WO2024048450A1 - 感熱記録体 - Google Patents

感熱記録体 Download PDF

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Publication number
WO2024048450A1
WO2024048450A1 PCT/JP2023/030713 JP2023030713W WO2024048450A1 WO 2024048450 A1 WO2024048450 A1 WO 2024048450A1 JP 2023030713 W JP2023030713 W JP 2023030713W WO 2024048450 A1 WO2024048450 A1 WO 2024048450A1
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WIPO (PCT)
Prior art keywords
heat
sensitive recording
group
phenolic
recording material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2023/030713
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English (en)
French (fr)
Japanese (ja)
Inventor
麻衣 藤井
英伸 播摩
雄介 江頭
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Osaka Sealing Printing Co Ltd
Original Assignee
Osaka Sealing Printing Co Ltd
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Filing date
Publication date
Application filed by Osaka Sealing Printing Co Ltd filed Critical Osaka Sealing Printing Co Ltd
Priority to EP23860212.2A priority Critical patent/EP4582261A4/en
Priority to NZ819156A priority patent/NZ819156B2/en
Priority to CN202380062444.5A priority patent/CN119768279B/zh
Priority to JP2023570135A priority patent/JP7452937B1/ja
Priority to KR1020257009258A priority patent/KR102849070B1/ko
Priority to US19/106,515 priority patent/US20260002039A1/en
Priority to AU2023335873A priority patent/AU2023335873B2/en
Publication of WO2024048450A1 publication Critical patent/WO2024048450A1/ja
Priority to MX2025002343A priority patent/MX2025002343A/es
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333—Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333—Non-macromolecular compounds
    • 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
    • B41M5/30—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
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/04—Direct thermal recording [DTR]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/28—Storage stability; Improved self life
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/40—Cover layers; Layers separated from substrate by imaging layer; Protective layers; Layers applied before imaging
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/3275—Fluoran compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3372—Macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3375—Non-macromolecular compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/41—Base layers supports or substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/426—Intermediate, backcoat, or covering layers characterised by inorganic compounds, e.g. metals, metal salts, metal complexes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds

Definitions

  • the present invention relates to a heat-sensitive recording material, and more particularly, to a heat-sensitive recording material that has low safety concerns and is excellent in color development, light fastness, and heat resistance.
  • Thermal recording media develops color through a chemical reaction when heated by a thermal head, etc., and can produce recorded images.They are used not only as recording media for facsimiles, automatic ticket vending machines, and scientific measuring instruments, but also for POS systems in retail stores, etc. It is used in a wide range of applications, including thermal recording labels and receipt paper.
  • thermosensitive recording materials are widely used. For this reason, various performances are required of thermosensitive recording materials. For example, when reading a barcode with a barcode reader, color development is required so that the accuracy of reading by the barcode reader is good. Further, when the heat-sensitive recording material is exposed to strong light including ultraviolet rays for a long time, the heat-sensitive recording material is required to have a property (light resistance) that does not easily yellow. Furthermore, it is also required to have excellent heat resistance so that the color development of the printed area does not deteriorate even when heated in a microwave oven or the like, while the non-print area does not easily develop color.
  • Such a heat-sensitive recording material is, for example, a heat-sensitive recording material in which a heat-sensitive recording layer containing a colorless or light-colored electron-donating leuco dye and an electron-accepting color developer is provided on a support,
  • the heat-sensitive recording layer contains a phenolic color developer such as 4-hydroxy-4'-isopropoxydiphenylsulfone as a color developer, and further contains 2-(3'-t-, an ultraviolet absorber) as a light stabilizer.
  • Products containing a phenolic light stabilizer having a phenolic hydroxyl group such as butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole have been proposed (for example, see Patent Documents 1 to 3). .
  • phenolic compounds such as phenolic color developers and phenolic light stabilizers used in Patent Documents 1 to 3 above
  • phenolic compounds such as phenolic color developers and phenolic light stabilizers used in Patent Documents 1 to 3 above
  • thermal recording materials that use additives such as color developers and light stabilizers that do not have a phenol skeleton.
  • the present invention was made in view of these circumstances, and provides a thermal recording medium that has low safety concerns such as endocrine disrupting substances, has excellent color development and light resistance, and is also excellent in heat resistance.
  • the purpose is to provide.
  • the inventors of the present application have developed a color developer that does not have a phenol skeleton (non-phenolic color developer) and a specific light stabilizer that does not have a phenol skeleton in the heat-sensitive recording layer.
  • a color developer that does not have a phenol skeleton
  • a specific light stabilizer that does not have a phenol skeleton in the heat-sensitive recording layer.
  • the present invention was completed based on this knowledge.
  • one aspect of the present invention provides a heat-sensitive recording material in which a heat-sensitive recording layer is laminated on a base material.
  • the heat-sensitive recording layer contains a color former, a non-phenolic color developer, and a non-phenol light stabilizer.
  • heat-sensitive recording materials generally contain phenolic compounds as color developers and light stabilizers.
  • phenolic compounds as color developers and light stabilizers.
  • the color developer and light stabilizer contained in the heat-sensitive recording layer are non-phenolic compounds. Therefore, the above concerns do not arise. Further, even when the above-mentioned non-phenolic compound is employed, the heat-sensitive recording material of the present invention has excellent color development, light resistance, and heat resistance.
  • the non-phenolic light stabilizer contains a hindered amine light stabilizer. This makes it possible to particularly improve light resistance.
  • the non-phenolic color developer may contain a compound represented by the following formula (1) and/or a compound represented by the following formula (2). preferable.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently a hydrogen atom or a substituent.
  • R 6 and R 12 each independently represent a substituent.
  • m represents an integer of 0 to 4. When m is 2 or more, multiple R 6 may be the same. , may be different.
  • n represents an integer from 0 to 4.
  • R 12s When n is 2 or more, multiple R 12s may be the same or different.)
  • R 13 , R 14 , R 15 , R 16 , R 17 , R 19 , R 20 , R 21 , R 22 , and R 23 are each independently a hydrogen atom or a substituent.
  • R 18 represents a substituent.
  • o represents an integer of 0 to 4. When o is 2 or more, multiple R 18s may be the same or different.
  • the non-phenolic color developer contains a compound represented by the following formula (1a) and/or a compound represented by the following formula (2a). is preferred.
  • a compound represented by the following formula (1a) is the same as in formula (1).
  • a compound represented by the following formula (2a) is preferred.
  • the heat-sensitive recording layer further contains a preservability improver.
  • the preservability improver preferably contains a urea urethane compound represented by the following formula (4).
  • the content of the non-phenolic color developer with respect to the entire heat-sensitive recording layer is 10% by mass or more and 50% by mass or less.
  • the content of the non-phenolic light stabilizer relative to the entire heat-sensitive recording layer is preferably 1% by mass or more and 10% by mass or less.
  • thermosensitive recording material with low safety concerns such as endocrine disrupting substances, excellent color development and light resistance, and further excellent heat resistance.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of the heat-sensitive recording material of the present invention.
  • the heat-sensitive recording material of the present invention has a laminated structure in which a heat-sensitive recording layer is laminated on a base material.
  • the heat-sensitive recording layer contains a color former, a non-phenolic color developer, and a non-phenol light stabilizer.
  • the non-phenolic light stabilizer contains a hindered amine light stabilizer.
  • thermal recording medium of the present invention will be described in detail based on the drawings, but the present invention is not limited to the following embodiments.
  • FIG. 1 is a schematic cross-sectional view showing one embodiment of the heat-sensitive recording medium of the present invention.
  • the heat-sensitive recording material 1 of this embodiment has an undercoat layer 6, a heat-sensitive recording layer 3, an intermediate layer 4, and a top coat layer 5 on a sheet-like base material 2 in this order. It has a laminated structure.
  • the base material 2 functions as a support for the thermosensitive recording medium 1.
  • the base material 2 include wood-free paper, art paper, coated paper, kraft paper, laminated paper made by laminating thermoplastic resin such as polyethylene on these paper base materials, synthetic paper, and porous nonwoven fabric. High quality materials can be used. Further, transparent synthetic resin films such as polypropylene film, polyethylene terephthalate film, polystyrene film, polycarbonate film, etc. can be used. Note that the thickness of the base material 2 is not particularly limited, but when the thickness of the base material 2 is adjusted to about 10 ⁇ m to 100 ⁇ m, a base material 2 with excellent coating properties can be obtained. Furthermore, a base material 2 with excellent transparency can be obtained.
  • the undercoat layer 6 has functions such as heat insulating properties that prevent the dissipation of heat applied from the thermal head and cushioning properties.
  • the undercoat layer 6 is formed, for example, by adding hollow particles as a filler to a binder.
  • the average particle diameter of the hollow particles added as a filler to the undercoat layer 6 is preferably 1 ⁇ m to 100 ⁇ m. Within this range, the heat insulating properties of the undercoat layer 6 are improved.
  • the average particle diameter is a weight average particle diameter measured by laser diffraction method.
  • the average particle diameter can be measured by laser diffraction using, for example, Microtrac Bell's product name “MT3300EX-II”.
  • the hollowness ratio of the hollow particles is preferably 30% to 99%. Within this range, the heat insulating properties of the undercoat layer 6 are improved. Furthermore, the higher the hollowness ratio of the hollow particles, the higher the heat insulating effect. Therefore, the color former can effectively develop color with a small amount of heat. In other words, when the hollowness ratio is increased, the printing quality of the thermal recording medium 1 is improved.
  • Hollowness ratio ⁇ (volume of voids)/(volume of hollow particles) ⁇ 100
  • the content of hollow particles in the undercoat layer 6 is preferably 40 parts by mass to 90 parts by mass with respect to 100 parts by mass of the undercoat layer.
  • the material constituting the hollow particles is, for example, a thermoplastic resin.
  • thermoplastic resins include polystyrene resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyvinyl acetate resins, polyacrylic ester resins, polyacrylonitrile resins, and polybutadiene resins. It will be done.
  • filler for the undercoat layer 6 materials other than hollow particles may be used.
  • materials other than hollow particles may be used.
  • these fillers can be used alone or in combination of two or more.
  • binder contained in the undercoat layer 6 examples include acrylic-styrene copolymer, styrene-butadiene copolymer, acrylic-butadiene-styrene copolymer, vinyl acetate resin, and vinyl acetate-acrylic acid copolymer. , styrene-acrylic ester copolymer, acrylic ester resin, polyurethane resin, and the like.
  • the coating amount (dry weight) of the undercoat layer 6 is preferably 1 g/m 2 to 10 g/m 2 .
  • the thickness of the undercoat layer 6 is preferably 1 ⁇ m to 20 ⁇ m.
  • the undercoat layer 6 properly exhibits a heat insulating function.
  • the heat-sensitive recording layer 3 is a layer that develops color through a chemical reaction when heated by a thermal head or the like, and forms a recorded image on the heat-sensitive recording body 1.
  • the heat-sensitive recording layer 3 contains a color former, a non-phenolic color developer, and a non-phenolic light stabilizer.
  • a coloring agent that develops color when heated is a component that develops color through a chemical reaction when heated by a thermal head or the like, and forms a recorded image on the thermal recording medium 1 of this embodiment.
  • the coloring agent that develops color upon heating commonly used leuco dyes can be used.
  • leuco dye examples include 3-(N-isobutyl-N-ethyl)amino-6-methyl-7-anilinofluorane, 3-(N-isopentyl-N-ethyl)amino-6-methyl- 7-o-chloroanilinofluorane, 3-(N-methyl-Np-toluidino)-6-methyl-7-anilinofluorane, 3-(N-ethyl-Np-toluidino)-6 -Methyl-7-anilinofluorane, 3-(N-ethyl-N-isopentyl)amino-6-methyl-7-anilinofluorane, 3-(N-ethoxypropyl-N-ethyl)amino-6- Methyl-7-anilinofluorane, 3-(N-cyclohexyl-N-methyl)amino-6-methyl-7-anilinofluorane, 3-(N-methyl-methyl
  • the particle size of the coloring agent is preferably 0.1 to 1.0 ⁇ m. Since the coloring agent reacts by melting, the reaction slows down as the particle size increases, resulting in lower sensitivity characteristics. On the other hand, as the particle size becomes smaller, the risk of color development at unexpected temperatures increases due to the heat used when drying the paint.
  • the particle size refers to a 50% average particle size measured using a Microtrack laser analysis/scattering particle size analyzer.
  • the coloring agent is preferably contained in an amount of about 10 to 20% by mass based on the entire heat-sensitive recording layer 3 in order to obtain excellent coloring properties.
  • the color developer described below is preferably contained in a dry weight ratio of 1 to 3 to 1 part of the color former.
  • the heat-sensitive recording layer 3 contains a non-phenolic color developer instead of the conventionally widely used phenolic color developer.
  • Non-phenolic color developers are various electron-accepting substances that react with the above-mentioned leuco dyes when heated to cause the leuco dyes to develop color, and are compounds that do not have phenolic hydroxyl groups.
  • the structure in which the heat-sensitive recording layer 3 contains a non-phenolic color developer means that a phenolic color developer whose safety is at risk as an endocrine disruptor is not intentionally used.
  • the leuco dye can be efficiently colored.
  • the heat-sensitive recording layer 3 may unavoidably contain a trace amount of a phenol compound as an impurity that does not cause safety concerns as an endocrine disruptor. A case where the heat-sensitive recording layer 3 inevitably contains such a trace amount of a phenolic compound is within the scope of the present invention.
  • any known color developer that does not have a phenolic hydroxyl group can be used without particular limitation, such as 2,2-bis[(4-methyl-3-phenoxycarbonyl). aminophenyl)urea] diphenylsulfone, 4,4'-bis(p-tolylsulfonylaminocarbonylamino)diphenylmethane, 2'-(3-phenylureido)benzenesulfonanilide, N-(p-toluenesulfonyl)-N'- (3-p-toluenesulfonyloxyphenyl)urea and the like can be used.
  • non-phenolic color developer can also be used as the color developer.
  • present inventors have found that compounds represented by the following formula (1) and the following formula (2) are suitable from the viewpoint of further improving the heat resistance of the thermosensitive recording material 3.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently a hydrogen atom or a substituent.
  • R 6 and R 12 each independently represent a substituent.
  • m represents an integer of 0 to 4. When m is 2 or more, multiple R 6 may be the same. , may be different.
  • n represents an integer from 0 to 4. When n is 2 or more, multiple R 12s may be the same or different.
  • R 13 , R 14 , R 15 , R 16 , R 17 , R 19 , R 20 , R 21 , R 22 , and R 23 are each independently a hydrogen atom or a substituent.
  • R 18 represents a substituent.
  • o represents an integer of 0 to 4. When o is 2 or more, multiple R 18s may be the same or different.
  • organic groups other than hydrogen atoms can be used without particular limitation, such as halogen atoms, nitro groups, amino groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, and alkylcarbonyl groups.
  • examples include an oxy group, an alkylcarbonylamino group, an arylcarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a monoalkylamino group, a dialkylamino group, and an arylamino group.
  • halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.
  • alkyl (group) examples include methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, secondary butyl group, tertiary butyl group, normal pentyl group, isopentyl group, tertiary Pentyl group, neopentyl group, 2,3-dimethylpropyl group, 1-ethylpropyl group, 1-methylbutyl group, 2-methylbutyl group, n-hexyl group, isohexyl group, 2-hexyl group, 3-hexyl group, 2-methyl Straight chain or branched alkyl having 1 to 12 carbon atoms such as pentyl group, 3-methylpentyl group, normal heptyl group, normal octyl group, normal nonyl group, normal decyl, normal undecyl group, normal dodecyl group, etc.
  • alkoxy group examples include methoxy group, ethoxy group, normal propoxy group, isopropoxy group, normal butoxy group, secondary butoxy group, tertiary butoxy group, normal pentyloxy group, isopentyloxy group, and tertiary pentyl group.
  • aryl (group) examples include aromatic hydrocarbon groups having 6 to 10 carbon atoms such as phenyl group, 1-naphthyl group, and 2-naphthyl group.
  • dialkylamino group the two alkyl groups may be the same or different.
  • a compound represented by the following formula (1a) is preferable from the viewpoint of imparting excellent color development and heat resistance to the thermosensitive recording material 1.
  • a compound represented by the following formula (2a) is preferable from the viewpoint of imparting excellent color development and heat resistance to the thermosensitive recording material 1.
  • a specific example is [3-(3-phenylureido)phenyl]-4-methylbenzenesulfonate represented by the following formula (2b).
  • the heat-sensitive recording layer 3 may contain a single non-phenolic color developer, or may contain two or more kinds of non-phenolic color developers.
  • thermosensitive recording material 1 By using at least one or both of the compound represented by the above general formula (1) and the above general formula (2) as a non-phenolic color developer in the heat-sensitive recording layer 3, The heat resistance and color development of the thermosensitive recording material 1 can be improved.
  • the content of the non-phenolic color developer with respect to the entire heat-sensitive recording layer 3 is preferably 10% by mass or more and 50% by mass or less.
  • a configuration in which the content of the non-phenolic color developer is 10% by mass or more is preferable in that it is possible to prevent poor color development (lower optical density) due to lack of color developer.
  • color development becomes poor optical density becomes low
  • too much color developer i.e., insufficient dye
  • a phenolic color developer is not intentionally used as a color developer in the heat-sensitive recording layer 3, but a trace amount of a phenolic compound is used as an impurity in the non-phenolic color developer. may be unavoidably included.
  • impurities include, for example, sulfonic acid esters (-SO 2 -O-) and substituents contained in non-phenolic color developers represented by formulas (1) and/or (2) above. Examples include compounds in which all or part of an alkoxy group, aryloxy group, alkylcarbonyloxy group, etc. is hydrolyzed. Phenolic compounds included as such impurities may function as color developers in some cases.
  • the above-mentioned phenolic compound that may be unavoidably contained as an impurity in the heat-sensitive recording layer 3 is contained in a trace amount of ppm level that can be detected by instrumental analysis (e.g., 100 ppm with respect to the entire heat-sensitive recording layer 3).
  • ppm level that can be detected by instrumental analysis
  • the heat-sensitive recording layer 3 contains a non-phenolic light stabilizer instead of a conventionally widely used phenolic light stabilizer such as a phenolic ultraviolet absorber.
  • a non-phenolic light stabilizer is a substance (light stabilizer) that suppresses photodeterioration such as deterioration of physical properties or discoloration due to exposure to light such as sunlight, and is a compound that does not have a phenolic hydroxyl group.
  • the configuration in which the heat-sensitive recording layer 3 contains a non-phenolic light stabilizer means that a phenolic compound whose safety is at risk as an endocrine disruptor is not intentionally used.
  • the heat-sensitive recording layer 3 of this embodiment may contain a phenolic light stabilizer that does not pose safety concerns as an endocrine disruptor and does not affect color development, light fastness, or heat resistance. shall be included within the scope of the invention.
  • any known light stabilizer that does not have a phenolic hydroxyl group can be used without particular limitation.
  • examples include hindered amine light stabilizers, oxalic acid anilide ultraviolet absorbers, and cyanoacrylate ultraviolet absorbers.
  • the inventors of the present invention have found that a hindered amine light stabilizer (HALS) is suitable from the viewpoint of further improving the light resistance and heat resistance of the thermosensitive recording material 1.
  • HALS hindered amine light stabilizer
  • Hindered amine light stabilizers are compounds that have one or more 2,2,6,6-tetraalkylpiperidine skeletons (for example, 2,2,6,6-tetramethylpiperidine skeletons) in the molecule, and the nitrogen of piperidine It is thought that nitroxy radicals generated by oxidation of atoms exert a stabilizing function by capturing radicals.
  • hindered amine light stabilizer compounds having one or more 2,2,6,6-tetraalkylpiperidine skeletons (for example, 2,2,6,6-tetramethylpiperidine skeletons) in the molecule can be used without particular limitation.
  • a compound having a group represented by the following formula (3) can be mentioned.
  • R a is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a hydroxyalkyl group having 1 to 30 carbon atoms, a carbon atom Represents a hydroxyalkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an oxy radical, and these alkyl groups, alkoxy groups, hydroxyalkyl groups, hydroxyalkoxy groups, and alkenyl groups are oxygen atoms or carbonyl groups. (Single or multiple groups may be interrupted. Also, the group of general formula (3) is bonded at the position marked * in general formula (3).)
  • the hindered amine light stabilizer may contain one or more groups of general formula (3).
  • Examples of the alkyl group having 1 to 30 carbon atoms that can be represented by R a in general formula (3) include straight-chain alkyl groups and branched alkyl groups.
  • Straight chain alkyl groups include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, Examples include pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetracosyl group, pentacosyl group, hexacosyl group, heptacyl group, octa
  • Examples of the alkoxy group having 1 to 30 carbon atoms that can be represented by R a in general formula (3) include alkoxy groups corresponding to the alkyl groups described above.
  • Examples of the hydroxyalkyl group having 1 to 30 carbon atoms that can be represented by R a in the general formula (3) include hydroxyalkyl groups corresponding to the alkyl groups described above.
  • Examples of the alkenyl group having 2 to 30 carbon atoms that R a in general formula (3) can include include ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, Decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icosenyl group, henicosenyl group, docosenyl group, tricosenyl group, tetracosenyl group, pentacocenyl group, hexacosenyl group , heptacosenyl group,
  • R a is preferably a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, from the viewpoint of thermal stability, coloring resistance, and heat coloring resistance.
  • An alkyl group having 1 to 30 carbon atoms is more preferred, an alkyl group having 1 to 4 carbon atoms is even more preferred, and a methyl group is most preferred.
  • examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 2,2, 6,6-tetramethyl-4-piperidylbenzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1 , 2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl) bis(tridecyl)-1,2,3,4-butanetetracarboxylate, poly[ ⁇ 6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl ⁇ (2,2,6,6-tetramethyl-4-piperidyl)imino ⁇ Hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidyl)
  • R a of the group represented by general formula (3) is preferably a hydrogen atom or a methyl group, and a methyl group is preferable. More preferred.
  • the heat-sensitive recording layer 3 may contain a single hindered amine light stabilizer, or may contain two or more kinds of hindered amine light stabilizers.
  • the content of the non-phenolic light stabilizer in the entire heat-sensitive recording layer 3 is not particularly limited, but is preferably 1% by mass or more and 10% by mass or less, more preferably 5% by mass or more and 10% by mass or less. .
  • the configuration in which the content of the non-phenolic light stabilizer is 1% by mass or more, more preferably 5% by mass or more is suitable because it can impart excellent light resistance to the thermal recording material 1 of the present embodiment. It is.
  • the configuration in which the content of the non-phenolic light stabilizer is 10% by mass or less is suitable in that excellent coloring properties can be imparted to the thermosensitive recording material 1 of this embodiment.
  • the content of the non-phenolic light stabilizer with respect to the total amount of light stabilizers contained in the heat-sensitive recording layer 3 is not particularly limited, but it is possible to reduce the safety concerns such as endocrine disrupting substances while improving light resistance. From the viewpoint of improving heat resistance, the content is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more.
  • the content of the hindered amine photostabilizer relative to the total amount of photostabilizers contained in the heat-sensitive recording layer 3 is not particularly limited, but it is possible to reduce safety concerns such as endocrine disrupting substances while improving light resistance. From the viewpoint of improving heat resistance, the content is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 99% by mass or more.
  • the heat-sensitive recording layer 3 may contain additives such as a binder, a sensitizer, a lubricant, a filler, a preservability improver, and a pigment as appropriate.
  • binder contained in the heat-sensitive recording layer 3 examples include polyvinyl alcohol, modified polyvinyl alcohol, starch, casein, gelatin, polyamide, polyacrylamide, modified polyacrylamide, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose, and polyvinylalcohol.
  • sensitizer examples include stearic acid, stearamide, stearanilide, methylolstearamide, methylenebisstearamide, ethylenebisstearamide, 1-benzyloxynaphthalene, 2-benzyloxynaphthalene, 2, 6-diisopropylnaphthalene, 1,2-diphenoxyethane, 1,2-diphenoxymethylbenzene, 1,2-bis(3,4-dimethylphenol)ethane, 1,2-bis(3-methylphenoxy)ethane , 1,2-bis(4-methylphenoxy)ethane, di(p-chlorobenzyl) oxalate, di(p-methylbenzyl) oxalate, dibenzyl oxalate, p-benzylbiphenyl, m-terphenyl, diphenylsulfone , benzyl p-benzyloxybenzoate, dibenzyl terephthalate, p-toluenes
  • lubricants examples include paraffin wax, fatty acids such as oleic acid, polyolefin waxes such as polyethylene wax, metal soaps such as zinc stearate, ester waxes such as carnauba wax, and oils such as silicone oil and whale oil. Can be mentioned. These lubricants can be used alone or in combination of two or more.
  • fillers examples include aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, aluminum silicate, calcium carbonate, magnesium carbonate, titanium oxide, barium sulfate, silica gel, activated clay, talc, clay, kaolin, calcined kaolin. , diatomaceous earth, white carbon, zinc oxide, silicon oxide, colloidal silica, polystyrene resin particles, urea-formalin resin particles, polyolefin resin particles and the like. These fillers can be used alone or in combination of two or more.
  • preservability improver examples include sodium-2,2'-methylenebis(4,6-di-t-butylphenyl)phosphite, 4,4,butylidenebis(3-methyl-6-t-butylphenol), 1 , 1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,1,3-tris(2-methyl-4-hydroxy-5-cyclohexylphenyl)butane, tris(2 , 6-dimethyl-4-t-butyl-3-hydroxybenzyl)isocyanurate, 4-(2-methylglycyloxy)-4'-benzyloxydiphenylsulfone, 2,2'-methylenebis(4-methyl-6 -t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), diethylthiourea, zinc dibutyldithiocarbamate, 4,4'-thiobis(6-t-butyl
  • preservability improvers can be used alone or in combination of two or more. Further, it may contain a known surfactant.
  • Perishable foods such as meat and fish are sold in packs wrapped in plastic wrap, and a label showing the price etc. is pasted on top of the plastic wrap. Also, because packs are typically displayed stacked, a label may come into contact with the wrap surrounding another pack. This wrap contains a plasticizer to impart plasticity. If the packs are left stacked for a long time, the plasticizer may migrate to the label and affect printing. Therefore, it is preferable that the heat-sensitive recording material has excellent properties such as a print that does not easily disappear even if the plasticizer migrates, that is, "plasticizer resistance.”
  • the heat-sensitive recording layer 3 preferably contains a preservability improver from the viewpoint of print preservability, particularly plasticizer resistance, and in particular, a urea-urethane compound represented by the above formula (4). It is preferable to include.
  • a preservability improver particularly the urea-urethane compound represented by formula (4)
  • the reaction efficiency between the leuco dye and the color developer increases, and an electron transfer complex is generated. It is believed that this makes it easier to print, makes it difficult for reverse reactions to occur, makes the heat-sensitive recording material excellent in color development, makes it difficult for the color density to decrease, and is excellent in print storage stability, especially plasticizer resistance.
  • the urea urethane compound represented by the formula (4) is specifically three types represented by the following formulas (4a) to (4c), and these may be used alone or in a mixture of two or more types.
  • the content of the preservability improver with respect to the entire heat-sensitive recording layer 3 is preferably 1% by mass or more and 20% by mass or less.
  • a configuration in which the content of the preservability improver is 1% by mass or more is preferable because it can suppress a decrease in color density due to plasticizers and the like, and the print preservability, especially plasticizer resistance, is excellent.
  • a configuration in which the content of the preservability improver is 20% by mass or less is preferable in terms of preventing poor color development (lowering of optical density).
  • the content ratio of the preservability improver to the non-phenolic color developer is 1/ 20 to 1/1 is preferable.
  • a configuration in which the content ratio is 1/1 or less is preferable in that it is possible to prevent poor color development (lower optical density).
  • a configuration in which the content ratio is 1/20 or more is preferable because it can suppress a decrease in color density due to plasticizers and the like, and provides excellent print storage stability, particularly plasticizer resistance.
  • the content of the urea-urethane compound represented by formula (4) with respect to the entire heat-sensitive recording layer 3 is 1 mass % or more and 20% by mass or less.
  • a configuration in which the content of the urea-urethane compound is 1% by mass or more is preferable because it can suppress a decrease in color density due to plasticizers and the like, and provides excellent print storage stability, particularly plasticizer resistance.
  • a configuration in which the content of the urea urethane compound is 20% by mass or less is preferable in terms of preventing poor color development (lowering of optical density).
  • the content ratio of the urea urethane compound represented by formula (4) to the non-phenolic color developer is preferably 1/20 to 1/1.
  • a configuration in which the content ratio is 1/1 or less is preferable in that it is possible to prevent poor color development (lower optical density).
  • a configuration in which the content ratio is 1/20 or more is preferable because it can suppress a decrease in color density due to plasticizers and the like, and provides excellent print storage stability, particularly plasticizer resistance.
  • the content of the urea urethane compound represented by formula (4) with respect to the total amount of the preservability improver contained in the heat-sensitive recording layer 3 is not particularly limited, but it suppresses the decrease in color density due to plasticizers etc. 90% by mass or more, more preferably 95% by mass or more, even more preferably 99% by mass or more, from the viewpoint of excellent print storage properties, especially plasticizer resistance.
  • Examples of materials constituting the intermediate layer 4 include polyvinyl alcohol, modified polyvinyl alcohol, starch, modified starch, casein, gelatin, glue, gum arabic, polyamide, polyacrylamide, modified polyacrylamide, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, Hydroxypropyl cellulose, polyvinyl acetate, polyacrylic ester, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, diisobutylene-maleic anhydride copolymer, vinyl acetate-maleic anhydride copolymer , methyl vinyl-maleic anhydride copolymer, isopropylene-maleic anhydride copolymer, styrene-butadiene copolymer, maleic acid copolymer, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer , polyurethane, poly
  • the resin has a water-soluble portion, for example, a polyvinyl alcohol (PVA) resin that has a hydroxyl group as a hydrophilic structural unit, or a core-shell structure in which hydrophobic core particles are coated with a water-soluble shell polymer. Transparency can be improved by using a resin such as a core-shell type acrylic resin.
  • PVA polyvinyl alcohol
  • core-shell type resin for example, a core-shell type acrylic resin commercially available under the name "Varistar (manufactured by Mitsui Chemicals)" can be used.
  • the coating amount (dry weight) of the intermediate layer 4 is preferably 0.3 g/m 2 to 10 g/m 2 .
  • the top coat layer 5 improves the suitability of the heat-sensitive recording material 1 for a thermal head, and allows the heat-sensitive recording layer 3 to develop color smoothly. Specifically, this means that the heat-sensitive recording layer 3 is colored in such a way that problems such as deposits on the thermal head and heat-induced distortion of the surface of the heat-sensitive recording body 1 are prevented as much as possible.
  • the top coat layer 5 of the thermal recording medium 1 plays the role of reducing wear of the thermal head and preventing shortening of the life of the thermal head, without adding elastic particles or the like. This means that so-called thermal head suitability is improved. Furthermore, it is necessary to improve the sticking resistance of the top coat layer 5 to the thermal head.
  • the sticking resistance means that problems caused by the components of the uppermost layer of the heat-sensitive recording material melting due to the heat of the thermal head and sticking to the thermal head are less likely to occur. More specifically, problems such as partial failure to print on the thermal recording medium or distortion of the printed surface are less likely to occur.
  • the top coat layer 5 of this embodiment has evaporation holes and cracks on its surface as recessed portions due to evaporation of water. This reduces the contact area between the surface of the top coat layer 5 and the thermal head.
  • a coating liquid containing hydrophobic resin particles is used as the coating liquid for forming the top coat layer 5.
  • the top coat layer 5 uses an emulsion of hydrophobic resin particles, for example, an emulsion in which hydrophobic acrylic resin particles are dispersed in water, as a binder.
  • the binder for the top coat layer 5 an emulsion of hydrophobic resin particles is used, and no water-soluble polymer is used.
  • a coating solution containing a water-soluble polymer is difficult to aggregate and forms a flexible coating film when it is applied and dried, so no cracks occur in the top coat layer 5 due to shrinkage.
  • this crack is formed by contraction due to aggregation of hydrophobic resin particles, it stops at the top coat layer 5 and does not reach the intermediate layer 4.
  • the three layers of the heat-sensitive recording layer 3, the intermediate layer 4, and the top coat layer 5 are covered with a curtain. Three layers are coated simultaneously using a coater.
  • each coating liquid for forming the heat-sensitive recording layer 3, the intermediate layer 4, and the top coat layer 5 is discharged from each of a plurality of slits and laminated, and the laminated coating liquid is continuously run. . At this time, the coating is applied by freely falling onto the undercoat layer 6 previously formed on the base material 2.
  • the evaporation holes formed in the top coat layer 5 stop at the intermediate layer 4. Therefore, even if oil or the like adheres to the surface of the top coat layer 5, which is the uppermost layer, it will not reach the heat-sensitive recording layer 3, and the heat-sensitive recording layer 3 will not change color.
  • the top coat layer 5 contains additives such as a lubricant, a crosslinking agent, a dispersant, an antifoaming agent, a waterproofing agent, and a filler, as necessary.
  • Examples of the lubricant include polyethylene, zinc stearate, and the like.
  • Examples of the crosslinking agent include zirconium carbonate.
  • fillers examples include aluminum hydroxide, aluminum oxide, aluminum silicate, heavy calcium carbonate, light calcium carbonate, titanium oxide, barium sulfate, silica gel, activated clay, talc, clay, kaolinite, diatomaceous earth, and white carbon. , magnesium carbonate, magnesium oxide, magnesium hydroxide, zinc oxide, polystyrene resin particles, urea-formalin resin particles, polyolefin resin particles and the like. These fillers can be used alone or in combination of two or more. Note that the particle size of the filler contained in the top coat layer 5 is preferably 1.0 ⁇ m or less.
  • thermosensitive recording material 1 As a coating liquid for forming the top coat layer 5, an emulsion in which a hydrophobic acrylic resin is dispersed in water, polyethylene wax as a lubricant, and calcium carbonate as a pigment are mixed in a ratio of 4:3:3.
  • the thermosensitive recording material 1 is manufactured using an aqueous dispersion suspension blended at a dry mass ratio of .
  • the coating amount (dry weight) of the top coat layer 5 is 1 g/m 2 .
  • cracks serving as recesses and moisture evaporation holes are formed on the surface of the top coat layer 5, which is the uppermost layer of the heat-sensitive recording material 1.
  • the surface becomes uneven. This reduces the contact area between the top coat layer 5 and the thermal head, reduces wear on the thermal head, improves suitability for the thermal head, and improves sticking resistance.
  • the thickness of the top coat layer 5 is adjusted to, for example, less than 1 ⁇ m. In this embodiment, the thickness is adjusted to about 0.8 ⁇ m. As a result, the distance from the surface of the top coat layer 5 to the heat-sensitive recording layer 3 is short, so that heat from the thermal head is efficiently conducted to the heat-sensitive recording layer 3. Moreover, since it is thin, it contributes to cost reduction.
  • the cracks on the surface of the top coat layer 5 develop in the thickness direction inside the top coat layer 5, the cracks cause the top coat layer 5 to be divided in the direction perpendicular to the thickness direction, that is, in the lateral direction. That will happen. This suppresses the radiation of heat from the thermal head in the lateral direction. As a result, heat from the thermal head is efficiently conducted to the lower heat-sensitive recording layer 3 located in the thickness direction.
  • the approximately circular moisture evaporation holes have an average diameter of 2 ⁇ m or more.
  • the average diameter of the evaporation pores is calculated by observing the surface of the top coat layer 5 using an electron microscope (SEM) and measuring the diameter of the evaporation pores per unit area, for example, 1 mm 2 . Further, the number of evaporation holes is preferably 30 or more, and more preferably 40 or more, per mm 2 with an average diameter of 5 ⁇ m or more.
  • the surface of the top coat layer 5 can be made to have a large number of evaporation holes and a small number of cracks.
  • the surface of the top coat layer 5 can be made to have only a large number of evaporation holes without cracks.
  • the three layers of the heat-sensitive recording layer 3, the intermediate layer 4, and the top coat layer 5 are simultaneously coated in multiple layers using a curtain coater, but the method is not limited to simultaneous multi-layer coating. , and top coat layer 5 may be formed individually and sequentially.
  • the undercoat layer 6 and the intermediate layer 4 are formed on the base material 2, but in another embodiment of the present invention, at least one of the undercoat layer 6 and the intermediate layer 4 is omitted. You may.
  • the heat-sensitive recording material of the above embodiment has the heat-sensitive recording layer having the above-mentioned structure, and therefore has excellent light resistance, color development, and heat resistance.
  • the amount of change in whiteness (%) expressed by the following formula of the heat-sensitive recording material of this embodiment is preferably ⁇ 5% or more, more preferably is -4.5% or more, more preferably -4% or more.
  • Amount of change in whiteness (%) Whiteness after standing for 100 hours at illuminance 5000 Lux - Whiteness before test Whiteness is determined according to JIS P 8148.
  • the minus sign (-) in the amount of change in whiteness (%) indicates the amount of decrease in whiteness, and the closer it is to 0%, the less decrease in whiteness and the better the light resistance.
  • the absolute value of ⁇ b expressed by the following formula of the thermosensitive recording material of this embodiment is preferably 2.5 or less from the viewpoint of having excellent light resistance and suppressing yellowing and blue discoloration (bluishness) caused by light irradiation. Yes, more preferably 2.4 or less, still more preferably 2.3 or less, particularly preferably 2.2 or less.
  • ⁇ b b value after being left for 100 hours at illuminance 5000 Lux - b value before test
  • the b value represents the chromaticity (b value) in the L * a * b * color space defined by JIS Z8781-4:2013.
  • the b value indicates a change from blue to yellow; the larger the value, the closer to yellow, and the smaller the value, the closer to blue.
  • ⁇ b indicates the amount of change in the b value, and a positive value indicates yellowing, and a negative value indicates bluening. Therefore, the closer the absolute value of ⁇ b is to 0, the less yellowing or blue discoloration occurs, indicating that the light resistance is excellent.
  • the dynamic sensitivity (OD value) of the printing part at 0.16 mj/dot of the thermal recording material of this embodiment is preferably 0.1 or more, more preferably 0.2 or more, from the viewpoint of excellent color development.
  • the dynamic sensitivity (OD value) of the printing part at 0.20 mj/dot of the thermal recording material of this embodiment is preferably 0.6 or more, more preferably 0.7 or more, from the viewpoint of excellent color development.
  • the dynamic sensitivity (OD value) of the printing part at 0.40 mj/dot of the thermal recording material of this embodiment is preferably 1.2 or more, more preferably 1.3 or more, from the viewpoint of excellent color development. .
  • the above-mentioned dynamic sensitivity (OD value) is measured in Examples described below, and the higher the value, the better the color development is.
  • the OD value of the non-printed area in the below-mentioned example (heat resistance evaluation) of the heat-sensitive recording material of this embodiment is determined from the viewpoint that it has excellent heat resistance and that the printed area can be clearly identified even after cooking in a microwave oven or the like. , preferably 0.2 or less, more preferably 0.19 or less, still more preferably 0.18 or less.
  • the OD value of the printed portion in the below-mentioned examples (water resistance evaluation) of the thermal recording material of this embodiment is preferably 1 or more from the viewpoint of excellent water resistance and the ability to clearly identify the printed portion even under humid conditions. Yes, more preferably 1.1 or more, still more preferably 1.2 or more.
  • the OD value of the printed portion of the thermal recording material of this embodiment in the below-mentioned example shows that it has excellent plasticizer resistance, and when left in close contact with plasticizer-containing wrap, etc. From the viewpoint that the printed portion can be clearly identified, it is preferably 1.25 or more, more preferably 1.3 or more, and even more preferably 1.4 or more.
  • heat-sensitive recording materials containing a non-phenolic color developer and a non-phenolic light stabilizer in the heat-sensitive recording layer were prepared, and the color development properties, light resistance, heat resistance, water resistance, and Plasticizer resistance was evaluated. Note that the present invention is not limited to these examples.
  • ⁇ Thermosensitive recording layer> Prepare the coating liquid for forming a heat-sensitive recording layer shown in Tables 1 and 2, and apply the prepared coating liquid for forming a heat-sensitive recording layer onto the above-mentioned undercoat layer at a dry weight of 4.0 g/m. 2 and then drying to form a heat-sensitive recording layer with a thickness of 3.5 ⁇ m on the undercoat layer.
  • the numerical value of each compounded material shows the weight ratio at the time of drying.
  • 3-dibutylamino-6-methyl-7-anilinofluorane with a particle size of 0.6 to 0.7 ⁇ m is used as the leuco dye
  • the color developer 1 is the formula (2b )
  • developer 2 is N,N'-di-[3-(3-phenylureido)phenyl]-4-methylbenzenesulfonate represented by formula (1b) 3-(p-Toluenesulfonyloxy)phenyl]urea was used.
  • light stabilizer 1 includes 1,2,2,6,6-pentamethyl-4-piperidyloctadecanoate, 1,2,3,4-butanetetracarboxylic acid tetramethyl ester, 1,2,2, Reaction product of 6,6-pentamethyl-4-piperidinol and ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol (trade name: ADEKA STAB LA-63P, number average molecular weight: approximately 2000, manufactured by ADEKA Co., Ltd.), and the light stabilizer 2 was a benzotriazole-based (phenol-based) ⁇ -3-(3-(2H- Benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)-1-oxopropyl- ⁇ -hydroxy poly(oxyethylene) was used.
  • the preservability improver 1 a urea urethane compound represented
  • the sensitizer used was 1,2-bis(3-methylphenoxy)ethane (dispersed in a PVA aqueous solution to make a dispersion with a solid content concentration of 20%), and the binder was styrene.
  • An acrylic copolymer emulsion was used, calcium carbonate (dispersed in a 5% sodium hexametaphosphate aqueous solution to make a dispersion with a solid content concentration of 30%) was used as a pigment, and a zinc stearate emulsion was used as a lubricant. It was used.
  • Top coat layer> A mixture of 40 parts by mass of acrylic emulsion (solid content concentration 20%), 5 parts by mass of calcium carbonate, 15 parts by mass of polyethylene wax (solid content concentration 40%), and 40 parts by mass of water was mixed and stirred. The resulting liquid was applied onto the intermediate layer and dried to form a top coat layer having a dry coating weight of 1.0 g/m 2 and a thickness of 0.9 ⁇ m.
  • thermal recording bodies of Examples 1 to 10 and Comparative Examples 1 to 4 were produced.
  • Light resistance evaluation In the light resistance evaluation, optical density (OD value of printed area/OD value of non-printed area), yellowing (yellowing), and Changes in whiteness were measured for each. The procedure for evaluating light resistance will be explained below.
  • the produced thermal recording medium was tested using a thermal paper printing test device (manufactured by Okura Engineering Co., Ltd., trade name: Pulse Simulator TH-M2/PP) at a printing speed of 50 mm/sec, an applied voltage of 17.0 V, and a head resistance of 870 ⁇ . , the pulse width was set to 0.488 to 1.394 ms, and printing was performed at a printing energy of 0.40 mJ/dot.
  • a thermal paper printing test device manufactured by Okura Engineering Co., Ltd., trade name: Pulse Simulator TH-M2/PP
  • the distance from the fluorescent lamp was confirmed so that the luminance was 5000 Lux, and the heat-sensitive recording material printed above was left at that position for 100 hours.
  • optical densities (OD value of the printed area/OD value of the non-printed area) of the printed area and the non-printed area of the sample of the thermal recording material before the test and after the above-mentioned storage were measured using a spectrophotometer (Videojet X-Rite Co., Ltd.). The measurement was performed using the company's product name: eXact).
  • the whiteness (%) and hue (L, a, b) of the sample of the heat-sensitive recording material before the test and after the above-mentioned standing were measured.
  • the whiteness was measured according to JIS P 8148 using a photovolt reflection densitometer (manufactured by Tokyo Denshoku Co., Ltd., trade name: TC-6DS/A).
  • the hue (L, a, b) was measured using a color difference meter (manufactured by Videojet X-Rite Co., Ltd., trade name: SpectroEye).
  • thermosensitivity evaluation In the dynamic sensitivity test, printing was performed on each thermal recording medium in each Example and each Comparative Example using different printing energies, and the optical density (OD value of the printed portion) at each printing energy was measured. Based on the measurement results, the dynamic sensitivity of each thermosensitive recording material in each Example and each Comparative Example was evaluated. The procedure for the dynamic sensitivity test will be explained below.
  • the produced thermal recording medium was tested using a thermal paper printing test device (manufactured by Okura Engineering Co., Ltd., trade name: Pulse Simulator TH-M2/PP) at a printing speed of 50 mm/sec, an applied voltage of 17.0 V, and a head resistance of 870 ⁇ .
  • the pulse width was set to 0.488 to 1.394 ms, and printing was performed under each condition of printing energy of 0.16 mJ/dot, 0.20 mJ/dot, and 0.40 mJ/dot, and the optical density under the printing energy condition was determined.
  • OD value was measured using a spectrophotometer (manufactured by X-rite, trade name: eXact).
  • the measurement results from the above test are shown in Tables 3 and 4. Similar to the light resistance test above, in the measurement results shown in Tables 3 and 4, when the optical density (OD value) value is large, the color is more developed, and when the value is small, the color development is insufficient. . For example, if the optical density (OD value) value is large even though the printing energy is small, it is evaluated that "color development is good.” On the other hand, if the numerical value of optical density (OD value) is small despite the printing energy being large, it is evaluated that "color development is poor”. In other words, the dynamic sensitivity test is an evaluation of color development.
  • Heat resistance evaluation In the heat resistance test, heat was applied to the printed and non-printed areas of each heat-sensitive recording material in each example and each comparative example, and the optical density (OD value of the printed area) of the printed and non-printed areas was measured. did. Based on the measurement results, the heat resistance of each heat-sensitive recording material in each Example and each Comparative Example was evaluated. Below, the procedure of the heat resistance test will be explained.
  • the produced thermal recording medium was tested using a thermal paper printing test device (manufactured by Okura Engineering Co., Ltd., trade name: Pulse Simulator TH-M2/PP) at a printing speed of 50 mm/sec, an applied voltage of 17.0 V, and a head resistance of 870 ⁇ . , the pulse width was set to 0.488 to 1.394 ms, and printing was performed at a printing energy of 0.40 mJ/dot.
  • a thermal paper printing test device manufactured by Okura Engineering Co., Ltd., trade name: Pulse Simulator TH-M2/PP
  • a container containing 100 g of water (diameter: 12 cm, content: 220 cc) was covered with vinyl chloride wrap (thickness: 10 ⁇ m), and a sample of the thermal recording material printed above was placed on the wrap. (length: 3 cm, width: 4 cm) was pasted.
  • this container was heated for 1 minute using a microwave oven (1500W), and then each optical density of the printed area and non-printed area in the sample of the thermal recording material was calculated (OD value of the printed area / OD value of the non-printed area).
  • the OD value was measured using a spectrophotometer (manufactured by X-rite, trade name: eXact).
  • the produced thermal recording material was tested using a thermal paper printing test device (manufactured by Okura Engineering Co., Ltd., trade name: Pulse Simulator TH-M2/PP) at a printing speed of 50 mm/sec, an applied voltage of 17.0 V, and a head resistance of 870 ⁇ . , pulse width was set to 0.488 to 1.394 ms, and printing was performed under conditions of printing energy of 0.171 mJ/dot.
  • a thermal paper printing test device manufactured by Okura Engineering Co., Ltd., trade name: Pulse Simulator TH-M2/PP
  • thermosensitive recording material A sample of the printed thermosensitive recording material was immersed in water at 23° C. for 24 hours, and then dried.
  • the optical density of the printed and non-printed areas (OD values of the printed and non-printed areas) of the thermal recording material sample was measured using a spectrophotometer (manufactured by Videojet X-Rite Co., Ltd., product name: eXact). Measured using
  • the measurement results from the above test are shown in Table 4.
  • the optical density (OD value) of the printed area when the optical density (OD value) of the printed area is large (in other words, the light reflectance is low), the color density is maintained better (the black color is maintained). If the value is small (in other words, the light reflectance is large), it indicates that the color density has decreased. In other words, it represents the degree of decrease in color density of the printed area when the thermosensitive recording material is immersed in water. Therefore, the water resistance evaluation of the printed portion can be confirmed by checking that the colored portion does not disappear when immersed in water. Specifically, when the optical density (OD value) of the printed portion is large, it means that the printed portion has excellent water resistance. Furthermore, since it is preferable that the non-printed area does not develop color as much as possible, it can be evaluated as having "good water resistance" when the numerical value of the optical density (OD value) is small.
  • Plasticizer resistance evaluation In the plasticizer resistance evaluation, optical density (OD value) was measured. Based on the measurement results, the plasticizer resistance of each heat-sensitive recording material in Examples 7 to 10 and Comparative Example 4 was evaluated. The procedure for plasticizer resistance evaluation will be explained below.
  • the produced thermal recording material was tested using a thermal paper printing test device (manufactured by Okura Engineering Co., Ltd., trade name: Pulse Simulator TH-M2/PP) at a printing speed of 50 mm/sec, an applied voltage of 17.0 V, and a head resistance of 870 ⁇ . , pulse width was set to 0.488 to 1.394 ms, and printing was performed under conditions of printing energy of 0.171 mJ/dot.
  • a thermal paper printing test device manufactured by Okura Engineering Co., Ltd., trade name: Pulse Simulator TH-M2/PP
  • thermosensitive recording sample Three sheets of vinyl chloride wrap (Denka Polymer Co., Ltd. ML-400) were layered on the printed thermosensitive recording sample and brought into close contact with both the front and back surfaces. A load of 300 g/cm 2 was applied and the sample was left in a 40°C environment for 15 hours.
  • optical density (OD value of the printed area) of the printed area and non-printed area of the sample of the thermal recording material after the above test was measured using a spectrophotometer (manufactured by Videojet X-Rite Co., Ltd., product name: eXact). did.
  • the measurement results from the above test are shown in Table 4.
  • the optical density (OD value) of the printed area when the optical density (OD value) of the printed area is large (in other words, the light reflectance is low), the color density is maintained better (the black color is maintained). If the value is small (in other words, the light reflectance is large), it indicates that the color density has decreased. In other words, it represents the degree of reduction in color density of the printed area due to the plasticizer transferred to the thermosensitive recording material when it is brought into close contact with the wrap. Therefore, the evaluation of the plasticizer resistance of the printed area can be confirmed by checking that the colored area does not disappear due to close contact with the wrap. Specifically, when the optical density (OD value) of the printed portion is large, it means that the printed portion has excellent plasticizer resistance. Furthermore, since it is preferable that the non-printed area does not develop color as much as possible, it can be evaluated as having "good plasticizer resistance" when the numerical value of the optical density (OD value) is small.
  • Examples 1 to 3 showed a smaller amount of change in whiteness than Comparative Example 1, and the whiteness after the test was also higher. This is presumed to be because Examples 1 to 3 contain light stabilizer 1 (non-phenolic light stabilizer).
  • the amount of change in whiteness of Comparative Example 2, which contains the same color developer 1 as Examples 1 to 3 and contains a different light stabilizer 2 (phenolic light stabilizer) than Examples 1 to 3, is as follows: It was -3.60. This is smaller than the amount of change in whiteness in Examples 1 to 3. For this reason, it seems that Examples 1 to 3 have inferior light resistance compared to Comparative Example 2.
  • the optical density (OD value) of Examples 1 to 3 was 1.35 to 1.41, and Comparative Examples 1 to 3.
  • the optical density (OD value) of Examples 1 to 3 was 1.51 to 1.55, and when the printing energy was set to 0.20 mJ/dot, the optical density (OD value) of Examples 1 to 3 was 0.88 to 0.93.
  • the optical density (OD value) of Comparative Examples 1 to 2 was 1.15 to 1.20, and when the printing energy was set to 0.16 mJ/dot, the optical density (OD value) of Examples 1 to 3 was 0.
  • the optical densities (OD values) of the non-printed areas in Examples 1 to 3 are all 0.11, whereas the optical densities (OD values) of the non-printed areas in Comparative Examples 1 to 2 are 0.11. .17 to 0.35, and the optical density (OD value) was higher than that of Examples 1 to 3.
  • the optical density (OD value) of the non-printed area of Comparative Example 2 is much higher than the optical density (OD value) of the non-printed area of Examples 1 to 3.
  • thermosensitive recording materials of Examples 4 to 6 containing non-phenolic light stabilizers had comparable color development properties to those of Comparative Example 3, which did not contain light stabilizers.
  • the optical density (OD value) of the printed portion of Examples 4 to 6 was 1.26 to 1.34, and the optical density (OD value) of the printed portion of Comparative Example 3 was: 1.39, and Examples 4 to 6 tended to have lower optical densities (OD values) than Comparative Example 3, which did not contain a light stabilizer.
  • the decrease was about 4 to 10%, and the color development property that could be used satisfactorily as a heat-sensitive recording material was maintained.
  • the optical density (OD value) of the non-printed area of Examples 4 to 6 is 1.16 to 1.18, whereas the optical density (OD value) of the non-printed area of Comparative Example 3 is 0. .23, and the optical density (OD value) was higher than that of Examples 4 to 6.
  • Examples 7 to 10 had smaller changes in whiteness than Comparative Example 4. Moreover, the whiteness after the test was also higher than that of Comparative Example 4. Based on these results, Examples 7 to 10 containing a non-phenolic light stabilizer and a storage stabilizer had lower whiteness than Comparative Example 4, which contained a storage stabilizer but did not contain a light stabilizer. It was confirmed that it is effective in suppressing the decline.
  • Examples 7 to 10 tended to have lower optical densities (OD values) than Comparative Example 4, which did not contain a light stabilizer. However, the decrease was about 0 to 27%, and the color development was good enough to be used as a heat-sensitive recording material.
  • the thermal recording materials of Examples 7 to 10 containing a non-phenolic light stabilizer and a storage stabilizer are the same as Comparative Example 4, which contains a storage stabilizer but does not contain a light stabilizer. It was confirmed that the coloring properties were comparable to each other.
  • the optical density (OD value) of the printed portion of Examples 7 to 10 was 1.24 to 1.29, and the optical density (OD value) of the printed portion of Comparative Example 4 was: 1.34, and Examples 7 to 10 tended to have lower optical densities (OD values) than Comparative Example 4, which did not contain a light stabilizer.
  • the decrease was about 4 to 7%, and the coloring property that could be used satisfactorily as a heat-sensitive recording material was maintained.
  • the optical density (OD value) of the non-printed area in Examples 7 to 10 is 0.05 to 0.06, which is about the same as the optical density (OD value) of 0.05 in the non-printed area of Comparative Example 4. Met.
  • thermal recording materials of Examples 7 to 10 containing a non-phenolic light stabilizer and a storage stabilizer are different from the thermal recording materials of Comparative Example 4, which contains a storage stabilizer but also does not contain a light stabilizer. It was confirmed that it exhibited excellent water resistance comparable to that of the recording medium.
  • the optical density (OD value) of the printed area of Examples 7 to 10 was 1.44 to 1.56, and the optical density (OD value) of the printed area of Comparative Example 4. is 1.20, and Examples 7 to 10 exhibit higher optical density (OD value) than Comparative Example 4, which does not contain a light stabilizer, and in particular, Example 10, which contains a large amount of storage stabilizer. showed a high optical density of 1.56.
  • the optical density (OD value) of the non-printed area in Examples 7 to 10 is 0.04 to 0.06, and the optical density (OD value) of the non-printed area in Comparative Example 4 is 0.05. It was about the same level.
  • the thermal recording materials of Examples 7 to 10 containing a non-phenolic light stabilizer and a storage stability stabilizer are different from the thermal recording materials of Comparative Example 4 which contains a storage stability stabilizer but not a light stabilizer. It can be seen that the plasticizer resistance is better than that of the recording medium, and in particular, the plasticizer resistance is improved by containing a large amount of storage stabilizer. [Conclusion] From the above measurement results, even if the thermal recording medium contains a non-phenolic color developer and a non-phenolic light stabilizer, it has better light resistance, color development, and heat resistance than a thermal recording medium containing a phenolic light stabilizer. It was not confirmed that the properties, water resistance, and plasticizer resistance were inferior.
  • non-phenolic light stabilizer when a non-phenolic light stabilizer is contained in a heat-sensitive recording material, it is possible to improve the light resistance while maintaining good heat resistance of the heat-sensitive recording material, and to suppress a decrease in whiteness and yellowing. It was found that the inclusion of a preservability improver can improve plasticizer resistance in a dose-dependent manner. Furthermore, non-phenolic color developers and non-phenolic light stabilizers are safer than phenolic ones. Therefore, the use of a non-phenolic color developer and a non-phenolic light stabilizer is very effective from an environmental standpoint.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , and R 11 are each independently a hydrogen atom or a substituent.
  • R 6 and R 12 each independently represent a substituent.
  • m represents an integer of 0 to 4. When m is 2 or more, multiple R 6 may be the same. , may be different.
  • n represents an integer from 0 to 4. When n is 2 or more, multiple R 12s may be the same or different.
  • R 13 , R 14 , R 15 , R 16 , R 17 , R 19 , R 20 , R 21 , R 22 , and R 23 are each independently a hydrogen atom or a substituent.
  • the present invention is particularly useful for thermal recording media on which barcodes and the like are printed.

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PCT/JP2023/030713 2022-08-29 2023-08-25 感熱記録体 Ceased WO2024048450A1 (ja)

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CN202380062444.5A CN119768279B (zh) 2022-08-29 2023-08-25 热敏记录体
JP2023570135A JP7452937B1 (ja) 2022-08-29 2023-08-25 感熱記録体
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US19/106,515 US20260002039A1 (en) 2022-08-29 2023-08-25 Heat-sensitive recording medium
AU2023335873A AU2023335873B2 (en) 2022-08-29 2023-08-25 Heat-sensitive recording medium
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