example in which a thermal base generator is included in place of the acid generator and the photothermal conversion agent and the auxiliary layer includes the thermal acid generator and the photothermal conversion agent in place of the thermal base generator will be described.
［５．１　光記録媒体の構成］
　第５の実施形態に係る光記録媒体１０は、第１の実施形態に係る光記録媒体１０と同一の層構成を有する。このため、以下では、図１を参照して、第５の実施形態に係る光記録媒体１０の構成について説明する。 [5.1 Configuration of Optical Recording Medium]
The optical recording medium 10 according to the fifth embodiment has the same layer structure as the optical recording medium 10 according to the first embodiment. Therefore, the configuration of the optical recording medium 10 according to the fifth embodiment will be described below with reference to FIG.
　第５の実施形態に係る光記録媒体１０は、記録層１３がマトリクス樹脂、消色状態の電子供与性色素および熱塩基発生剤を含み、補助層１２がマトリクス樹脂、熱酸発生剤および光熱変換剤を含む点において、第１の実施形態に係る光記録媒体１０とは異なっている。 In the optical recording medium 10 according to the fifth embodiment, the recording layer 13 contains a matrix resin, a decolorized electron-donating dye and a thermal base generator, and the auxiliary layer 12 contains a matrix resin, a thermal acid generator and a photothermal converter. It differs from the optical recording medium 10 according to the first embodiment in that it contains an agent.
　第１の実施形態と同様に、熱塩基発生剤の塩基発生温度は、熱酸発生剤の酸発生温度と略一致することが好ましい。 As in the first embodiment, it is preferable that the base generation temperature of the thermal base generator substantially coincides with the acid generation temperature of the thermal acid generator.
［５．２　光記録媒体の描画方法］
　以下、第５の実施形態に係る光記録媒体１０の描画方法の一例について説明する。 [5.2 Drawing method for optical recording medium]
An example of a drawing method for the optical recording medium 10 according to the fifth embodiment will be described below.
　描画前（すなわち初期状態）の光記録媒体１０では、記録層１３に含まれる電子供与性色素、熱塩基発生剤はそれぞれ、消色状態、中性状態にある。また、補助層１２に含まれる熱酸発生剤はそれぞれ、中性状態にある。 In the optical recording medium 10 before drawing (that is, in the initial state), the electron-donating dye and thermal base generator contained in the recording layer 13 are in a decolored state and a neutral state, respectively. Moreover, each of the thermal acid generators contained in the auxiliary layer 12 is in a neutral state.
　近赤外レーザー光等のレーザー光が補助層１２の所定の位置に照射されると、補助層１２の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し、この発熱により熱酸発生剤が活性化し酸を発生する。発生した酸が補助層１２から記録層１３に拡散し消色状態の電子供与性色素に作用すると、電子供与性色素は色相変化を呈し、発色状態となる。これにより、記録層１３に所望の画像が描画される。 When a predetermined position of the auxiliary layer 12 is irradiated with a laser beam such as a near-infrared laser beam, the photothermal conversion agent contained in the irradiated portion of the auxiliary layer 12 absorbs the laser beam and generates heat. The generator is activated to generate acid. When the generated acid diffuses from the auxiliary layer 12 to the recording layer 13 and acts on the decolorized electron-donating dye, the electron-donating dye exhibits a hue change and becomes colored. A desired image is thus drawn on the recording layer 13 .
　記録層１３は光熱変換剤を含んでいないため、上記レーザー光照射によっても、記録層１３に含まれる熱塩基発生剤には、当該熱塩基発生剤が活性化するのに十分な熱は与えられない。したがって、熱塩基発生剤は中性状態を維持し、塩基を発生しない。よって、描画時には、記録層１３内に塩基が拡散されることはない。 Since the recording layer 13 does not contain a photothermal conversion agent, the thermal base generator contained in the recording layer 13 is not given sufficient heat to activate the thermal base generator even by the laser light irradiation. Absent. Therefore, the thermal base generator remains neutral and does not generate base. Therefore, the base is not diffused into the recording layer 13 during writing.
［５．３　作用効果］
　第５の実施形態に係る光記録媒体１０では、高温保存により光記録媒体１０の全体が昇温されると、補助層１２に含まれる熱酸発生剤が塩基を発生すると共に、記録層１３に含まれる熱塩基発生剤が塩基を発生する。発生した塩基および酸が拡散し反応することで、中和される。これにより、発生した酸が電子供与性色素に作用することを抑制することができるので、高温保存時の地肌発色が抑制される。 [5.3 Effects]
In the optical recording medium 10 according to the fifth embodiment, when the temperature of the entire optical recording medium 10 is raised due to high-temperature storage, the thermal acid generator contained in the auxiliary layer 12 generates a base, and the recording layer 13 The included thermal base generator generates a base. The generated base and acid diffuse and react to neutralize. As a result, it is possible to suppress the action of the generated acid on the electron-donating dye, thereby suppressing the coloring of the background during high-temperature storage.
　上記地肌発色の抑制効果は、描画後の光記録媒体１０において得られるものであってもよいし、描画前（初期状態）の光記録媒体１０において得られるものであってもよい。 The effect of suppressing background coloring may be obtained in the optical recording medium 10 after drawing, or may be obtained in the optical recording medium 10 before drawing (initial state).
＜６　第６の実施形態＞
　第１の実施形態では、記録層が光熱変換剤を含む例について説明したのに対して、第６の実施形態では、補助層が光熱変換剤を含む例について説明する。 <6 Sixth Embodiment>
In the first embodiment, an example in which the recording layer contains a photothermal conversion agent has been described, while in the sixth embodiment, an example in which the auxiliary layer contains a photothermal conversion agent will be described.
［６．１　光記録媒体の構成］
　第６の実施形態に係る光記録媒体１０は、第１の実施形態に係る光記録媒体１０と同一の層構成を有する。このため、以下では、図１を参照して、第６の実施形態に係る光記録媒体１０の構成について説明する。 [6.1 Configuration of Optical Recording Medium]
The optical recording medium 10 according to the sixth embodiment has the same layer structure as the optical recording medium 10 according to the first embodiment. Therefore, the configuration of the optical recording medium 10 according to the sixth embodiment will be described below with reference to FIG.
　第６の実施形態に係る光記録媒体１０は、記録層１３がマトリクス樹脂、発色状態の電子供与性色素および熱酸発生剤を含み、補助層１２がマトリクス樹脂、熱塩基発生剤および光熱変換剤を含む点において、第１の実施形態に係る光記録媒体１０とは異なっている。 In the optical recording medium 10 according to the sixth embodiment, the recording layer 13 contains a matrix resin, an electron-donating dye in a colored state, and a thermal acid generator, and the auxiliary layer 12 contains a matrix resin, a thermal base generator, and a photothermal conversion agent. is different from the optical recording medium 10 according to the first embodiment.
（記録層）
　未記録状態（初期状態）の記録層１３は、発色状態にある。記録層１３は、レーザー光（外部刺激）により発色状態から消色状態に変化可能である。記録層１３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。 (Recording layer)
The recording layer 13 in an unrecorded state (initial state) is in a colored state. The recording layer 13 can change from a colored state to a decolored state by laser light (external stimulus). The recording layer 13 can exhibit a predetermined color in a colored state.
　熱酸発生剤の酸発生温度は、熱塩基発生剤の塩基発生温度と略一致することが好ましい。熱酸発生剤の酸発生温度が熱塩基発生剤の塩基発生温度と略一致していると、光記録媒体１０が高温保存された際に、熱塩基発生剤が塩基を発生すると略同時に熱酸発生剤が酸を発生し拡散する。第４の実施形態では、地肌とは、記録層１３の発色状態の部分をいう。 The acid generation temperature of the thermal acid generator is preferably approximately the same as the base generation temperature of the thermal base generator. If the acid generation temperature of the thermal acid generator substantially coincides with the base generation temperature of the thermal base generator, when the optical recording medium 10 is stored at a high temperature, thermal acid is generated substantially at the same time as the thermal base generator generates a base. A generator generates and diffuses acid. In the fourth embodiment, the background refers to a colored portion of the recording layer 13 .
（補助層）
　補助層１２は、レーザー光が照射されると、レーザー光の照射部分から塩基を発生し記録層１３に拡散することが可能である。 (auxiliary layer)
When the auxiliary layer 12 is irradiated with a laser beam, a base can be generated from the irradiated portion of the laser beam and diffused into the recording layer 13 .
［６．２　光記録媒体の描画方法］
　以下、第６の実施形態に係る光記録媒体１０の描画方法の一例について説明する。 [6.2 Drawing method for optical recording medium]
An example of a drawing method for the optical recording medium 10 according to the sixth embodiment will be described below.
　描画前（すなわち初期状態）の光記録媒体１０では、記録層１３に含まれる電子供与性色素、熱酸発生剤はそれぞれ、発色状態、中性状態にある。また、補助層１２に含まれる熱塩基発生剤は、中性状態にある。 In the optical recording medium 10 before drawing (that is, in the initial state), the electron-donating dye and the thermal acid generator contained in the recording layer 13 are in a colored state and a neutral state, respectively. Moreover, the thermal base generator contained in the auxiliary layer 12 is in a neutral state.
　近赤外レーザー光等のレーザー光が補助層１２の所定の位置に照射されると、補助層１２の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し、この発熱により熱塩基発生剤が活性化し塩基を発生する。発生した塩基が補助層１２から記録層１３に拡散し発色状態の電子供与性色素に作用すると、電子供与性色素は色相変化を呈し、消色状態となる。これにより、記録層１３に所望の画像が描画される。 When a predetermined position of the auxiliary layer 12 is irradiated with a laser beam such as a near-infrared laser beam, the photothermal conversion agent contained in the irradiated portion of the auxiliary layer 12 absorbs the laser beam and generates heat. A generator is activated to generate a base. When the generated base diffuses from the auxiliary layer 12 to the recording layer 13 and acts on the electron-donating dye in the colored state, the electron-donating dye changes its hue and becomes decolored. A desired image is thus drawn on the recording layer 13 .
　記録層１３は光熱変換剤を含んでいないため、上記レーザー光の照射によっても、記録層１３に含まれる熱酸発生剤には、当該熱酸発生剤が活性化するのに十分な熱は与えられない。したがって、熱酸発生剤は中性状態を維持し、酸を発生しない。よって、描画時には、記録層１３内に酸が拡散されることはない。 Since the recording layer 13 does not contain a photothermal conversion agent, the thermal acid generator contained in the recording layer 13 does not receive enough heat to activate the thermal acid generator even when irradiated with the laser beam. can't Therefore, the thermal acid generator remains neutral and does not generate acid. Therefore, the acid does not diffuse into the recording layer 13 during writing.
［６．３　作用効果］
　第６の実施形態に係る光記録媒体１０では、高温保存により光記録媒体１０の全体が昇温されると、補助層１２に含まれる熱塩基発生剤が塩基を発生すると共に、記録層１３に含まれる熱酸発生剤が酸を発生する。発生した塩基および酸が拡散し反応することで、中和される。これにより、発生した塩基が電子供与性色素に作用することを抑制することができるので、高温保存時の地肌発色が抑制される。 [6.3 Effects]
In the optical recording medium 10 according to the sixth embodiment, when the temperature of the entire optical recording medium 10 is raised by high-temperature storage, the thermal base generator contained in the auxiliary layer 12 generates a base, and the recording layer 13 The included thermal acid generator generates acid. The generated base and acid diffuse and react to neutralize. As a result, it is possible to suppress the action of the generated base on the electron-donating dye, thereby suppressing the background color development during high-temperature storage.
　上記地肌発色の抑制効果は、描画後の光記録媒体１０において得られるものであってもよいし、描画前（初期状態）の光記録媒体１０において得られるものであってもよい。 The effect of suppressing background coloring may be obtained in the optical recording medium 10 after drawing, or may be obtained in the optical recording medium 10 before drawing (initial state).
＜７　変形例＞
（変形例１）
　第１の実施形態では、補助層１２上に記録層１３が備えられている例（図１参照）について説明したが、図８に示すように、記録層１３上に補助層１２が備えられていてもよい。 <7 Modifications>
(Modification 1)
In the first embodiment, the example in which the recording layer 13 is provided on the auxiliary layer 12 (see FIG. 1) has been described. may
（変形例２）
　第３の実施形態では、記録層１３Ａと補助層１２Ｂとが隣接し、記録層１３Ｂと補助層１２Ｃとが隣接している例（図６参照）について説明したが、図９に示すように、記録層１３Ａと補助層１２Ｂとの間に断熱層１４Ａが備えられ、記録層１３Ｂと補助層１２Ｃとの間に断熱層１４Ｂが備えられていてもよい。 (Modification 2)
In the third embodiment, the example in which the recording layer 13A and the auxiliary layer 12B are adjacent and the recording layer 13B and the auxiliary layer 12C are adjacent (see FIG. 6) has been described. A heat insulating layer 14A may be provided between the recording layer 13A and the auxiliary layer 12B, and a heat insulating layer 14B may be provided between the recording layer 13B and the auxiliary layer 12C.
　断熱層１４Ａ、１４Ｂは、例えば一般的な透光性を有する高分子材料により構成されている。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。なお、断熱層１４Ａ、１４Ｂは、例えば紫外線吸収剤等の各種添加剤を含んで構成されていてもよい。 The heat insulating 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 heat insulating layers 14A and 14B may contain various additives such as ultraviolet absorbers.
　また、断熱層１４Ａ、１４Ｂは、透光性を有する無機材料により構成されていてもよい。例えば、多孔質のシリカ、アルミナ、チタニア、カーボン、またはこれらの複合体等を用いると、熱伝導率が低くなり断熱効果が高く好ましい。断熱層１４Ａ、１４Ｂは、例えばゾル－ゲル法によって形成することができる。 Also, the heat insulating layers 14A and 14B may be made of a translucent inorganic material. For example, it is preferable to use porous silica, alumina, titania, carbon, or a composite of these, because the thermal conductivity is low and the heat insulating effect is high. The heat insulating layers 14A, 14B can be formed by, for example, a sol-gel method.
　断熱層１４Ａ、１４Ｂの厚みは、例えば３μｍ以上１００μｍ以下であることが好ましく、より好ましくは、例えば５μｍ以上５０μｍ以下である。断熱層１４Ａ、１４Ｂの厚みが薄すぎると充分な断熱効果が得られなくなる虞がある。一方、断熱層１４Ａ、１４Ｂの厚みが厚すぎると、透光性が低下する虞がある。また、光記録媒体１０Ｂの曲げ耐性が低下し、ひび割れ等の欠陥を生じやすくなる虞もある。 The thickness of the heat insulating layers 14A and 14B is preferably, for example, 3 μm or more and 100 μm or less, and more preferably, for example, 5 μm or more and 50 μm or less. If the heat insulating layers 14A and 14B are too thin, there is a possibility that a sufficient heat insulating effect cannot be obtained. On the other hand, if the heat insulating layers 14A and 14B are too thick, there is a possibility that the translucency will be lowered. In addition, the bending resistance of the optical recording medium 10B is lowered, and defects such as cracks are likely to occur.
（変形例３）
　第１から第３、第５の実施形態では、電子供与性色素が、酸および塩基の作用により可逆的色相変化を呈することが可能である例について説明したが、電子供与性色素が、酸の作用により非可逆的色相変化を呈することが可能であってもよい。この場合、熱塩基発生剤の塩基発生温度は、熱酸発生剤の酸発生温度未満であってもよい。変形例３では、レーザー描画後に光記録媒体１０、１０Ａ、１０Ｂを塩基発生温度に加熱し塩基過多の状態にすることにより、画像を定着することができる。 (Modification 3)
In the first to third and fifth embodiments, the electron-donating dye is capable of exhibiting a reversible hue change under the action of an acid and a base. It may be possible to exhibit an irreversible hue change upon action. In this case, the base generation temperature of the thermal base generator may be lower than the acid generation temperature of the thermal acid generator. In Modified Example 3, the image can be fixed by heating the optical recording media 10, 10A, and 10B to the base-generating temperature after the laser drawing to create an excess base state.
（変形例４）
　第１の実施形態では、補助層１２が記録層１３に隣接している例について説明したが、補助層１２と記録層１３の間に中間層が備えられ、この中間層が補助層１２から記録層１３に塩基を拡散可能に構成されていてもよい。
　第２の実施形態においても同様に、補助層１２Ａと記録層１３Ａの間に中間層が備えられ、この中間層が補助層１２Ａから記録層１３Ａに塩基を拡散可能に構成されていてもよい。また、補助層１２Ｂと記録層１３Ｂの間に中間層が備えられ、この中間層が補助層１２Ｂから記録層１３Ｂに塩基を拡散可能に構成されていてもよい。また、補助層１２Ｃと記録層１３Ｃの間に中間層が備えられ、この中間層が補助層１２Ｃから記録層１３Ｃに塩基を拡散可能に構成されていてもよい。
　第３の実施形態においても同様に、補助層１２と記録層１５の間に中間層が備えられ、この中間層が補助層１２から記録層１５に塩基を拡散可能に構成されていてもよい。 (Modification 4)
In the first embodiment, an example in which the auxiliary layer 12 is adjacent to the recording layer 13 has been described. The layer 13 may be configured to allow the base to diffuse.
Similarly, in the second embodiment, an intermediate layer may be provided between the auxiliary layer 12A and the recording layer 13A, and the intermediate layer may be configured to allow the base to diffuse from the auxiliary layer 12A to the recording layer 13A. Further, an intermediate layer may be provided between the auxiliary layer 12B and the recording layer 13B, and the intermediate layer may be configured to allow the base to diffuse from the auxiliary layer 12B to the recording layer 13B. Further, an intermediate layer may be provided between the auxiliary layer 12C and the recording layer 13C, and the intermediate layer may be configured to allow the base to diffuse from the auxiliary layer 12C to the recording layer 13C.
Similarly, in the third embodiment, an intermediate layer may be provided between the auxiliary layer 12 and the recording layer 15 so that the intermediate layer can diffuse the base from the auxiliary layer 12 to the recording layer 15 .
（変形例５）
　第１の実施形態では、塗布法を用いて光記録媒体１０を製造する例について説明したが、その他の方法を用いて光記録媒体１０を製造してもよい。すなわち、塗布以外の方法を用いて補助層１２を形成してもよいし、塗布以外の方法を用いて記録層１３を形成してもよい。 (Modification 5)
In the first embodiment, an example of manufacturing the optical recording medium 10 using the coating method has been described, but the optical recording medium 10 may be manufactured using other methods. That is, the auxiliary layer 12 may be formed using a method other than coating, and the recording layer 13 may be formed using a method other than coating.
　例えば、補助層１２を以下のようにして形成してもよい。予め別の基材に塗布して形成された補助層１２を、例えば接着層を介して基材１１上に貼付してもよい。あるいは、基材１１を補助層形成用塗料に浸漬して補助層１２を形成するようにしてもよい。 For example, the auxiliary layer 12 may be formed as follows. The auxiliary layer 12 that is formed by coating another base material in advance may be attached onto the base material 11 via an adhesive layer, for example. Alternatively, the auxiliary layer 12 may be formed by immersing the substrate 11 in the auxiliary layer forming coating material.
　例えば、記録層１３を以下のようにして形成してもよい。例えば、予め別の基材に塗布して形成された記録層１３を、例えば接着層を介して補助層１２上に貼付してもよい。あるいは、補助層１２が形成された基材１１を、記録層形成用塗料に浸漬して記録層１３を形成するようにしてもよい。 For example, the recording layer 13 may be formed as follows. For example, the recording layer 13 formed by coating another base material in advance may be attached onto the auxiliary layer 12 via an adhesive layer, for example. Alternatively, the recording layer 13 may be formed by immersing the substrate 11 with the auxiliary layer 12 formed thereon in a recording layer forming coating material.
（変形例６）
　第２の実施形態では、光記録媒体１０Ａが、３つの記録層１３Ａ、１３Ｂ、１３Ｃと、３つの補助層１２Ａ、１２Ｂ、１２Ｃとを備える例について説明したが、光記録媒体１０Ａが、３つ以外の複数の記録層と、３つ以外の複数の補助層とを備えるようにしてもよい。複数の記録層と複数の補助層は、記録層と補助層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。複数の記録層にそれぞれ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。 (Modification 6)
In the second embodiment, the optical recording medium 10A includes three recording layers 13A, 13B, 13C and three auxiliary layers 12A, 12B, 12C. A plurality of recording layers other than three and a plurality of auxiliary layers other than three may be provided. The plurality of recording layers and the plurality of auxiliary layers may be laminated such that the recording layers and the auxiliary layers are alternately positioned. Each of the plurality of recording layers may be capable of exhibiting different hues in a colored state. The photothermal conversion agents contained in each of the plurality of recording layers may have absorption wavelength peaks different from each other.
（変形例７）
　第３の実施形態では、記録層１５が、３種のマイクロカプセルを含む例について説明したが、記録層１５が、３種以外の複数種のマイクロカプセルを含んでいてもよい。複数種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。複数種のマイクロカプセルにそれぞれ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。 (Modification 7)
In the third embodiment, the example in which the recording layer 15 contains three types of microcapsules has been described, but the recording layer 15 may contain more than three types of microcapsules. Each of the plurality of types of microcapsules may be capable of exhibiting different hues in a colored state. The photothermal conversion agents contained in the plurality of types of microcapsules may have absorption wavelength peaks different from each other.
（変形例８）
　第２の実施形態における記録層１３Ａ、１３Ｂ、１３Ｃに、第４の実施形態における記録層１３の構成を適用し、第２の実施形態における補助層１２Ａ、１２Ｂ、１２Ｃに、第４の実施形態における補助層１２の構成を適用してもよい。この場合、記録層１３Ａ、１３Ｂ、１３Ｃにそれぞれ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する。 (Modification 8)
The structure of the recording layer 13 in the fourth embodiment is applied to the recording layers 13A, 13B, and 13C in the second embodiment, and the auxiliary layers 12A, 12B, and 12C in the second embodiment are applied to the recording layers 13A, 13B, and 13C of the fourth embodiment. You may apply the structure of the auxiliary layer 12 in . In this case, the photothermal conversion agents contained in the recording layers 13A, 13B, and 13C have different absorption wavelength peaks.
　第２の実施形態における記録層１３Ａ、１３Ｂ、１３Ｃに、第５の実施形態における記録層１３の構成を適用し、第２の実施形態における補助層１２Ａ、１２Ｂ、１２Ｃに、第５の実施形態における補助層１２の構成を適用してもよい。この場合、補助層１２Ａ、１２Ｂ、１２Ｃにそれぞれ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する。 The structure of the recording layer 13 in the fifth embodiment is applied to the recording layers 13A, 13B, and 13C in the second embodiment, and the auxiliary layers 12A, 12B, and 12C in the second embodiment are applied to the recording layers 13A, 13B, and 13C of the fifth embodiment. You may apply the structure of the auxiliary layer 12 in . In this case, the photothermal conversion agents contained in the auxiliary layers 12A, 12B, and 12C have different absorption wavelength peaks.
　第２の実施形態における記録層１３Ａ、１３Ｂ、１３Ｃに、第６の実施形態における記録層１３の構成を適用し、第２の実施形態における補助層１２Ａ、１２Ｂ、１２Ｃに、第６の実施形態における補助層１２の構成を適用してもよい。この場合、補助層１２Ａ、１２Ｂ、１２Ｃにそれぞれ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する。 The structure of the recording layer 13 in the sixth embodiment is applied to the recording layers 13A, 13B, and 13C in the second embodiment, and the auxiliary layers 12A, 12B, and 12C in the second embodiment are applied to the recording layers 13A, 13B, and 13C of the sixth embodiment. You may apply the structure of the auxiliary layer 12 in . In this case, the photothermal conversion agents contained in the auxiliary layers 12A, 12B, and 12C have different absorption wavelength peaks.
（変形例９）
　第３の実施形態におけるマイクロカプセル１５Ａが、発色状態の第１の電子供与性色素、第１の熱塩基発生剤および第１の光熱変換剤を含み、マイクロカプセル１５Ｂが、マイクロカプセル１５Ｂが、発色状態の第２の電子供与性色素、第２の熱塩基発生剤および第２の光熱変換剤を含み、マイクロカプセル１５Ｃが、発色状態の第３の電子供与性色素、第３の熱塩基発生剤および第３の光熱変換剤を含んでいてもよい。補助層１２が、マトリクス樹脂および熱酸発生剤を含んでいてもよい。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していてもよい。 (Modification 9)
The microcapsules 15A in the third embodiment contain the first electron-donating dye in the coloring state, the first thermal base generator and the first photothermal conversion agent, and the microcapsules 15B and 15B are color-developing a second electron-donating dye, a second thermal base generator, and a second photothermal conversion agent in a state of and a third photothermal conversion agent. The auxiliary layer 12 may contain a matrix resin and a thermal acid generator. The first, second and third photothermal conversion agents may have different absorption wavelength peaks.
（変形例１０）
　第１の実施形態の説明のようにして求められる熱酸発生剤の酸発生温度ＴＡおよび熱塩基発生剤の塩基発生温度ＴＢに代えて、下記のようにして求められる熱酸発生剤の酸発生温度ＴＣおよび熱塩基発生剤の塩基発生温度ＴＤを用いてもよい。 (Modification 10)
Instead of the acid generation temperature T A of the thermal acid generator and the base generation temperature T B of the thermal base generator determined as described in the first embodiment, the temperature of the thermal acid generator determined as follows: The acid generation temperature T C and the base generation temperature T D of the thermal base generator may be used.
　熱酸発生剤の酸発生温度ＴＣは次のようにして求められる。まず、第１の実施形態における熱酸発生剤の酸発生温度ＴＡの求め方と同様にして、４０℃以上２８０℃以下の範囲における最大ＯＤｍａｘ（ｆＡ（Ｔ）の最大値）と最小ＯＤｍｉｎ（ｆＡ（Ｔ）の最小値）を求める。次に、以下の式から最小ＯＤｍｉｎから５％増加したＯＤＡを求める。
　ＯＤＡ＝ＯＤｍｉｎ＋（ＯＤｍａｘ－ＯＤｍｉｎ）×０．０５
　次に、上記のようにして求めたＯＤＡを式（Ａ）で表される近似曲線ｆＡ（Ｔ）に代入するか、もしくはグラフの内挿によってＯＤＡが得られる温度を算出し、この温度を熱酸発生剤の酸発生温度ＴＣとする。 The acid generation temperature TC of the thermal acid generator is obtained as follows. First, the maximum OD max ( maximum value of f A ( T)) and the minimum Find OD min (minimum value of f A (T)). Next, the OD A increased by 5% from the minimum OD min is obtained from the following formula.
OD A = OD min + (OD max - OD min ) x 0.05
Next, the OD A obtained as described above is substituted into the approximation curve f A (T) represented by the formula (A), or the temperature at which the OD A is obtained is calculated by interpolation of the graph. The temperature is defined as the acid generation temperature T C of the thermal acid generator.
　熱塩基発生剤の塩基発生温度ＴＤは次のようにして求められる。まず、第１の実施形態における熱塩基発生剤の塩基発生温度ＴＢの求め方と同様にして、４０℃以上２８０℃以下の範囲における最大ＯＤｍａｘ（ｆＢ（Ｔ）の最大値）と最小ＯＤｍｉｎ（ｆＢ（Ｔ）の最小値）を求める。次に、以下の式から最大ＯＤｍａｘから５％減少したＯＤＢを求める。
　ＯＤＢ＝ＯＤｍａｘ－（ＯＤｍａｘ－ＯＤｍｉｎ）×０．０５
　次に、上記のようにして求めたＯＤＢを式（Ｂ）で表される近似曲線ｆＢ（Ｔ）に代入するか、もしくはグラフの内挿によってＯＤＢが得られる温度を算出し、この温度を熱塩基発生剤の塩基発生温度ＴＤとする。 The base generation temperature TD of the thermal base generator is determined as follows. First, the maximum OD max (maximum value of f B ( T )) and the minimum Find OD min (minimum value of f B (T)). Next, the OD B reduced by 5% from the maximum OD max is obtained from the following formula.
OD B =OD max −(OD max −OD min )×0.05
Next, the OD B obtained as described above is substituted into the approximate curve f B (T) represented by the formula (B), or the temperature at which the OD B is obtained is calculated by interpolation of the graph, and this The temperature is defined as the base generation temperature TD of the thermal base generator.
　上記のようにして求められた熱酸発生剤の酸発生温度ＴＣおよび熱塩基発生剤の塩基発生温度ＴＤが、以下の関係式（Ｂ）を満たしていてもよい。
　｜ＴＣ－ＴＤ｜≦２０［Ｋ］　・・・（Ｂ）
　熱酸発生剤の酸発生温度ＴＣおよび熱塩基発生剤の塩基発生温度ＴＤが上記の関係式（Ｂ）を満たすことで、熱酸発生剤が発生する酸の量と、熱塩基発生剤が発生する塩基の量とを拮抗させることができる。したがって、発色と消色とを拮抗させ、発色および消色のいずれか一方が進行することを抑制することができる。 The acid generation temperature TC of the thermal acid generator and the base generation temperature TD of the thermal base generator obtained as described above may satisfy the following relational expression ( B ).
|T C −T D |≦20 [K] (B)
When the acid generation temperature TC of the thermal acid generator and the base generation temperature TD of the thermal base generator satisfy the above relational expression ( B ), the amount of acid generated by the thermal acid generator and the thermal base generator can be antagonized with the amount of base generated. Therefore, it is possible to antagonize coloring and decoloring, and to suppress progress of either coloring or decoloring.
　第２の実施形態において、以下の関係が満たされるようにしてもよい。
　光記録媒体１０Ａが高温に保存された際に、記録層１３Ａにて発色と消色とを拮抗させる観点からすると、第１の熱酸発生剤の酸発生温度ＴＣ１および第１の熱塩基発生剤の塩基発生温度ＴＤ１が、以下の関係式（Ｂ１）を満たすことが好ましい。
　｜ＴＣ１－ＴＤ１｜≦２０［Ｋ］　・・・（Ｂ１） In the second embodiment, the following relationship may be satisfied.
When the optical recording medium 10A is stored at a high temperature, from the viewpoint of balancing the color development and decoloration in the recording layer 13A, the acid generation temperature T C1 of the first thermal acid generator and the first thermal base generation The base generation temperature T D1 of the agent preferably satisfies the following relational expression (B1).
|T C1 −T D1 |≦20 [K] (B1)
　光記録媒体１０Ａが高温に保存された際に、記録層１３Ｂにて発色と消色とを拮抗させる観点からすると、第２の熱酸発生剤の酸発生温度ＴＣ２および第２の熱塩基発生剤の塩基発生温度ＴＤ２が、以下の関係式（Ｂ２）を満たすことが好ましい。
　｜ＴＣ２－ＴＤ２｜≦２０［Ｋ］　・・・（Ｂ２） When the optical recording medium 10A is stored at a high temperature, from the viewpoint of balancing the color development and decoloration in the recording layer 13B, the acid generation temperature TC2 of the second thermal acid generator and the second thermal base generation The base generation temperature TD2 of the agent preferably satisfies the following relational expression (B2).
|T C2 −T D2 |≦20 [K] (B2)
　光記録媒体１０Ａが高温に保存された際に、記録層１３Ｃにて発色と消色とを拮抗させる観点からすると、第３の熱酸発生剤の酸発生温度ＴＣ３および第３の熱塩基発生剤の塩基発生温度ＴＤ３が、以下の関係式（Ｂ３）を満たすことが好ましい。
　｜ＴＣ３－ＴＤ３｜≦２０［Ｋ］　・・・（Ｂ３） When the optical recording medium 10A is stored at a high temperature, from the viewpoint of balancing the color development and decoloration in the recording layer 13C, the acid generation temperature TC3 of the third thermal acid generator and the third thermal base generation The base generation temperature TD3 of the agent preferably satisfies the following relational expression (B3).
|T C3 −T D3 |≦20 [K] (B3)
（その他の変形例）
　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。 (Other modifications)
The embodiments and modifications of the present disclosure have been specifically described above, but the present disclosure is not limited to the above embodiments and modifications, and various modifications are possible based on the technical ideas of the present disclosure. is.
　例えば、上記の実施形態および変形例において挙げた構成、方法、工程、形状、材料および数値等はあくまでも例に過ぎず、必要に応じてこれと異なる構成、方法、工程、形状、材料および数値等を用いてもよい。 For example, the configurations, methods, steps, shapes, materials, numerical values, etc. given in the above embodiments and modifications are merely examples, and different configurations, methods, steps, shapes, materials, numerical values, etc., may be used if necessary. may be used.
　上記の実施形態および変形例の構成、方法、工程、形状、材料および数値等は、本開示の主旨を逸脱しない限り、互いに組み合わせることが可能である。 The configurations, methods, steps, shapes, materials, numerical values, etc. of the above embodiments and modifications can be combined with each other as long as they do not deviate from the gist of the present disclosure.
　上記の実施形態および変形例で段階的に記載された数値範囲において、ある段階の数値範囲の上限値または下限値は、他の段階の数値範囲の上限値または下限値に置き換えてもよい。 In the numerical ranges described step by step in the above embodiments and modifications, 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.
　上記の実施形態および変形例に例示した材料は、特に断らない限り、１種を単独でまたは２種以上を組み合わせて用いることができる。 The materials exemplified in the above embodiments and modifications can be used singly or in combination of two or more unless otherwise specified.
　また、本開示は以下の構成を採用することもできる。
（１）
　マトリクス樹脂、消色状態の電子供与性色素、熱酸発生剤および光熱変換剤を含む記録層と、
　マトリクス樹脂および熱塩基発生剤を含む補助層と
　を備え、
　前記熱酸発生剤が、アンモニウム塩、スルホニウム塩およびヨードニウム塩からなる群より選ばれた少なくとも１種を含む光記録媒体。
（２）
　前記電子供与性色素は、酸および塩基の作用により可逆的色相変化を呈することが可能である（１）に記載の光記録媒体。
（３）
　前記電子供与性色素は、酸の作用により非可逆的色相変化を呈することが可能である（１）に記載の光記録媒体。
（４）
　前記記録層が、複数備えられ、
　前記補助層が、複数備えられ、
　前記記録層と前記補助層とが交互に設けられ、
　複数の前記記録層にそれぞれ含まれる電子供与性色素は、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り、
　複数の前記記録層にそれぞれ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する（１）から（３）のいずれか１項に記載の光記録媒体。
（５）
　前記記録層は、複数種のカプセルを含み、
　複数種の前記カプセルは、前記電子供与性色素、前記熱酸発生剤および前記光熱変換剤を含み、
　複数種の前記カプセルそれぞれに含まれる前記電子供与性色素は、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り、
　複数種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（１）から（３）のいずれか１項に記載の光記録媒体。
（６）
　前記熱酸発生剤の酸発生温度ＴＡおよび前記熱塩基発生剤の塩基発生温度ＴＢが、以下の関係式（Ａ）を満たす（１）から（５）のいずれか１項に記載の光記録媒体。
　｜ＴＡ－ＴＢ｜≦２０［Ｋ］　・・・（Ａ）
（７）
　前記アンモニウム塩、前記スルホニウム塩および前記ヨードニウム塩のアニオンが、硫黄、リン、ホウ素またはアンチモンを含む化合物である（１）から（６）のいずれか１項に記載の光記録媒体。
（８）
　前記熱塩基発生剤が、ジアザビシクロウンデセン塩およびジアザビシクロウンデセン誘導体塩からなる群より選ばれた少なくとも１種を含む（１）から（７）のいずれか１項に記載の光記録媒体。
（９）
　前記ジアザビシクロウンデセン塩および前記ジアザビシクロウンデセン誘導体塩のアニオンが、フェノール、オクチル酸またはホウ酸である（８）に記載の光記録媒体。
（１０）
　マトリクス樹脂、発色状態の電子供与性色素、熱塩基発生剤および光熱変換剤を含む記録層と、
　マトリクス樹脂および熱酸発生剤を含む補助層と
　を備え、
　前記熱酸発生剤が、アンモニウム塩、スルホニウム塩およびヨードニウム塩からなる群より選ばれた少なくとも１種を含む光記録媒体。
（１１）
　マトリクス樹脂、消色状態の電子供与性色素および熱塩基発生剤を含む記録層と、
　マトリクス樹脂、熱酸発生剤および光熱変換剤を含む補助層と
　を備え、
　前記熱酸発生剤が、アンモニウム塩、スルホニウム塩およびヨードニウム塩からなる群より選ばれた少なくとも１種を含む光記録媒体。
（１２）
　マトリクス樹脂、発色状態の電子供与性色素および熱酸発生剤を含む記録層と、
　マトリクス樹脂、熱塩基発生剤および光熱変換剤を含む補助層と
　を備え、
　前記熱酸発生剤が、アンモニウム塩、スルホニウム塩およびヨードニウム塩からなる群より選ばれた少なくとも１種を含む光記録媒体。
（１３）
　（１）から（１２）のいずれか１項に記載の光記録媒体を備える身分証明書。
（１４）
　（１）から（１２）のいずれか１項に記載の光記録媒体を備える冊子。
（１５）
　（１）から（１２）のいずれか１項に記載の光記録媒体を備えるカード。 In addition, the present disclosure can also employ the following configuration.
(1)
a recording layer containing a matrix resin, an electron-donating dye in a decolorized state, a thermal acid generator and a photothermal conversion agent;
an auxiliary layer comprising a matrix resin and a thermal base generator;
The optical recording medium, wherein the thermal acid generator contains at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
(2)
The optical recording medium according to (1), wherein the electron-donating dye is capable of exhibiting a reversible hue change under the action of acid and base.
(3)
The optical recording medium according to (1), wherein the electron-donating dye is capable of exhibiting an irreversible hue change under the action of an acid.
(4)
A plurality of the recording layers are provided,
A plurality of the auxiliary layers are provided,
The recording layers and the auxiliary layers are alternately provided,
The electron-donating dyes contained in each of the plurality of recording layers are capable of exhibiting different hues in a colored state,
The optical recording medium according to any one of (1) to (3), wherein the photothermal conversion agents contained in the plurality of recording layers have different absorption wavelength peaks.
(5)
The recording layer contains a plurality of types of capsules,
The plurality of types of capsules contain the electron-donating dye, the thermal acid generator and the photothermal conversion agent,
The electron-donating dyes contained in each of the plurality of types of capsules are capable of exhibiting different hues in a colored state,
The optical recording medium according to any one of (1) to (3), wherein the photothermal conversion agents contained in each of the plurality of types of capsules have absorption wavelength peaks different from each other.
(6)
The light according to any one of (1) to (5), wherein the acid generation temperature T A of the thermal acid generator and the base generation temperature T B of the thermal base generator satisfy the following relational expression (A): recoding media.
|T A −T B |≦20 [K] (A)
(7)
The optical recording medium according to any one of (1) to (6), wherein the anion of the ammonium salt, sulfonium salt and iodonium salt is a compound containing sulfur, phosphorus, boron or antimony.
(8)
Optical recording according to any one of (1) to (7), wherein the thermal base generator contains at least one selected from the group consisting of diazabicycloundecene salts and diazabicycloundecene derivative salts. medium.
(9)
The optical recording medium according to (8), wherein the anion of the diazabicycloundecene salt and the diazabicycloundecene derivative salt is phenol, octylic acid or boric acid.
(10)
a recording layer containing a matrix resin, an electron-donating dye in a colored state, a thermal base generator and a photothermal conversion agent;
an auxiliary layer comprising a matrix resin and a thermal acid generator;
The optical recording medium, wherein the thermal acid generator contains at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
(11)
a recording layer containing a matrix resin, an electron-donating dye in a decolorized state, and a thermal base generator;
an auxiliary layer comprising a matrix resin, a thermal acid generator and a photothermal conversion agent;
The optical recording medium, wherein the thermal acid generator contains at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
(12)
a recording layer containing a matrix resin, an electron-donating dye in a colored state and a thermal acid generator;
an auxiliary layer containing a matrix resin, a thermal base generator and a photothermal conversion agent;
The optical recording medium, wherein the thermal acid generator contains at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
(13)
An identification card comprising the optical recording medium according to any one of (1) to (12).
(14)
A booklet comprising the optical recording medium according to any one of (1) to (12).
(15)
A card comprising the optical recording medium according to any one of (1) to (12).
＜８　適用例＞
　次に、上記第１、第２の実施形態および変形例１から９に係る光記録媒体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。上記光記録媒体１０、１０Ａ、１０Ｂは、各種の電子機器あるいは服飾品の一部、例えば、いわゆるウェアラブル端末として、例えば、時計（腕時計）、鞄、衣服、帽子、眼鏡および靴等の服飾品の一部に適用可能であり、その電子機器等の種類は特に限定されない。また、電子機器や服飾品に限らず、例えば、外装部材として、建造物の壁等の内装や外装、机等の家具の外装等にも適用することができる。 <8 Application example>
Next, application examples of the optical recording media 10, 10A, and 10B according to the first and second embodiments and modified examples 1 to 9 will be described. However, the configuration of the electronic device and the like described below is merely an example, and the configuration can be changed as appropriate. The optical recording media 10, 10A, and 10B are used as a part of various electronic devices or accessories, such as so-called wearable terminals, such as watches (watches), bags, clothes, hats, glasses, and shoes. It can be applied to some, and the type of the electronic equipment is not particularly limited. Moreover, it can be applied not only to electronic devices and furnishings, but also to interiors and exteriors such as walls of buildings as exterior members, exteriors of furniture such as desks, and the like.
　以下の適用例１から９では、光記録媒体１０を身分証明書、カードおよび電子機器等に適用した例について説明するが、光記録媒体１０に代えて光記録媒体１０Ａ、１０Ｂのうちのいずれかを身分証明書、カードおよび電子機器等に適用することも可能であるし、光記録媒体１０、１０Ａ、１０Ｂのうちの２以上を組み合わせて身分証明書、カードおよび電子機器等に適用することも可能である。 In the following application examples 1 to 9, examples in which the optical recording medium 10 is applied to an identification card, a card, an electronic device, etc. will be described. can be applied to identification cards, cards, electronic devices, etc., and two or more of the optical recording media 10, 10A, 10B can be combined and applied to identification cards, cards, electronic devices, etc. It is possible.
　また、以下の適用例１から９では、光記録媒体１０には所定の画像が描画され、記録層１３に記録部と未記録部とが形成されている例について説明する。記録部には、発色状態の電子供与性色素が含まれ、未記録部には、消色状態の電子供与性色素が含まれている。 Further, in application examples 1 to 9 below, an example in which a predetermined image is drawn on the optical recording medium 10 and a recorded portion and an unrecorded portion are formed on the recording layer 13 will be described. The recorded portion contains the electron-donating dye in the colored state, and the unrecorded portion contains the electron-donating dye in the decolored state.
（適用例１）
　図１０Ａは、カード型の身分証明書の外観を表したものである。図１０Ｂは、図１０ＡのＸＢ－ＸＢ線に沿った断面図である。カード型の身分証明書は、カードの一例であり、基材２１と、接着層２２と、光記録媒体２３と、接着層２４と、オーバーレイ層２５とを順次備える。ここでは、光記録媒体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、光記録媒体２３が基材２１の両面に設けられていてもよい。 (Application example 1)
FIG. 10A shows the appearance of a card-type identification card. FIG. 10B is a cross-sectional view along line XB-XB of FIG. 10A. A card-type identification card is an example of a card, and includes a substrate 21, an adhesive layer 22, an optical recording medium 23, an adhesive layer 24, and an overlay layer 25 in sequence. Here, an example in which the optical recording medium 23 is provided on one side of the base material 21 will be described, but the optical recording medium 23 may be provided on both sides of the base material 21 .
　基材２１は、光記録媒体２３を支持する支持基材である。基材２１は、例えば、プラスチック基板である。光記録媒体２３は、光記録媒体１０である。接着層２２は、基材２１と光記録媒体２３とを貼り合わせる。接着層２４は、光記録媒体２３とオーバーレイ層２５とを貼り合わせる。オーバーレイ層２５は、光記録媒体２３を保護する。オーバーレイ層２５は、光記録媒体２３の一方の面を覆っている。 The base material 21 is a supporting base material that supports the optical recording medium 23 . The base material 21 is, for example, a plastic substrate. The optical recording medium 23 is the optical recording medium 10 . The adhesive layer 22 bonds the base material 21 and the optical recording medium 23 together. The adhesive layer 24 bonds the optical recording medium 23 and the overlay layer 25 together. Overlay layer 25 protects optical recording medium 23 . An overlay layer 25 covers one side of the optical recording medium 23 .
　カード型の身分証明書の具体例としては、例えば、運転免許書、健康保険証、住民基本台帳カードまたは個人番号カード（マイナンバーカード）等が挙げられる。 Specific examples of card-type identification include a driver's license, health insurance card, basic resident register card, or individual number card (my number card).
（適用例２）
　図１１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、冊子の一例であり、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、光記録媒体１０が設けられる。光記録媒体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。 (Application example 2)
FIG. 11 shows the appearance of a booklet-type identification card. A booklet-type identification card is an example of a booklet, and includes a plurality of sheets 31 . The plurality of sheets 31 are saddle-stitched. An optical recording medium 10 is provided on at least one surface of the sheet 31 . On the optical recording medium 10, characters, numerical values, facial photographs, etc. are drawn. A specific example of a booklet-type identification card is, for example, a passport.
（適用例３）
　図１２Ａおよび図１２Ｂは、リライト機能付きIntegrated Circuit（ＩＣ）カードの外観を表したものである。このＩＣカードでは、カードの表面が印字面１１０となっており、例えば、シート状の光記録媒体１０が貼付されて構成されている。ＩＣカードの印字面１１０に光記録媒体１０を配置することで、図１２Ａおよび図１２Ｂに示したように、適宜、印字面１１０に描画が可能となる。 (Application example 3)
12A and 12B show the appearance of an integrated circuit (IC) card with a rewrite function. This IC card has a printed surface 110 on the front side of the card, to which, for example, a sheet-like optical recording medium 10 is attached. By placing the optical recording medium 10 on the printing surface 110 of the IC card, it is possible to appropriately draw on the printing surface 110 as shown in FIGS. 12A and 12B.
（適用例４）
　図１３Ａおよび図１３Ｂ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に光記録媒体１０を配置することで、図１３Ａおよび図１３Ｂ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。 (Application example 4)
13A and 13B 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. By placing the optical recording medium 10 on the front side 120B and the back side 120A of the credit card, it is possible to draw on the front side 120B and the back side 120A of the credit card as shown in FIGS. 13A and 13B.
（適用例５）
　図１４Ａ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１４Ｂは、図１４Ａ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、例えば光記録媒体１０が設けられており、これにより、図１４Ｂ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。 (Application example 5)
FIG. 14A shows the external configuration of the front surface of the smartphone. FIG. 14B shows the external configuration of the back surface of the smartphone shown in FIG. 14A. This smartphone includes, for example, a display section 210 , a non-display section 220 , and a housing 230 . An optical recording medium 10, for example, is provided as an exterior member of the housing 230 on, for example, one surface of the housing 230 on the back side, thereby displaying various colors and patterns as shown in FIG. 14B. can be done. Note that although 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.
（適用例６）
　図１５Ａおよび図１５Ｂは、鞄の外観を表したものである。この鞄は、例えば収納部３１０と持ち手３２０とを有しており、例えば、収納部３１０に、例えば光記録媒体１０が取り付けられている。収納部３１０には、例えば光記録媒体１０により、様々な文字や図柄が表示される。また、持ち手３２０部分に光記録媒体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、図１５Ａの例から図１５Ｂ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。 (Application example 6)
15A and 15B show the appearance of the bag. This bag has, for example, a storage section 310 and a handle 320. For example, the optical recording medium 10 is attached to the storage section 310, for example. Various characters and patterns are displayed on the storage unit 310 by the optical recording medium 10, for example. Also, by attaching the optical recording medium 10 to the handle 320 portion, various colored patterns can be displayed, and the design of the storage portion 310 can be changed from the example in FIG. 15A to the example in FIG. 15B. can. It becomes possible to realize an electronic device that is also useful for fashion applications.
（適用例７）
　図１６Ａは自動車の上面の外観を、図１６Ｂは自動車の側面の外観を表したものである。本開示の光記録媒体１０は、上記のように、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、光記録媒体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。 (Application example 7)
FIG. 16A shows the appearance of the top surface of the automobile, and FIG. 16B shows the appearance of the side surface of the automobile. As described above, the optical recording medium 10 of the present disclosure can be used in various parts of the vehicle body such as the bonnet 411, bumper 412, roof 413, trunk cover 414, front door 415, rear door 416 and rear bumper 417. Information and colors can be displayed. Also, the optical 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.
（適用例８）
　図１７は、化粧容器の外観を表したものである。この化粧容器は、例えば収容部５１０と収容部５１０を覆う蓋５２０を有しており、例えば、蓋５２０に、例えば光記録媒体１０が貼付されている。蓋５２０は、この光記録媒体１０により、例えば図１７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、光記録媒体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。 (Application example 8)
FIG. 17 shows the appearance of the cosmetic container. This cosmetic container has, for example, a storage portion 510 and a lid 520 covering the storage portion 510. For example, the optical recording medium 10 is attached to the lid 520, for example. The cover 520 is decorated by the optical recording medium 10, for example, with patterns, colors, or characters as shown in FIG. The pattern, color pattern, characters, etc. of the lid 520 can be written by a predetermined drawing device. It should be noted that the optical recording medium 10 can be attached not only to the front surface (cover 520) of the cosmetic container, but also to the back surface (accommodating portion 510) or the like.
（適用例９）
　図１８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、表面に光記録媒体１０を備える。このようにネイルチップが表面に光記録媒体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光記録媒体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、光記録媒体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。 (Application example 9)
FIG. 18 shows the appearance of the nail tip. A nail tip is an example of an exterior member. The nail tip has an optical recording medium 10 on its surface. By providing the optical recording medium 10 on the surface of the nail tip in this way, various colors and patterns can be displayed. In the above example, the configuration in which the nail tip has the optical recording medium 10 on its surface has been described, but the configuration of the nail tip is not limited to this, and the optical recording medium 10 itself may be the nail tip. . In this case, the substrate 11 has a nail-like shape.
（適用例１０）
　図１９Ａは、ネイルシールの外観を表したものである。図１９Ｂは、図１９ＡのＸＩＸＢ－ＸＩＸＢ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、光記録媒体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が光記録媒体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、光記録媒体１０の基材１１側の面に設けられている。光記録媒体１０は、記録層１３上に保護層１６をさらに備えていてもよい。 (Application example 10)
FIG. 19A shows the appearance of the nail seal. FIG. 19B shows a cross section along line XIXB-XIXB in FIG. 19A. 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 an optical recording medium 10 and an adhesive layer 611 . By including the optical recording medium 10 in the recording medium 610 with an adhesive layer in this manner, various colors and patterns can be displayed. The adhesive layer 611 is provided on the surface of the optical recording medium 10 on the substrate 11 side. The optical recording medium 10 may further include a protective layer 16 on the recording layer 13 .
　光記録媒体１０等は、両手の各指の爪にそれぞれ貼り合わされる複数のネイルシール部６１２を有している。ネイルシール部６１２は、ネイルシールに対して切断または半切断の状態で保持され、粘着層６１１と剥離シート６２０の界面で剥離可能に構成されている。 The optical recording medium 10 and the like have a plurality of nail seal portions 612 that are 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 .
　適用例９、１０では、本開示をネイルチップおよびネイルシートに適用した例について説明したが、ネイルに対する本開示の適用例はこれに限定されるものではない。例えば、支持基材としての地爪（人体の爪）上に補助層１２および記録層１３が直接積層されていてもよい。補助層１２および記録層１３は、地爪に塗料を塗布、硬化することにより形成されてもよいし、補助層１２および記録層１３からなる積層シートが別途形成され、地爪に貼り合わされてもよい。 In Application Examples 9 and 10, examples in which the present disclosure is applied to nail tips and nail sheets have been described, but application examples of the present disclosure to nails are not limited thereto. For example, the auxiliary layer 12 and the recording layer 13 may be directly laminated on a natural nail (human nail) as a supporting substrate. The auxiliary layer 12 and the recording layer 13 may be formed by applying a paint to the base nail and curing it, or a laminated sheet composed of the auxiliary layer 12 and the recording layer 13 may be separately formed and attached to the base nail. good.
＜９　実施例＞
　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。 <9 Examples>
EXAMPLES The present disclosure will be specifically described below with reference to Examples, but the present disclosure is not limited to these Examples.
［実施例１］
（記録層形成用塗料の調製工程）
　下記の材料を配合し、記録層形成用塗料を調製した。
　マトリクス樹脂（三菱ガス化学株式会社製、ＦＰＣ０３３０）：１１質量％
　ロイコ染料（山本化成株式会社製、ＲＥＤ－３）：２質量％
　熱酸発生剤（King Industries Inc.製、ＴＡＧ－２６８９）：２質量％
　光熱変換剤（山田化学株式会社製、ＦＤＮ－００５）：０．０４６質量％
　溶媒（富士フイルム和光純薬株式会社製、メチルエチルケトン（ＭＥＫ））：８４．９５４質量％ [Example 1]
(Preparation step of coating material for forming recording layer)
A coating material for forming a recording layer was prepared by blending the following materials.
Matrix resin (manufactured by Mitsubishi Gas Chemical Company, Inc., FPC0330): 11% by mass
Leuco dye (manufactured by Yamamoto Kasei Co., Ltd., RED-3): 2% by mass
Thermal acid generator (TAG-2689, manufactured by King Industries Inc.): 2% by mass
Photothermal conversion agent (manufactured by Yamada Chemical Co., Ltd., FDN-005): 0.046% by mass
Solvent (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., methyl ethyl ketone (MEK)): 84.954% by mass
（塩基層形成用塗料の調製工程）
　下記の材料を配合し、塩基層形成用塗料（補助層形成用塗料）を調製した。
　マトリクス樹脂（日本合成化工株式会社、ＮＨ－１４）：１０質量％
　熱塩基発生剤（サンアプロ株式会社、ＳＡ１０２）：１質量％
　溶媒（純水）：８９質量％ (Preparation step of paint for forming base layer)
The following materials were blended to prepare a basic layer-forming paint (auxiliary layer-forming paint).
Matrix resin (Nippon Gosei Kako Co., Ltd., NH-14): 10% by mass
Thermal base generator (San-Apro Co., Ltd., SA102): 1% by mass
Solvent (pure water): 89% by mass
　熱酸発生剤の酸発生温度ＴＡおよび熱塩基発生剤の塩基発生温度ＴＢが、上記の関係式（Ａ）を満たすように、熱酸発生剤および熱塩基発生剤は選択された。
　なお、熱酸発生剤の酸発生温度ＴＡ、熱塩基発生剤の塩基発生温度ＴＢはそれぞれ、上記の第１の実施形態にて説明した熱酸発生剤の酸発生温度ＴＡの求め方、熱塩基発生剤の塩基発生温度ＴＢの求め方により求められた値である。 The thermal acid generator and the thermal base generator were selected such that the acid generation temperature T A of the thermal acid generator and the base generation temperature T B of the thermal base generator satisfy the above relational expression (A).
Note that the acid generation temperature T A of the thermal acid generator and the base generation temperature T B of the thermal base generator are each determined by the method for obtaining the acid generation temperature T A of the thermal acid generator described in the first embodiment. , is a value obtained by the method for obtaining the base generation temperature T B of the thermal base generator.
（記録層および塩基層の形成工程）
　まず、上記の塩基層形成用塗料をＰＥＴ基板上に塗布し乾燥させることにより、厚さ５μｍの塩基層（補助層）を形成した。次に、上記の記録層形成用塗料を塩基層上に塗布し乾燥させることにより、厚さ５μｍの記録層を形成した。これにより、目的とする光記録媒体が得られた。 (Step of forming recording layer and base layer)
First, a base layer (auxiliary layer) having a thickness of 5 μm was formed by applying the base layer-forming coating composition onto a PET substrate and drying it. Next, the above recording layer forming coating material was applied onto the base layer and dried to form a recording layer having a thickness of 5 μm. Thus, an intended optical recording medium was obtained.
［比較例１］
　塩基層の形成工程を省いて、ＰＥＴ基板上に記録層を直接形成すること以外は実施例１と同様にして光記録媒体を得た。 [Comparative Example 1]
An optical recording medium was obtained in the same manner as in Example 1 except that the step of forming the base layer was omitted and the recording layer was directly formed on the PET substrate.
［地肌の色相変化の評価］
　上記のようにして得られた実施例１、比較例１の光記録媒体を８０℃、３０％ＲＨの高温環境に保存し、ＯＤ（光学濃度）を測定した。 [Evaluation of Hue Change of Background]
The optical recording media of Example 1 and Comparative Example 1 obtained as described above were stored in a high temperature environment of 80° C. and 30% RH, and OD (optical density) was measured.
［評価結果］
　図２０に、高温保存時間に対するＯＤの変化を示す。図２０から以下のことがわかる。
記録層に隣接して塩基層が備えられた実施例１の光記録媒体では、高温保存時におけるＯＤの上昇が抑制されている。したがって、地肌の色相変化が抑制されている。
　一方、記録層に隣接して塩基層が備えられていない比較例１の光記録媒体では、高温保存時にＯＤが上昇している。したがって、高温保存時における地肌の色相変化が抑制されていない。 [Evaluation results]
FIG. 20 shows changes in OD with respect to high temperature storage time. The following can be understood from FIG.
In the optical recording medium of Example 1 having the base layer adjacent to the recording layer, the increase in OD during high temperature storage is suppressed. Therefore, the hue change of the background is suppressed.
On the other hand, in the optical recording medium of Comparative Example 1, in which the basic layer was not provided adjacent to the recording layer, the OD increased during high temperature storage. Therefore, the hue change of the background during high-temperature storage is not suppressed.
　１０、１０Ａ、１０Ｂ、２３　　光記録媒体
　１１、２１　　基材
　１２、１２Ａ、１２Ｂ、１２Ｃ　　補助層
　１３、１３Ａ、１３Ｂ、１３Ｃ、１５　　記録層
　１４Ａ、１４Ｂ　　断熱層
　１５Ａ、１５Ｂ、１５Ｃ　　マイクロカプセル
　１６　　保護層
　２２、２４　　接着層
　２５　　オーバーレイ層
　３１　　シート
　１１０　　印字面
　裏面　　１２０Ａ
　表面　　１２０Ｂ
　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 Reference Signs List 10, 10A, 10B, 23 Optical recording medium 11, 21 Substrate 12, 12A, 12B, 12C Auxiliary layer 13, 13A, 13B, 13C, 15 Recording layer 14A, 14B Thermal insulation layer 15A, 15B, 15C Microcapsule 16 Protective layer 22, 24 adhesive layer 25 overlay layer 31 sheet 110 printed surface back surface 120A
Surface 120B
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 part

Claims (15)

  1. 　マトリクス樹脂、消色状態の電子供与性色素、熱酸発生剤および光熱変換剤を含む記録層と、
    　マトリクス樹脂および熱塩基発生剤を含む補助層と
    　を備え、
    　前記熱酸発生剤が、アンモニウム塩、スルホニウム塩およびヨードニウム塩からなる群より選ばれた少なくとも１種を含む光記録媒体。     a recording layer containing a matrix resin, an electron-donating dye in a decolorized state, a thermal acid generator and a photothermal conversion agent;
    an auxiliary layer comprising a matrix resin and a thermal base generator;
    The optical recording medium, wherein the thermal acid generator contains at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
  2. 　前記電子供与性色素は、酸および塩基の作用により可逆的色相変化を呈することが可能である請求項１に記載の光記録媒体。 The optical recording medium according to claim 1, wherein the electron-donating dye is capable of exhibiting a reversible hue change under the action of acid and base.
  3. 　前記電子供与性色素は、酸の作用により非可逆的色相変化を呈することが可能である請求項１に記載の光記録媒体。 The optical recording medium according to claim 1, wherein the electron-donating dye is capable of exhibiting an irreversible hue change under the action of acid.
  4. 　前記記録層が、複数備えられ、
    　前記補助層が、複数備えられ、
    　前記記録層と前記補助層とが交互に設けられ、
    　複数の前記記録層にそれぞれ含まれる電子供与性色素は、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り、
    　複数の前記記録層にそれぞれ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する請求項１に記載の光記録媒体。     A plurality of the recording layers are provided,
    A plurality of the auxiliary layers are provided,
    The recording layers and the auxiliary layers are alternately provided,
    The electron-donating dyes contained in each of the plurality of recording layers are capable of exhibiting different hues in a colored state,
    2. The optical recording medium according to claim 1, wherein the photothermal conversion agents contained in the plurality of recording layers respectively have absorption wavelength peaks different from each other.
  5. 　前記記録層は、複数種のカプセルを含み、
    　複数種の前記カプセルは、前記電子供与性色素、前記熱酸発生剤および前記光熱変換剤を含み、
    　複数種の前記カプセルそれぞれに含まれる前記電子供与性色素は、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り、
    　複数種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１に記載の光記録媒体。     The recording layer contains a plurality of types of capsules,
    The plurality of types of capsules contain the electron-donating dye, the thermal acid generator and the photothermal conversion agent,
    The electron-donating dyes contained in each of the plurality of types of capsules are capable of exhibiting different hues in a colored state,
    2. The optical recording medium according to claim 1, wherein the photothermal conversion agents contained in each of the plurality of types of capsules have absorption wavelength peaks different from each other.
  6. 　前記熱酸発生剤の酸発生温度ＴＡおよび前記熱塩基発生剤の塩基発生温度ＴＢが、以下の関係式（Ａ）を満たす請求項１に記載の光記録媒体。
    　｜ＴＡ－ＴＢ｜≦２０［Ｋ］　・・・（Ａ）     2. The optical recording medium according to claim 1, wherein the acid generation temperature TA of the thermal acid generator and the base generation temperature TB of the thermal base generator satisfy the following relational expression ( A ).
    |T A −T B |≦20 [K] (A)
  7. 　前記アンモニウム塩、前記スルホニウム塩および前記ヨードニウム塩のアニオンが、硫黄、リン、ホウ素またはアンチモンを含む化合物である請求項１に記載の光記録媒体。 The optical recording medium according to claim 1, wherein the anions of said ammonium salts, said sulfonium salts and said iodonium salts are compounds containing sulfur, phosphorus, boron or antimony.
  8. 　前記熱塩基発生剤が、ジアザビシクロウンデセン塩およびジアザビシクロウンデセン誘導体塩からなる群より選ばれた少なくとも１種を含む請求項１に記載の光記録媒体。 The optical recording medium according to claim 1, wherein the thermal base generator contains at least one selected from the group consisting of diazabicycloundecene salts and diazabicycloundecene derivative salts.
  9. 　前記ジアザビシクロウンデセン塩および前記ジアザビシクロウンデセン誘導体塩のアニオンが、フェノール、オクチル酸またはホウ酸である請求項８に記載の光記録媒体。 The optical recording medium according to claim 8, wherein the anion of said diazabicycloundecene salt and said diazabicycloundecene derivative salt is phenol, octylic acid or boric acid.
  10. 　マトリクス樹脂、発色状態の電子供与性色素、熱塩基発生剤および光熱変換剤を含む記録層と、
    　マトリクス樹脂および熱酸発生剤を含む補助層と
    　を備え、
    　前記熱酸発生剤が、アンモニウム塩、スルホニウム塩およびヨードニウム塩からなる群より選ばれた少なくとも１種を含む光記録媒体。     a recording layer containing a matrix resin, an electron-donating dye in a colored state, a thermal base generator and a photothermal conversion agent;
    an auxiliary layer comprising a matrix resin and a thermal acid generator;
    The optical recording medium, wherein the thermal acid generator contains at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
  11. 　マトリクス樹脂、消色状態の電子供与性色素および熱塩基発生剤を含む記録層と、
    　マトリクス樹脂、熱酸発生剤および光熱変換剤を含む補助層と
    　を備え、
    　前記熱酸発生剤が、アンモニウム塩、スルホニウム塩およびヨードニウム塩からなる群より選ばれた少なくとも１種を含む光記録媒体。     a recording layer containing a matrix resin, an electron-donating dye in a decolorized state, and a thermal base generator;
    an auxiliary layer comprising a matrix resin, a thermal acid generator and a photothermal conversion agent;
    The optical recording medium, wherein the thermal acid generator contains at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
  12. 　マトリクス樹脂、発色状態の電子供与性色素および熱酸発生剤を含む記録層と、
    　マトリクス樹脂、熱塩基発生剤および光熱変換剤を含む補助層と
    　を備え、
    　前記熱酸発生剤が、アンモニウム塩、スルホニウム塩およびヨードニウム塩からなる群より選ばれた少なくとも１種を含む光記録媒体。     a recording layer containing a matrix resin, an electron-donating dye in a colored state and a thermal acid generator;
    an auxiliary layer containing a matrix resin, a thermal base generator and a photothermal conversion agent;
    The optical recording medium, wherein the thermal acid generator contains at least one selected from the group consisting of ammonium salts, sulfonium salts and iodonium salts.
  13. 　請求項１に記載の光記録媒体を備える身分証明書。 An identification card comprising the optical recording medium according to claim 1.
  14. 　請求項１に記載の光記録媒体を備える冊子。 A booklet comprising the optical recording medium according to claim 1.
  15. 　請求項１に記載の光記録媒体を備えるカード。 A card comprising the optical recording medium according to claim 1.
PCT/JP2022/016141 2021-07-19 2022-03-30 Optical recording medium, identification card, card and booklet WO2023002719A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01150575A (en) * 1987-12-07 1989-06-13 Fuji Photo Film Co Ltd Multicolor thermal recording material
JPH08503455A (en) * 1992-10-23 1996-04-16 ポラロイド コーポレーシヨン Medium and method for recording heat-sensitive image
WO2013068729A1 (en) * 2011-11-10 2013-05-16 Datalase Ltd. Method of forming an image on a substrate

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01150575A (en) * 1987-12-07 1989-06-13 Fuji Photo Film Co Ltd Multicolor thermal recording material
JPH08503455A (en) * 1992-10-23 1996-04-16 ポラロイド コーポレーシヨン Medium and method for recording heat-sensitive image
WO2013068729A1 (en) * 2011-11-10 2013-05-16 Datalase Ltd. Method of forming an image on a substrate

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