WO2014181745A1 - 金色メタル調の色調を示す感熱記録体、及び/又は異なる2色の発色色調を示す感熱記録体 - Google Patents
金色メタル調の色調を示す感熱記録体、及び/又は異なる2色の発色色調を示す感熱記録体 Download PDFInfo
- Publication number
- WO2014181745A1 WO2014181745A1 PCT/JP2014/062042 JP2014062042W WO2014181745A1 WO 2014181745 A1 WO2014181745 A1 WO 2014181745A1 JP 2014062042 W JP2014062042 W JP 2014062042W WO 2014181745 A1 WO2014181745 A1 WO 2014181745A1
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- WO
- WIPO (PCT)
- Prior art keywords
- dye precursor
- color
- heat
- pyridinyl
- develops
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/41—Base layers supports or substrates
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/315—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by selective application of heat to a heat sensitive printing or impression-transfer material
- B41J2/32—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by selective application of heat to a heat sensitive printing or impression-transfer material using thermal heads
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/333—Colour developing components therefor, e.g. acidic compounds
- B41M5/3333—Non-macromolecular compounds
- B41M5/3335—Compounds containing phenolic or carboxylic acid groups or metal salts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/34—Multicolour thermography
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/04—Direct thermal recording [DTR]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/22—Printing methods or features related to printing methods; Location or type of the layers improving gradation of image
Definitions
- the present invention relates to a heat-sensitive recording material utilizing a color development reaction between a dye precursor and a developer.
- a heat-sensitive recording material that uses a reaction between a dye precursor and a developer and reacts both substances with thermal energy to obtain a color image is well known.
- Such a heat-sensitive recording material is relatively inexpensive, and since the recording device is compact and easy to maintain, it is used not only as a recording medium for facsimiles and printers but also in a wide range of fields.
- the two-color thermal recording material having a color tone with a metallic luster such as a golden metal tone as one of the colors can make the characters and figures more emphasized by taking advantage of the combination of colors that has not existed before. There is a high demand for conversion.
- the two-color thermal recording medium having a yellow color tone can make the characters and figures more emphasized by utilizing the vivid yellow color tone, there is a high demand for practical use.
- thermosensitive recording medium having a yellow coloring color tone
- only the low temperature coloring layer develops color by the low temperature coloring operation, and in the high temperature coloring operation, it has an erasing effect on the coloring system of the low temperature coloring layer.
- the colorant acts to obtain a color of only the high-temperature color-developing layer (see Patent Documents 3 to 5), and two heat-sensitive recording color-developing layers that produce colors of different colors are stacked and discriminated by applying different amounts of heat 2
- Patent Document 6 the present situation is that a satisfactory result is not necessarily obtained in color separation, color density, color image storage stability, and the like.
- the present invention provides a heat-sensitive recording material using a color development reaction between a dye precursor and a developer, and a heat-sensitive recording material in which a color-developed image has a metallic luster and has a brilliant golden metallic tone. Let it be the first issue.
- the present invention provides a heat-sensitive recording material that exhibits a yellow color tone or a gold metal tone color tone and a different color tone, and has a high color density in each color tone and excellent color separation of the recording portion. This is the second issue. It is another object of the present invention to provide a heat-sensitive recording material that combines the first and second problems.
- the present invention relates to the following thermal recording material.
- thermosensitive recording medium comprising a thermosensitive recording layer containing a dye precursor and a developer on a support, wherein the dye precursor is a dye precursor that develops a yellow color tone
- the dye precursor is a dye precursor that develops a yellow color tone
- the support has a metallic luster, and is a support having a metallic luster imparted to the surface of a substrate not having the metallic luster, And / or (b) the dye precursor that develops a yellow color tone is a first dye precursor, and further contains a second dye precursor that develops a color tone different from the first dye precursor
- the first dye precursor is represented by the following general formula (1):
- R 1 and R 2 represent a hydrogen atom or an alkoxy group having 1 to 8 carbon atoms
- R 1 and R 2 may be the same or different
- R 3 has 1 to 4 carbon atoms Represents an alkyl group
- the second dye precursor is (B1) A form of composite fine particles containing a second dye precursor and a polymer compound, or (b2) a thermal recording material which is a dye precursor having a melting point of 200 ° C. or higher.
- Item 2 (a) The support has a metallic luster, and the surface of the substrate not having the metallic luster is provided with a metallic luster, The dynamic recording yellow density obtained by printing the thermal recording body with a thermal head at an applied energy of 0.97 mJ / dot is 1.00 or more, and the thermal recording body is placed on a hot plate at 40 to 220 ° C.
- Item 2 The thermal recording material according to Item 1, wherein the static color development starting temperature at which the color density obtained by contact at 8 ⁇ 10 4 Pa for 5 seconds is 0.2 is 50 ° C. or higher.
- Item 3 (a) The support has a metallic luster, and is a support having a metallic luster applied to the surface of a substrate that does not have a metallic luster, Item 3.
- the heat-sensitive recording material according to Item 1 or 2, wherein the content of the dye precursor that develops the yellow color tone is 0.7 g / m 2 or more.
- Item 4 (a) The support has a metallic luster, and the surface of the substrate not having the metallic luster is provided with a metallic luster,
- the dye precursor that develops the yellow color tone is represented by the following general formula (1):
- Item 4 The heat-sensitive recording material according to any one of Items 1 to 3, which is a dye precursor having a pyridine skeleton in the molecular structure represented by:
- the thermal recording material is a two-color thermal recording material
- the support has a metallic luster, and is a support provided with a metallic luster on the surface of a substrate having no metallic luster
- the dye precursor that develops a yellow color tone is a first dye precursor, and further contains a second dye precursor that develops a color tone different from the first dye precursor
- the first dye precursor is a compound having a pyridine skeleton in the molecular structure represented by the general formula (1)
- the second dye precursor is (B1) a composite fine particle comprising a second dye precursor and a polymer compound
- the thermosensitive recording layer has a multilayer structure comprising at least a first thermosensitive recording layer and a second thermosensitive recording layer, the first dye precursor is contained in the first thermosensitive recording layer, and at least the second dye precursor.
- Item 2 The heat-sensitive recording material according to Item 1, wherein is contained in the second heat-sensitive recording layer in the form of composite fine particles.
- the thermal recording material is a two-color thermal recording material
- the support has a metallic luster, and is a support provided with a metallic luster on the surface of a substrate having no metallic luster
- the dye precursor that develops a yellow color tone is a first dye precursor, and further contains a second dye precursor that develops a color tone different from the first dye precursor
- the first dye precursor is a compound having a pyridine skeleton in the molecular structure represented by the general formula (1)
- the second dye precursor is (B1) a composite fine particle comprising a second dye precursor and a polymer compound
- the first dye precursor having the pyridine skeleton is 4- [2- (2-butoxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2- (2-pentyl).
- the thermal recording material is a two-color thermal recording material
- the support has a metallic luster, and is a support provided with a metallic luster on the surface of a substrate having no metallic luster
- the dye precursor that develops a yellow color tone is a first dye precursor, and further contains a second dye precursor that develops a color tone different from the first dye precursor
- the first dye precursor is a compound having a pyridine skeleton in the molecular structure represented by the general formula (1)
- the second dye precursor is (B1) a composite fine particle comprising a second dye precursor and a polymer compound,
- the thermal recording material is a two-color thermal recording material
- (B) The dye precursor that develops a yellow color tone is a first dye precursor, and further contains a second dye precursor that develops a color tone different from the first dye precursor
- the first dye precursor is a compound having a pyridine skeleton in the molecular structure represented by the general formula (1)
- the second dye precursor is (B1) A thermal recording material in the form of composite fine particles comprising a second dye precursor and a polymer compound
- the thermosensitive recording layer has a multilayer structure comprising at least a first thermosensitive recording layer and a second thermosensitive recording layer, the first dye precursor is contained in the first thermosensitive recording layer, and at least the second dye precursor.
- Item 2 The heat-sensitive recording material according to Item 1, wherein is contained in the second heat-sensitive recording layer in the form of composite fine particles.
- the thermal recording material is a two-color thermal recording material
- the dye precursor that develops a yellow color tone is a first dye precursor, and further contains a second dye precursor that develops a color tone different from the first dye precursor
- the first dye precursor is a compound having a pyridine skeleton in the molecular structure represented by the general formula (1)
- the second dye precursor is (B1)
- the first dye precursor having the pyridine skeleton is 4- [2- (2-butoxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2- (2-pentyl).
- the thermal recording material is a two-color thermal recording material
- (B) The dye precursor that develops a yellow color tone is a first dye precursor, and further contains a second dye precursor that develops a color tone different from the first dye precursor
- the first dye precursor is a compound having a pyridine skeleton in the molecular structure represented by the general formula (1)
- the second dye precursor is (B1) A thermal recording material in the form of composite fine particles comprising a second dye precursor and a polymer compound,
- the yellow color of dynamic color obtained by printing the two-color thermal recording medium with a thermal head with an applied energy of 0.66 mJ / dot is 1.00 or more, and the thermal head with an applied energy of 0.97 mJ / dot.
- Item 10 The heat-sensitive recording material according to Item 1, 8, or 9, wherein the yellow color of dynamic color obtained by printing is 1.00 or more.
- the thermal recording material is a two-color thermal recording material
- (B) The dye precursor that develops a yellow color tone is a first dye precursor, and further contains a second dye precursor that develops a color tone different from the first dye precursor
- the first dye precursor is a compound having a pyridine skeleton in the molecular structure represented by the general formula (1)
- the second dye precursor is (B2) a dye precursor having a melting point of 200 ° C. or higher
- the thermosensitive recording layer has a multilayer structure comprising at least a first thermosensitive recording layer and a second thermosensitive recording layer, the first thermosensitive recording layer contains a first dye precursor, and the second thermosensitive recording layer is Item 2.
- the heat-sensitive recording material according to Item 1 containing a second dye precursor.
- the thermal recording material is a two-color thermal recording material
- the dye precursor that develops a yellow color tone is a first dye precursor, and further contains a second dye precursor that develops a color tone different from the first dye precursor
- the first dye precursor is a compound having a pyridine skeleton in the molecular structure represented by the general formula (1)
- the second dye precursor is (B2) a dye precursor having a melting point of 200 ° C. or higher
- the first dye precursor having the pyridine skeleton is 4- [2- (2-butoxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2- (2-pentyl).
- the thermal recording material is a two-color thermal recording material
- (B) The dye precursor that develops a yellow color tone is a first dye precursor, and further contains a second dye precursor that develops a color tone different from the first dye precursor
- the first dye precursor is a compound having a pyridine skeleton in the molecular structure represented by the general formula (1)
- the second dye precursor is (B2) a dye precursor having a melting point of 200 ° C. or higher
- the yellow color of dynamic color obtained by printing the two-color thermal recording medium with a thermal head with an applied energy of 0.66 mJ / dot is 1.00 or more, and the thermal head with an applied energy of 0.97 mJ / dot.
- the thermal recording material is a two-color thermal recording material
- the dye precursor that develops a yellow color tone is a first dye precursor, and further contains a second dye precursor that develops a color tone different from the first dye precursor
- the first dye precursor is a compound having a pyridine skeleton in the molecular structure represented by the general formula (1)
- the second dye precursor is (B2) a dye precursor having a melting point of 200 ° C. or higher, Item 14.
- the thermal recording material according to any one of Items 1 and 11 to 13, wherein the support has a metallic luster.
- Item 15 (b2) The thermal recording material according to any one of Items 1 and 11 to 14, wherein the dye precursor having a melting point of 200 ° C. or higher is a dye precursor that develops a black color tone.
- Item 16 A dye precursor having a pyridine skeleton in the molecular structure represented by the general formula (1), wherein R 1 and R 2 are dye precursors excluding a case where they are simultaneously hydrogen atoms, The thermosensitive recording material according to any one of 1 to 15.
- thermosensitive recording medium comprising a thermosensitive recording layer containing a dye precursor and a developer on a support, the support has a metallic luster, and the dye precursor develops a yellow color.
- a heat-sensitive recording material which is a dye precursor.
- Item 18 The dynamic color density (dynamic yellow color density) obtained by printing the thermal recording body with a thermal head at an applied energy of 0.97 mJ / dot is 1.00 or more, and the thermal recording medium is 40 Item 18.
- Item 19 The heat-sensitive recording material according to Item 17 or 18, wherein the content of the dye precursor that develops the yellow color tone is 0.7 g / m 2 or more.
- Item 20 The dye precursor that develops the yellow color tone is represented by the following general formula (1):
- R 1 and R 2 represent a hydrogen atom or an alkoxy group having 1 to 8 carbon atoms, and may be the same or different.
- R 3 represents an alkyl group having 1 to 4 carbon atoms.
- Item 20 The thermal recording material according to any one of items 17 to 19, which is a dye precursor having a pyridine skeleton in the molecular structure represented by:
- Item 21 The heat-sensitive recording material according to any one of Items 17 to 20, wherein the support has a metallic luster on the surface of a substrate having no metallic luster.
- Item 22 The method for recording a thermal recording material according to any one of Items 1 to 4 and Items 16 to 21, wherein the gold metal is applied with an applied energy that is equal to or higher than a static color development start temperature by heating with a thermal head.
- a method for recording a heat-sensitive recording material comprising: recording a tone color image and recording a silver metal tone with an applied energy at which a dynamic color density (dynamic color yellow density) is less than 1.00.
- Item 23 A heat-sensitive recording material comprising a heat-sensitive recording layer containing a dye precursor and a developer on a support, wherein the support has a metallic luster, and the dye precursor is represented by the following general formula (1 ):
- R 1 and R 2 represent a hydrogen atom or an alkoxy group having 1 to 8 carbon atoms
- R 3 represents an alkyl group having 1 to 4 carbon atoms.
- R 1 and R 2 may be the same or different. May be.
- a two-color heat-sensitive recording material which is contained in the heat-sensitive recording layer in the form of
- Item 24 A heat-sensitive recording material comprising a heat-sensitive recording layer containing a dye precursor and a developer on a support, wherein the support has a metallic luster, and the dye precursor is represented by the following general formula (1 ):
- R 1 and R 2 represent a hydrogen atom or an alkoxy group having 1 to 8 carbon atoms
- R 3 represents an alkyl group having 1 to 4 carbon atoms.
- R 1 and R 2 may be the same or different. May be.
- the color tone of the body is a metallic tone having a metallic luster of the support
- the second color is a color tone of a mixed color due to the coloring of the first dye precursor and the second dye precursor.
- Two-color thermal recording material Two-color thermal recording material.
- thermosensitive recording layer has a multilayer structure comprising at least a first thermosensitive recording layer and a second thermosensitive recording layer, the first dye precursor is contained in the first thermosensitive recording layer, and at least the second thermosensitive recording layer.
- the first dye precursor having the pyridine skeleton is 4- [2- (2-butoxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2- ( 2-Pentyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2- (2-hexyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N- Dimethylbenzenamine, 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- (2,6-diphenyl-4-pyridinyl) -N, N-dimethylbenzenamine, 4- [2,6-bis (2-butoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2,6-bis (2-pepyl)
- Item 27 The two-color thermosensitive recording according to any one of Items 23 to 26, wherein the second dye precursor is contained in the thermosensitive recording layer in the form of composite fine particles containing the second dye precursor and a polymer compound. Recorded body.
- Item 28 The color tone of the first dye precursor is a metallic color with a metallic luster of the support, and the color tone of the color mixture of the first dye precursor and the second dye precursor is red.
- Item 27 The two-color heat-sensitive recording material according to any one of Items 1, 5 to 7, 16, and 23 to 26, which is black or green.
- Item 29 A dynamic color density (dynamic color yellow density) obtained by printing the thermal recording material with a thermal head with an applied energy of 0.66 mJ / dot is 1.00 or more and 0.97 mJ / dot.
- Item 30 A heat-sensitive recording material comprising a heat-sensitive recording layer containing a dye precursor and a developer on a support, wherein the dye precursor is represented by the following general formula (1):
- R 1 and R 2 represent a hydrogen atom or an alkoxy group having 1 to 8 carbon atoms
- R 3 represents an alkyl group having 1 to 4 carbon atoms.
- R 1 and R 2 may be the same or different. May be.
- a two-color heat-sensitive recording material which is contained in the heat-sensitive recording layer in the form of
- Item 31 A heat-sensitive recording material comprising a heat-sensitive recording layer containing a dye precursor and a developer on a support, wherein the dye precursor is represented by the following general formula (1):
- R 1 and R 2 represent a hydrogen atom or an alkoxy group having 1 to 8 carbon atoms
- R 3 represents an alkyl group having 1 to 4 carbon atoms.
- R 1 and R 2 may be the same or different. May be.
- a two-color thermal recording material characterized in that the color tone is due to color development of the body, and the second color is a color tone of color mixture due to color development of the first dye precursor and the second dye precursor.
- thermosensitive recording layer has a multilayer structure comprising at least a first thermosensitive recording layer and a second thermosensitive recording layer, the first dye precursor is contained in the first thermosensitive recording layer, and at least the second thermosensitive recording layer.
- the first dye precursor having the pyridine skeleton is 4- [2- (2-butoxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2- ( 2-Pentyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2- (2-hexyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N- Dimethylbenzenamine, 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- (2,6-diphenyl-4-pyridinyl) -N, N-dimethylbenzenamine, 4- [2,6-bis (2-butoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2,6-bis (2-pepyl)
- the item according to any one of Items 30 to 32 which is at least one selected from the group consisting of [2,6-bis (2-octyloxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine.
- Two-color thermal recording material is at least one selected from the group consisting of [2,6-bis (2-octyloxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine.
- Item 34 The two-color thermosensitive recording according to any one of Items 30 to 33, wherein the second dye precursor is contained in the thermosensitive recording layer in the form of composite fine particles containing the second dye precursor and a polymer compound. Recorded body.
- Item 35 The color tone of the first dye precursor is yellow, and the color mixture of the first dye precursor and the second dye precursor is red, black, or green 35.
- the two-color thermosensitive recording material according to any one of 1, 8, 10 and 16, and 30 to 34.
- Item 36 The two-color thermosensitive recording material according to any one of Items 1, 8 to 10, 16 and 30 to 35, which emits fluorescence under ultraviolet light by color development of the first dye precursor.
- Item 37 The dynamic color density (dynamic color yellow density) obtained by printing the two-color thermal recording medium with a thermal head at an applied energy of 0.66 mJ / dot is 1.00 or more and 0.97 mJ / Item 37.
- Item 38 A heat-sensitive recording material comprising a heat-sensitive recording layer containing a dye precursor and a developer on a support, wherein the dye precursor is represented by the following general formula (1):
- R 1 and R 2 represent a hydrogen atom or an alkoxy group having 1 to 8 carbon atoms, and R 3 represents an alkyl group having 1 to 4 carbon atoms. R 1 and R 2 may be the same, May be different.
- a two-color heat-sensitive recording material is provided.
- Item 39 The two-color thermosensitive recording according to any one of Items 1, 11 to 16, and 38, wherein both the first dye precursor and the second dye precursor are contained in the heat-sensitive recording layer in the form of solid dispersed fine particles. Recorded body.
- thermosensitive recording layer has a multilayer structure comprising at least a first thermosensitive recording layer and a second thermosensitive recording layer, the first thermosensitive recording layer contains a first dye precursor, and the second thermosensitive recording layer.
- Item 40 The two-color thermal recording material according to Item 38 or 39, wherein the recording layer contains a second dye precursor.
- the total content of the dye precursor that develops a black color tone including the second dye precursor is more than 0.5 times and more than 2.5 times the content of the first dye precursor Item 41.
- the two-color thermosensitive recording material according to any one of Items 1, 11 to 16, and 38 to 40, which is a small range.
- the first dye precursor having the pyridine skeleton is 4- [2- (2-butoxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2- ( 2-Pentyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2- (2-hexyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N- Dimethylbenzenamine, 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine, 4- [2,6-bis (2-butoxyphenyl) -4 -Pyridinyl] -N, N-dimethylbenzenamine, 4- [2,6-bis (2-pentyloxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine,
- Item 43 The dynamic color density (dynamic color yellow density) obtained by printing the two-color thermal recording material with a thermal head at an applied energy of 0.66 mJ / dot is 1.00 or more and 0.97 mJ / Item 43.
- Item 44 The two-color thermal recording material according to any one of Items 38 to 43, wherein the support has a metallic luster.
- the heat-sensitive recording material of the present invention has a metallic luster, a vivid golden metallic tone, and a special color printing product that has been mainly used in the printing field.
- variable information with excellent design can be recorded.
- the color density is high, and the color image has excellent storage stability and light resistance.
- the heat-sensitive recording material of the present invention is a two-color heat-sensitive recording material
- a yellow-colored color tone or a gold-colored color tone when the support has a metallic luster and a color tone different from this color tone.
- the color density is high in each color tone, and the color separation of the recording portion is excellent.
- the present invention is a heat-sensitive recording material comprising a heat-sensitive recording layer containing a dye precursor and a developer on a support, wherein the dye precursor is a dye precursor that develops a yellow color tone,
- the dye precursor is a dye precursor that develops a yellow color tone
- the support has a metallic luster, and is a support having a metallic luster imparted to the surface of a substrate not having the metallic luster, And / or
- the dye precursor that develops a yellow color tone is a first dye precursor, and further contains a second dye precursor that develops a color tone different from that of the first dye precursor.
- the support in the present invention is not particularly limited in type, shape, dimensions, etc., for example, high-quality paper (acidic paper, neutral paper), medium-quality paper, coated paper, art paper, cast-coated paper, glassine paper, paperboard
- high-quality paper acidic paper, neutral paper
- medium-quality paper coated paper, art paper, cast-coated paper, glassine paper, paperboard
- resin-laminated paper polyolefin-based synthetic paper
- synthetic fiber paper nonwoven fabric, synthetic resin film, and the like
- various transparent supports can be appropriately selected and used.
- the support in the present invention has a metallic luster
- a support having a metallic luster itself such as a metal plate, a metal foil, or a metal film, or a support having a metallic luster added to the above-mentioned substrate having no metallic luster, is appropriately selected and used.
- the substrate may be transparent, translucent, or opaque.
- a support having a metallic luster imparted to a film or synthetic paper is preferable.
- a method for imparting a metallic luster to the surface of the substrate there are a plating method, a method of bonding a metal foil such as an aluminum foil, and a method of bonding a paper or film having a metal vapor deposition layer. Furthermore, there is a method in which a metal vapor deposition film such as aluminum or silver is directly provided on the substrate. In this case, a smooth resin layer is preliminarily provided on the surface of the substrate, and a direct vapor deposition method in which a metal vapor is deposited thereon to form a metal layer, or a metal vapor deposition layer previously provided on the film is bonded via an adhesive. There is a method in which the film is peeled off and transferred to a substrate.
- a method of providing a metallic luster layer by printing or coating on a substrate there is also a method of providing a metallic luster layer by printing or coating on a substrate.
- a metal ink obtained by mixing a metal powder such as an aluminum powder or an aluminum paste in which an aluminum powder is dispersed in a solvent with a vehicle.
- an ink using an inorganic pearl pigment such as a mica or a pigment obtained by coating mica with titanium oxide instead of a metal powder.
- the heat-sensitive recording layer in the present invention is formed on a support, and when the support has a metallic luster, it covers part or all of the metallic luster of the support as viewed from the recording surface side.
- the heat-sensitive recording layer may be formed on the side of the support having the metallic luster, and is a metal that can be visually confirmed through the substrate such as a transparent substrate. If it is a support body which has glossiness, you may form in the opposite side of the surface which has metal glossiness of a support body.
- An undercoat layer can also be provided between the support and the heat-sensitive recording layer. When the support has a metallic luster, the undercoat layer preferably does not hide the metallic luster of the support.
- the dye precursor in the thermosensitive recording layer develops a yellowish color tone, but since the colored image has a metallic luster when viewed from the recording surface side, It is possible to present a vivid golden metal tone.
- the dye precursor present in the form of fine particles in the heat-sensitive recording layer and the developer that develops the color of the dye precursor by reacting with heating is once melted by the applied energy of a thermal head and solidified again.
- the irregular reflection in the heat-sensitive recording layer is reduced and a golden metal tone can be obtained through the heat-sensitive recording layer.
- the heat-sensitive recording layer covers the metallic luster of the support, but since the color image exhibits a golden metal tone, the degree to which the thermo-sensitive recording layer conceals the metallic luster of the support is limited.
- it is not particularly limited, and it may be a mat-like plain paper like when viewed from the recording surface side, or may be such that the metallic luster can be visually confirmed through the heat-sensitive recording layer.
- the dynamic color density obtained by printing the thermal recording medium with a thermal head at an applied energy of 0.97 mJ / dot is 1.00 or more, and the thermal recording medium is placed on a hot plate at 40 to 220 ° C.
- the static color development start temperature at which the color density obtained by contact at 8 ⁇ 10 4 Pa for 5 seconds is 0.2 is 50 ° C. or higher.
- the upper limit of the dynamic color density is not particularly limited, but if it exceeds 2.0, the color developability is saturated.
- the static color development start temperature is more preferably 60 ° C. or higher.
- the upper limit of the static color development start temperature is not particularly limited, but is preferably 90 ° C. or lower, more preferably 80 ° C. or lower, and still more preferably 70 ° C. or lower in order to reduce the load on the printer.
- the color density indicates the Y (yellow) density
- the dynamic color density indicates the Y (yellow) density of the dynamic color.
- the method of adjusting the content of the dye precursor or adjusting the form of the dye precursor can be used.
- the dynamic color development is a color obtained by printing with a thermal head
- the static color development means a color obtained by contacting with a hot plate.
- the content of the dye precursor that develops a yellow color tone is preferably 0.7 g / m 2 or more in terms of the dry weight in the heat-sensitive recording layer. More preferably, it is 1.0 g / m ⁇ 2 > or more, More preferably, it is 1.5 g / m ⁇ 2 > or more. Thereby, it is possible to increase the color density and obtain a clearer golden metal tone.
- the upper limit of the content is not particularly limited, greater than 6 g / m 2 and color developing property from saturating, it is preferable that the 6 g / m 2 or less.
- dye precursor that develops a yellow color tone examples include, for example, The following general formula (1):
- Dye precursor having a pyridine skeleton in the molecular structure; dye precursors having a yellow color without a pyridine skeleton include, for example, 3,6-dimethoxyfluorane, 1- (4-n -Dodecyloxy-3-methoxyphenyl) -2- (2-quinolyl) ethylene, 2,2-bis (4- (2- (4-diethylaminophenyl) quinazolyl) oxyphenyl) propane, 1- (2-quinolyl) -2- (3-methoxy-4-dodecyloxyphenyl) ethene, 4-chloro-N- (4- (N- (4-methylbenzyl) -N-methylamino) benzylidene) aniline and the like.
- the color image has excellent storage stability. If the color image fades, the reason is because the components in the heat-sensitive recording layer crystallize, but if the support has a metallic luster, the metal tone is impaired more than the yellow color tone can be visually reduced. There is a fear.
- a dye precursor having a pyridine skeleton in the molecular structure represented by the general formula (1) is preferable as a dye precursor that develops a yellow color tone from the viewpoint of improving the storage stability of a color image.
- R 1 and R 2 is more preferable that unless at the same time hydrogen atoms, it is preferred that R 1 and R 2 are different.
- R 1 and R 2 are a hydrogen atom or an alkoxy group having 1 to 8 carbon atoms which may be branched, and may be the same or different, and R 3 has 1 to 4 carbon atoms.
- at least R 1 and R 2 are preferable because a linear saturated hydrocarbon group can be easily introduced industrially.
- any one of R 1 and R 2 is an alkoxy group having 4 to 8 carbon atoms because the effects of the present invention can be exhibited without any regret. Furthermore, from the viewpoint of further increasing the color density, it is preferable that either R 1 or R 2 represents a hydrogen atom.
- the form of the dye precursor contained in the heat-sensitive recording layer is not particularly limited, and may be contained in the heat-sensitive recording layer in the form of solid dispersed fine particles. May be contained in the heat-sensitive recording layer in a form in which composite fine particles containing a polymer compound such as a photosensitive resin are formed.
- the present invention is a two-color heat-sensitive recording material
- it is a heat-sensitive recording material comprising a heat-sensitive recording layer containing a dye precursor and a developer on a support, and the general formula (1
- the first dye precursor having a pyridine skeleton in the molecular structure represented by (2) and a second dye precursor that develops a color tone different from that of the first dye precursor.
- thermosensitive recording material comprising a thermosensitive recording layer containing a dye precursor and a developer on a support, wherein the molecular structure represented by the general formula (1) is used as the dye precursor.
- a first dye precursor having a pyridine skeleton and a second dye precursor that develops a color tone different from that of the first dye precursor, wherein the first color is a color tone of the first dye precursor;
- the color 2 is the color tone of the mixed color due to the color development of the first dye precursor and the second dye precursor.
- the second dye precursor is in the form of composite fine particles (b1) containing the second dye precursor and a polymer compound, or a dye precursor having a melting point of 200 ° C. or higher. It is a body (b2).
- the color development of the first dye precursor is excellent in color separation and exhibits a vivid yellowish color tone with respect to the color mixture resulting from the color development of the first dye precursor and the second dye precursor.
- the first dye precursor can also be used in the form of composite fine particles having a color development start temperature and recording sensitivity different from those of the second dye precursor composite fine particles.
- the second dye precursor Since the yellow color tone due to the color development of the first dye precursor is mixed with the color development, a vivid yellow color tone is not obtained, and both colors are close to the color tone of the second dye precursor, and color separation Since it is inferior in property, it is not preferable.
- the second dye precursor (b2) having a melting point of 200 ° C. or higher preferably contains a second dye precursor that develops a black color tone, and the first dye precursor has a color tone different from that of the black color.
- a specific first dye precursor that is limited to yellow and has a high color density and a bright yellow color tone the color separation from the second dye precursor is excellent, and visibility It is possible to obtain a heat-sensitive recording material exhibiting two colors of a yellowish first color and a blackish second color which are excellent in color.
- the first color is a yellowish color tone.
- the first dye precursor having a pyridine skeleton in the present invention develops a bright yellow color tone, so that the yellow color image formed by the first dye precursor is an actual size. Excellent color expansion effect that makes it look bigger and closer.
- variable information such as characters or figures can be obtained by combining the first color and the second color obtained by color-mixing the first dye precursor and the second dye precursor. Can be displayed with a negative / positive selection as a yellow warning color.
- the first color when the support has a metallic luster and is a two-color heat-sensitive recording material, the first color has the metallic luster that the support has on the color development of the first dye precursor. It is a metallic color tone.
- the first dye precursor having a pyridine skeleton in the present invention develops a bright yellow color tone and has a metallic luster that the support has.
- a golden metal tone is obtained as the color tone of the.
- variable information such as characters or figures can be obtained by combining the first color and the second color obtained by color-mixing the first dye precursor and the second dye precursor. Can be displayed by selecting negative / positive in golden metal tone.
- the first dye precursor having the pyridine skeleton develops a color and can emit fluorescence under ultraviolet light.
- a yellow colored image by the first dye precursor can be displayed as a reflected image in a dark place.
- the dynamic color density (dynamic color yellow density) obtained by printing with a thermal head with an applied energy of 0.66 mJ / dot is 1.00 or more, and 0
- the dynamic color density (dynamic color yellow density) obtained by printing with a thermal head with an applied energy of .97 mJ / dot is preferably 1.00 or more.
- the dynamic color density (dynamic color yellow density)
- the resulting dynamic coloring density (dynamic coloring yellow density) is 1.10 or more, more preferably 1.15 or more. More preferably, the dynamic coloring density (dynamic coloring yellow density) obtained by printing with a thermal head with an applied energy of 0.97 mJ / dot is 1.40 or more, and more preferably 1.80 or more.
- the color density indicates the Y (yellow) density.
- the method of adjusting the content of the dye precursor or adjusting the form of the dye precursor can be used.
- the second dye precursor develops a color tone different from that of the first dye precursor.
- the second dye precursor include, for example, a dye precursor that develops a color tone of black, blue, cyan, green, red, and magenta, and is colored and absorbs in the near infrared region. Examples thereof include dye precursors.
- the second dye precursor is not limited to a single compound, and a desired color tone can be obtained by mixing two or more dye precursors having different color tone.
- Examples of the dye precursor that develops a green color are 3- (N-ethyl-Nn-hexylamino) -7-anilinofluorane, 3-diethylamino-7-dibenzylaminofluorane, 3,3 -Bis (4-diethylamino-2-ethoxyphenyl) -4-azaphthalide, 3- (N-ethyl-Np-tolylamino) -7- (N-phenyl-N-methylamino) fluorane, 3- [p- (P-anilinoanilino) anilino] -6-methyl-7-chlorofluorane and 3,6-bis (dimethylamino) fluorene-9-spiro-3 '-(6'-dimethylamino) phthalide it can.
- dye precursors that develop a red color tone include 3,6-bis (diethylamino) fluorane- ⁇ -anilinolactam, 3,6-bis (diethylamino) fluorane- ⁇ - (p-nitro) anilinolactam, 3,6-bis (diethylamino) fluorane- ⁇ - (o-chloro) anilinolactam, 3-dimethylamino-7-bromofluorane, 3-diethylaminofluorane, 3-diethylamino-6-methylfluorane, 3- Diethylamino-7-methylfluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-bromofluorane, 3-diethylamino-7,8-benzofluorane, 3-diethylamino-6,8-dimethylfluorane Oran, 3-diethylamino-6-methyl-7-chlorofluor
- the dye precursors that produce a magenta color are 3- (N-ethyl-N-isoamylamino) -7,8-benzofluorane, 3,3-bis (1-n-butyl-2-methyl).
- Indole-3-yl) phthalide, 3- (N-ethyl-N-isoamylamino) -7-phenoxyfluorane and the like can also be mentioned.
- the second dye precursor has a melting point of 200 ° C. or higher and is a dye precursor that develops a black color tone.
- 3-pyrrolidino-6-methyl-7-anilinofluorane (melting point 226 ° C.), 3- (N-ethyl-p-toluidino) -6-methyl-7-anilinofluorane (melting point 207 ° C.), 3-diethylamino-7- (2-chloroanilino) fluorane (melting point 220 ° C.), 3- (N-ethyl-p-toluidino) -6-methyl-7- (p-toluidino) fluorane (melting point 228 ° C.), 3- Diethylamino-7- (o-fluoroanilino) fluorane (melting point 215 ° C.), 3- (N-cyclohexyl-N-methylamin
- the first dye precursor and the second dye are colored depending on the form of the composite fine particles.
- the first dye precursor can also be used in the form of composite fine particles having a color development start temperature and recording sensitivity different from those of the second dye precursor composite fine particles.
- the second dye precursor Since the yellow color tone due to the color development of the first dye precursor is mixed in the color development, a vivid yellow color tone cannot be obtained and a golden metal tone cannot be obtained, and the second dye precursor for both colors This is not preferable because the color tone is close to that of the body and color separation is poor.
- the dye precursor is used in the form of solid dispersed fine particles
- water is used as a dispersion medium and pulverized by various wet pulverizers such as a sand mill, an attritor, a ball mill, and a cobo mill to obtain a dispersion.
- wet pulverizers such as a sand mill, an attritor, a ball mill, and a cobo mill to obtain a dispersion.
- water-soluble polymer compounds such as polyacrylamide, polyvinylpyrrolidone, polyvinyl alcohol, modified polyvinyl alcohols such as sulfone-modified polyvinyl alcohol, methylcellulose, carboxymethylcellulose, styrene-maleic anhydride copolymer salts and derivatives thereof, are necessary.
- this solution is emulsified and dispersed in water using the above water-soluble polymer compound as a stabilizer, and then the organic solvent is evaporated from the emulsion to make the dye precursor into solid dispersed fine particles.
- a surfactant an antifoaming agent or the like
- the volume average particle diameter of the solid dispersed fine particles of the dye precursor used in the form of the solid dispersed fine particles is preferably about 0.2 to 3.0 ⁇ m, more preferably in order to obtain appropriate recording sensitivity. Is about 0.3 to 1.0 ⁇ m.
- the load on the printer is reduced, This is a preferred embodiment because it can exhibit sufficient color separation.
- the composite fine particles in the present invention contain a dye precursor and a polymer compound. It is preferable that at least the second dye precursor is contained in the heat-sensitive recording layer in a form in which composite fine particles including the second dye precursor and a hydrophobic resin as a polymer compound are formed.
- a form in which composite fine particles containing a dye precursor and a hydrophobic resin are formed (1) A form in which one or more dye precursors are microencapsulated using a hydrophobic resin as a wall film, (2) A form in which one or more dye precursors are contained in a base material made of a hydrophobic resin obtained from a polyvalent isocyanate or the like, (3) A form in which a compound having an unsaturated carbon bond is polymerized on the surface of one or more dye precursor fine particles, Etc.
- a method described in JP-A-60-244594 can be cited as a method for producing particles having the form (1).
- Examples of the method for producing particles having the form (2) include the method described in JP-A-9-263057.
- Examples of the method for producing particles having the form (3) include the method described in JP-A No. 2000-158822.
- the hydrophobic resin forming the composite fine particles is not particularly limited, and examples thereof include urea resins, urethane resins, urea-urethane resins, styrene resins, acrylic resins, and the like. Among these, since the urea-based resin and the urea-urethane resin are excellent in heat-resistant surface fogging property, it is preferable that the second dye precursor forms composite fine particles with the polyurea or polyurea-polyurethane resin.
- the polyvalent isocyanate compound used for the production of the composite fine particles is a compound that forms polyurea or polyurea-polyurethane by reacting with water, and may be a polyvalent isocyanate compound alone or a polyvalent isocyanate. It may be a compound, a polyol that reacts with this, a mixture of polyamines, or an adduct of a polyvalent isocyanate compound and a polyol, a multimer such as a biuret or isocyanurate of a polyvalent isocyanate compound.
- a dye precursor is dissolved in these polyvalent isocyanate compounds, and this solution is dissolved in an aqueous medium containing a protective colloidal substance such as polyvinyl alcohol.
- the volume average particle diameter is preferably 0.2 to 3.0 ⁇ m.
- the polyisocyanate compound is obtained by emulsifying and dispersing to a degree, more preferably about 0.2 to 1.5 ⁇ m, and further, if necessary, mixing a reactive substance such as polyamine and then heating the emulsified dispersion. Polymerize. As a result, the polyvalent isocyanate compound can be polymerized to form composite fine particles containing the dye precursor.
- the dye precursor contained in the composite fine particles is highly separable from the outside, and the color former is very good storage stability, especially oils and plasticizers, compared to the color former colored in the state of solid dispersed fine particles. It is excellent in resistance to. The reason for this is not necessarily clear, but it is considered that the color former and the polymer substance (matrix) have some interaction and are stabilized.
- the appearance of the composite fine particles used in the present invention is almost spherical when observed with an electron microscope, or is somewhat erythrocytic.
- the shape In cross-sectional observation with an electron microscope, the shape is an internal body, a porous body, or a hollow body.
- the volume average particle diameter is preferably about 0.2 to 1.5 ⁇ m in order to obtain appropriate recording sensitivity.
- By setting the thickness to 0.2 ⁇ m or more, it is desirable from the viewpoint of improving the storage stability of the color image with respect to oil, plasticizer and the like.
- the composite fine particles used in the present invention include, in addition to the dye precursor, a UV absorber, an antioxidant, a release agent, which will be described later, and a sensitizer known as a heat-sensitive recording material, if necessary. May be added.
- Examples of the method of encapsulating the dye precursor in microcapsules include, for example, a method of microencapsulating a dye precursor wet-pulverized to a volume average particle size of about 0.2 to 3 ⁇ m by a coacervation method or an in-situ method, In addition, there is a method of microencapsulating a dye precursor emulsified and dispersed together with a polyvalent isocyanate compound and optionally an organic solvent by an interfacial polymerization method.
- the wall film agent of the microcapsule for example, gelatin is used in the coacervation method, and for example, a melamine-formaldehyde resin is used in the in-situ method.
- a polyurea polyurethane resin can be used in the interfacial polymerization method.
- the amount of the membrane wall material is about 1 to 30% by weight with respect to the total solid amount of the microcapsules.
- the volume average particle diameter of the microcapsules is about 0.5 to 5 ⁇ m.
- the forms (1) and (2) of these composite fine particles are superior in the transparency of the heat-sensitive recording layer as compared with the case where the dye precursor is used in the form of solid dispersed fine particles, and the heat-sensitive recording layer having high transparency. Can also be provided.
- the heat-sensitive recording layer in the present invention is formed by containing the first dye precursor and the second dye precursor in the same recording layer.
- the first dye precursor and the second dye precursor may be contained in separate recording layers, and these may be laminated. That is, in the present invention, one or two or more thermosensitive recording layers can be provided.
- the thermosensitive recording layer has a multilayer structure composed of at least a first thermosensitive recording layer and a second thermosensitive recording layer, and the first thermosensitive recording layer contains a first dye precursor and a developer,
- the second heat-sensitive recording layer can be in a form containing a second dye precursor and a developer. Thereby, the color densities of the first color and the second color can be adjusted.
- the order of lamination of the heat-sensitive recording layers may be the first heat-sensitive recording layer or the second heat-sensitive recording layer on the side close to the support.
- the second color is formed by color mixing, the storability of the color image can be enhanced without including a decoloring agent for the first color.
- the first dye precursor first develops a color by increasing the temperature, and then exhibits the first color.
- a second color can be obtained.
- the two-color thermal recording can be performed by changing the applied energy by, for example, using a thermal head and controlling the width of one pulse and the number of repetitions with a constant applied voltage. .
- an applied energy that is sufficient to reach the color development start temperature of the first dye precursor and is insufficient to reach the color development start temperature of the composite fine particles containing the second dye precursor is used.
- the first color having a metallic luster can be obtained when the first dye precursor has a metallic luster and the support has a metallic luster.
- both the first dye precursor and the second dye precursor are A second color is obtained by coloring and mixing.
- a red, black or green color tone is preferable.
- the second dye precursor is a dye precursor that develops a magenta color tone
- a red color tone is obtained
- a black color tone is obtained.
- a green color tone is obtained.
- the color development start temperature also depends on the polymer characteristics of the composite fine particles and the type of the developer, it is not limited by the type of the dye precursor having a specific melting point. These dye precursors can be selected and used in combination.
- the polymer characteristics of the composite fine particles can be controlled by the composition and production conditions of the composite fine particles such as the polyvalent isocyanate compound and reaction accelerator used.
- the forms (1) and (2) of these composite fine particles are superior in the transparency of the heat-sensitive recording layer compared to the case where the dye precursor is used in the form of solid dispersed fine particles.
- the present invention by providing a heat-sensitive recording layer having high transparency, it is possible to obtain a heat-sensitive recording material in which the background portion exhibits a silver metal tone and the color image exhibits a gold metal tone through the heat-sensitive recording layer.
- the dynamic color development characteristics and the static color development characteristics for example, by providing a heat-sensitive recording layer so as to conceal the metallic luster of the support using an aluminum-deposited support, It is also possible to record both a color image and a silver metal image.
- a preferred recording method in this case for example, by heating with a thermal head of a printer, a gold metal-tone color image is recorded with an applied energy equal to or higher than the static color development start temperature, and the dynamic color density (dynamic color yellow density) is 1. It can be recorded in a silver metal tone with an applied energy of less than 0.00.
- the temperature is higher than the static color development start temperature, sufficient energy is applied to exhibit a gold color, and when the dynamic color density (dynamic color yellow density) is less than 1.00, it is insufficient to exhibit a gold color.
- the dynamic color density dynamic color yellow density
- a part of the dye precursor or developer can be melted to develop the metallic luster of the support, and can exhibit a silver color.
- the content of the dye precursor is preferably about 5 to 30% by mass, more preferably about 7 to 30% by mass, and still more preferably about 7 to 25% by mass in the total solid content of each heat-sensitive recording layer.
- the color density can be improved by setting it to 5% by mass or more.
- Heat resistance can be improved by setting it as 30 mass% or less.
- the total content of the dye precursor that develops a black color tone including the second dye precursor in the thermosensitive recording layer is more than 0.5 times the coating amount of the first dye precursor.
- a range less than 5 times is preferable. More preferably, it is the range of 1.0 times or more and 2.0 times or less.
- the developer contained in the heat-sensitive recording layer in the present invention is selected from those having the property of being liquefied or dissolved by increasing the temperature, and having the property of developing the color by contacting the dye precursor.
- Specific examples include organic acidic substances such as phenol compounds, aromatic carboxylic acids, and polyvalent metal salts of these compounds.
- the developer may be usually present in the composite fine particles or in the microcapsules, or may be present in the state of solid dispersed fine particles.
- the developer content is preferably about 30 to 1500 parts by weight, more preferably about 50 to 1000 parts by weight, and still more preferably 100 to 600 parts per 100 parts by weight of the dye precursor in each heat-sensitive recording layer.
- the composite fine particles can be prepared by a method similar to the method of preparing the composite fine particles containing the dye precursor.
- Typical developers include, for example, 4-tert-butylphenol, 4-acetylphenol, 4-tert-octylphenol, 4,4'-sec-butylidenediphenol, 4-phenylphenol, 4,4'-dihydroxy Diphenylmethane, 4,4′-isopropylidene diphenol, 4,4′-dihydroxydiphenyl ether, 4,4′-cyclohexylidene diphenol, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4 -Hydroxyphenyl) -1-phenylethane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-thiobis (3-methyl-6-tert-butylphenol), 4,4'-dihydroxydiphenylsulfone, 2,4 ' -Dihydroxydiphenylsulfone, 4-hydro Cis-4'-isopropoxydiphenylsulfone, 4-hydroxy-4'-n-propoxy
- compounds that can be used as a developer include 4-hydroxybenzophenone, dimethyl 4-hydroxyphthalate, methyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, 4-hydroxybenzoate-sec-butyl.
- Phenyl compounds such as phenyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, tolyl 4-hydroxybenzoate, chlorophenyl 4-hydroxybenzoate, 4,4′-dihydroxydiphenyl ether, or benzoic acid;
- Aromatic carboxylic acids such as Le acid, and the phenolic compounds, aromatic carboxylic acid and, for example
- a preservability improving agent can be further contained in the heat-sensitive recording layer mainly in order to further improve the preservability of the color image.
- preservatives include 1,1,3-tris (2-methyl-4-hydroxy-5-cyclohexylphenyl) butane, 1,1,3-tris (2-methyl-4-hydroxy- 5-tert-butylphenyl) butane, 1,1-bis (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 4,4 ′-[1,4-phenylenebis (1-methylethylidene) ] Phenol compounds such as bisphenol and 4,4 '-[1,3-phenylenebis (1-methylethylidene)] bisphenol; 4-benzyloxyphenyl-4'-(2-methyl-2,3-epoxypropyloxy) ) Phenylsulfone, 4- (2-methyl-1,2-epoxyethyl) diphenylsulfone, and 4- (2-methyl-1,2-
- a sensitizer can be further contained in the heat-sensitive recording layer in order to improve the recording sensitivity.
- compounds conventionally known as sensitizers for thermal recording materials can be used.
- thermosensitive coloring layer Auxiliary agents such as developers, preservatives and sensitizers used in the thermosensitive coloring layer are dispersed in water in the same manner as when the dye precursor is used in the form of solid dispersed fine particles. What is necessary is just to mix with this in the case of preparation of a coating liquid. Moreover, these adjuvants can be dissolved in a solvent and emulsified in water using a water-soluble polymer compound as an emulsifier. Further, the preservability improver and the sensitizer may be contained in the composite fine particles containing the dye precursor.
- a fine pigment having a high whiteness and an average particle diameter of 10 ⁇ m or less can be contained in the heat-sensitive recording layer.
- a fine pigment having a high whiteness and an average particle diameter of 10 ⁇ m or less can be contained in the heat-sensitive recording layer.
- organic pigments such as urea-formalin resin, styrene-methacrylic acid copolymer resin, and polystyrene resin can be used.
- a binder As other component materials constituting the heat-sensitive recording layer, a binder is used, and if necessary, a crosslinking agent, waxes, metal soaps, colored dyes, colored pigments, fluorescent dyes, and the like can be used.
- the binder include polyvinyl alcohol and derivatives thereof; starch and derivatives thereof; cellulose derivatives such as hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, and ethylcellulose; sodium polyacrylate, polyvinylpyrrolidone, acrylamide-acrylate copolymer Water-soluble polymer materials such as acrylamide-acrylic acid ester-methacrylic acid ester copolymer, styrene-maleic anhydride copolymer, isobutylene-maleic anhydride copolymer, casein, gelatin and derivatives thereof; and poly Vinyl acetate, polyurethane, polyacrylic acid, polyacrylate, vinyl chloride-vinyl acetate cop
- crosslinking agent examples include aldehyde compounds such as glyoxal and polyamine compounds such as polyethyleneimine; Epoxy compounds, polyamide resins, melamine resins, glyoxylate, dimethylol urea compounds, aziridine compounds, blocked isocyanate compounds, and inorganic compounds such as ammonium persulfate, ferric chloride, magnesium chloride, sodium tetraborate, potassium tetraborate Or boric acid, boric acid triester, boron-based polymer, hydrazide compound, glyoxylate and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
- the amount of the crosslinking agent used is preferably in the range of about 1 to 10 parts by mass with respect to 100 parts by mass of the total solid content of the thermosensitive recording layer. Thereby, the water resistance of the thermosensitive recording layer can be improved.
- waxes such as paraffin wax, carnauba wax, microcrystalline wax, polyolefin wax, and polyethylene wax
- higher fatty acid amides such as stearic acid amide and ethylenebisstearic acid amide, higher fatty acid esters, and derivatives thereof. Can be mentioned.
- the metal soap examples include higher fatty acid polyvalent metal salts such as zinc stearate, aluminum stearate, calcium stearate, and zinc oleate. Further, if necessary, various auxiliary agents such as an oil repellent, an antifoaming agent and a viscosity modifier can be further added to the heat-sensitive recording layer as long as the effects of the present invention are not impaired.
- light resistance can be greatly improved by incorporating microcapsules encapsulating an ultraviolet absorber or solid dispersed fine particles of the ultraviolet absorber in the heat-sensitive recording layer.
- UV absorber examples include salicylic acid UV absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate; 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxy Benzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2- Mention may be made of benzophenone ultraviolet absorbers such as hydroxy-4-methoxy-5sulfobenzophenone.
- salicylic acid UV absorbers such as phenyl salicylate, p-tert-butylphenyl salicylate, p-octylphenyl salicylate
- 2,4-dihydroxybenzophenone 2-hydroxy-4-octyloxy Benzophen
- benzotriazole UV absorbers are preferable, and in particular, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-dodecyl-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-4 '-(2 "-ethylhexyl) Condensation of oxyphenyl] benzotriazole, polyethylene glycol (molecular weight about 300) with methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate In particular, it is more preferable because it exhibits a remarkable light resistance improvement effect.
- the addition ratio of the microcapsules encapsulating the ultraviolet absorber or the solid dispersed fine particles of the ultraviolet absorber is not particularly limited, but is preferably about 5 to 70% by mass in the total solid content of the heat-sensitive recording layer. Particularly preferably, it is adjusted to a range of about 15 to 50% by mass. Light resistance can be improved by setting it as 5 mass% or more. If it exceeds 70% by mass, the light resistance is saturated, so that it is preferably about 70% by mass or less from the viewpoint of improving the recording sensitivity. It is to be noted that the light resistance can be improved more effectively when the microcapsules encapsulating the ultraviolet absorber or the solid dispersed fine particles of the ultraviolet absorber are contained in the protective layer described later rather than being contained in the heat-sensitive recording layer. .
- the microcapsules encapsulating the ultraviolet absorber can be prepared by various known methods.
- the core substance obtained by dissolving the above-described solid or liquid ultraviolet absorber in an organic solvent as required at room temperature Oily liquid
- Oily liquid is prepared by a method of emulsifying and dispersing an oily liquid in an aqueous medium to form a wall film made of a polymer substance around oily droplets.
- polymer substance that becomes the wall film of the microcapsule include, for example, polyurethane resin, polyurea resin, polyamide resin, polyester resin, polycarbonate resin, aminoaldehyde resin, melamine resin, polystyrene resin, styrene-methacrylate copolymer resin, Examples include styrene-acrylate resin, gelatin, and polyvinyl alcohol.
- the heat-sensitive recording layer in the present invention uses, for example, water as a dispersion medium, a specific dye precursor, a developer, if necessary, a preservability improver, a sensitizer and the like, or a dispersion in which they are separately dispersed, Using a coating solution for a heat-sensitive recording layer prepared by mixing a pigment, a binder, a crosslinking agent, and other auxiliary agents as required, the coating amount is preferably about 2 to 12 g / m 2 by dry weight, more preferably It is formed by coating and drying on the support or on the support so as to cover the metallic luster of the support so as to be about 2 to 8 g / m 2 , more preferably about 2 to 7 g / m 2 .
- a protective layer containing a water-soluble polymer material and a pigment as used in a conventionally known thermal recording material on the thermal recording layer.
- a water-soluble polymer material and the pigment materials exemplified in the above-mentioned heat-sensitive recording layer can be used.
- a crosslinking agent to impart water resistance to the protective layer.
- the light resistance can be greatly improved by incorporating microcapsules enclosing an ultraviolet absorber or solid dispersed fine particles of the ultraviolet absorber in the protective layer.
- microcapsules having a wall film made of polyurethane-polyurea resin or aminoaldehyde resin are excellent in heat resistance, and are therefore added to the thermal recording layer or the protective layer for the purpose of preventing sticking to the thermal head.
- the refractive index is lower than that of other wall membrane microcapsules and ordinary pigments, and the shape is spherical. Even if it is contained in a large amount, it is preferably used because it does not cause a decrease in density due to irregular reflection of light.
- the oil absorption amount of the pigment it is preferable to use a pigment of 50 ml / 100 g or more.
- the pigment content is preferably an amount that does not decrease the color density, that is, 50% by mass or less of the total solid content of the protective layer.
- the protective layer is a protective layer coating solution prepared by mixing, for example, water as a dispersion medium and mixing a binder, and if necessary, a crosslinking agent, a pigment, and other auxiliaries. It is formed by applying and drying on the heat-sensitive recording layer so as to be about ⁇ 15 g / m 2 , more preferably about 0.5 to 8 g / m 2 .
- the heat-sensitive recording material can be printed with UV ink, flexographic ink, or the like.
- printing may be performed on a support, a heat-sensitive recording layer, a protective layer, or the like.
- a resin layer cured with an electron beam or ultraviolet light can be provided on the heat-sensitive recording layer or the protective layer.
- resins that can be cured with an electron beam are described in JP-A-58-177392, JP-A-58-177392, and the like.
- auxiliary agents such as a non-electron beam curable resin, a pigment, an antifoaming agent, a leveling agent, a lubricant, a surfactant, and a plasticizer can be appropriately added.
- pigments such as calcium carbonate and aluminum hydroxide, and lubricants such as waxes and silicon because this helps prevent sticking to the thermal head.
- a pressure-sensitive adhesive paper, a re-humidified adhesive paper, or a delayed tack paper can be obtained by applying coating processing on the back surface with a pressure-sensitive adhesive, a re-humidified adhesive, a delayed tack type pressure-sensitive adhesive, or the like.
- the anti-counterfeit recording material of the present invention that has been subjected to adhesive processing is useful as a heat-sensitive label.
- a function as a thermal transfer paper, an ink jet recording paper, a carbonless paper, an electrostatic recording paper, and a zeography paper can be added to form a recording paper capable of double-sided recording.
- a double-sided thermal recording material can also be used.
- a back layer can be provided for suppressing permeation of oil and plasticizer from the back surface of the heat-sensitive recording material, and for curling control and antistatic.
- Examples of methods for forming each layer on the support include air knife method, blade method, gravure method, roll coater method, spray method, dipping method, bar method, curtain method, slot die method, slide die method, and extrusion method. Any of the known coating methods may be used.
- At least one layer formed on the support is a layer formed by a curtain coating method.
- a layer having a uniform thickness can be formed, and the recording sensitivity can be increased, and the barrier property against oil, plasticizer, alcohol, etc. can be increased.
- the curtain coating method is a method in which the coating liquid is allowed to flow and fall freely, and is applied to the support in a non-contact manner, and known methods such as a slide curtain method, a couple curtain method, and a twin curtain method can be employed.
- a layer having a more uniform thickness can be formed by simultaneous multilayer coating. In simultaneous multi-layer coating, each coating solution is laminated and then applied, and then dried to form each layer.
- the lower surface coating surface After applying a coating solution that forms the lower layer, the lower surface coating surface is wet without drying. In a state, you may apply
- an embodiment in which a heat-sensitive recording layer and a protective layer are simultaneously applied in multiple layers is preferable from the viewpoint of improving barrier properties.
- the heat-sensitive recording surface may be applied to either a metal roll or an elastic roll of the calendar.
- the first dye precursor present in a fine particle state in the heat-sensitive recording layer and a developer that reacts under heating to develop the first dye precursor are applied to a thermal head or the like. It is considered that once the material is melted and solidified again, irregular reflection in the heat-sensitive recording layer is reduced, and a golden metal tone can be obtained through the heat-sensitive recording layer.
- the thermosensitive recording layer covers the metallic luster of the support, but since the color image exhibits a golden metal tone, the thermosensitive recording layer has the support.
- the degree of hiding the metallic luster is not particularly limited.
- the recording surface when the recording surface is viewed as a mat-like plain paper-like recording with a margin left, it is possible to display three colors: a golden metal tone, black as a mixed color, and a white background. Further, if the metallic luster can be visually confirmed through the heat-sensitive recording layer, the recording can be performed with leaving a blank space, so that it is possible to display three colors of gold metal tone, black as a mixed color, and silver on the background. .
- an undercoat layer can be provided between the support and the heat-sensitive recording layer as necessary. Thereby, the recording sensitivity can be further increased.
- the undercoat layer supports an undercoat layer coating solution containing an oil-absorbing pigment having an oil absorption of 70 ml / 100 g or more, particularly about 80 to 150 ml / 100 g, at least one of organic hollow particles and thermally expandable particles, and a binder. It is formed by applying and drying on top.
- the oil absorption is a value determined according to the method described in JIS K 5101.
- a pigment having a high porosity such as silica or calcined kaolin
- the coating amount of the undercoat layer coating solution is preferably about 3 to 20 g / m 2 by dry weight, more preferably about 4 to 12 g / m 2 .
- the binder in the undercoat layer can be appropriately selected from those that can be used in the heat-sensitive recording layer.
- these binders starch-vinyl acetate graft copolymer, polyvinyl alcohol, styrene-butadiene latex and the like are preferable from the viewpoint of improving barrier properties.
- Example 1-1 Preparation of Dye Precursor Dispersion (Ai Solution) 4- [2- (2-Octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N- as a dye precursor that develops a yellowish color tone 40 parts of dimethylbenzenamine, 40 parts of a 10% aqueous solution of polyvinyl alcohol (polymerization degree 500, saponification degree 88%), and 20 parts of water are mixed, and average particle size is measured using a vertical sand mill (made by Imex Corporation, sand grinder). Ai liquid was obtained by pulverizing to a diameter of 0.7 ⁇ m.
- developer dispersion 40 parts of 4-hydroxy-4'-isopropoxydiphenylsulfone, 40 parts of a 10% aqueous solution of polyvinyl alcohol (polymerization degree 500, saponification degree 88%), and water 20 parts It mixed and grind
- sensitizer dispersion 40 parts of 1,2-di (3-methylphenoxy) ethane, 40 parts of 10% aqueous solution of polyvinyl alcohol (polymerization degree 500, saponification degree 88%), and 20 parts water
- a vertical sand mill a sand grinder, manufactured by IMEX Co., Ltd.
- kaolin dispersion liquid (Di liquid) Kaolin (trade name: UW-90 (registered trademark), manufactured by BASF) 80 parts, 40% aqueous solution of sodium polyacrylate (trade name: Aron T-50, Toagosei Co., Ltd.) 1 part) and 53 parts of water were mixed and pulverized using a sand mill until the volume average particle diameter became 1.6 ⁇ m to obtain a Di liquid.
- Example 1-2 In the preparation of the Ai solution of Example 1-1, a dye precursor that develops a yellowish color tone is 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethyl. Heat sensitive as in Example 1-1, except that 4- [2- (2-butoxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine was used instead of benzeneamine. A record was obtained.
- Example 1-3 In the preparation of the Ai solution of Example 1-1, a dye precursor that develops a yellowish color tone is 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethyl.
- a thermosensitive recording material was obtained in the same manner as in Example 1-1 except that 1- (4-n-dodecyloxy-3-methoxyphenyl) -2- (2-quinolyl) ethylene was used instead of benzeneamine. It was.
- Example 1-4 In the preparation of the Ai liquid of Example 1-1, 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethyl was used as a dye precursor that develops a yellowish color.
- Example 1-1 was used except that 4- [2- (2-hexyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine was used instead of benzeneamine.
- a heat-sensitive recording material was obtained.
- Example 1-5 In the preparation of the Ai liquid of Example 1-1, 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethyl was used as a dye precursor that develops a yellowish color. The same procedure as in Example 1-1 except that 4- [2- (2-pentyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine was used instead of benzeneamine. A heat-sensitive recording material was obtained.
- Example 1-6 In the preparation of the Ai liquid of Example 1-1, 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethyl was used as a dye precursor that develops a yellowish color. Heat sensitive in the same manner as in Example 1-1 except that 4- [2,6-bis (2-butoxyphenyl) -4-pyridinyl] -N, N-dimethylbenzenamine was used instead of benzeneamine. A record was obtained.
- Example 1-7 In the preparation of the Ai liquid of Example 1-1, 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethyl was used as a dye precursor that develops a yellowish color.
- a thermosensitive recording material was obtained in the same manner as in Example 1-1 except that 4- (2,6-diphenyl-4-pyridinyl) -N, N-dimethylbenzenamine was used in place of benzeneamine.
- Example 1-8 In the production of the heat-sensitive recording material of Example 1-1, the coating amount after drying of the heat-sensitive recording layer coating liquid was changed to 5.5 g / m 2 , and 2.5 g / m 2 (colored in a yellowish color tone).
- a thermosensitive recording material was obtained in the same manner as in Example 1-1 except that the content of the dye precursor was 0.7 g / m 2 ).
- Example 1-9 In the preparation of heat-sensitive recording material of Example 1-1, instead of the coating amount after drying of the heat-sensitive recording layer coating composition to 5.5 g / m 2, coloring in color tone of 4.0 g / m 2 (yellow A thermosensitive recording material was obtained in the same manner as in Example 1-1 except that the content of the dye precursor was 1.1 g / m 2 .
- Example 1-10 In the production of the thermosensitive recording material of Example 1-1, the coating amount after drying of the thermosensitive recording layer coating liquid was changed to 5.5 g / m 2 and 20.0 g / m 2 (colored in a yellowish color tone). A thermosensitive recording material was obtained in the same manner as in Example 1-1 except that the content of the dye precursor was 5.6 g / m 2 ).
- Example 1-11 In the production of the thermosensitive recording material of Example 1-1, except that an aluminum vapor-deposited film (trade name: VM-PET, manufactured by Toray Industries, Inc., thickness 50 ⁇ m) was used instead of the aluminum vapor-deposited paper as a support. A heat-sensitive recording material was obtained in the same manner as in 1-1.
- an aluminum vapor-deposited film (trade name: VM-PET, manufactured by Toray Industries, Inc., thickness 50 ⁇ m) was used instead of the aluminum vapor-deposited paper as a support.
- a heat-sensitive recording material was obtained in the same manner as in 1-1.
- thermosensitive recording material of Example 1-1 instead of the aluminum vapor-deposited paper as the support, it was changed to a synthetic paper (product name: FPG-80, manufactured by YUPO Corporation, thickness 80 ⁇ m) having no metallic luster. Except for the above, a heat-sensitive recording material was obtained in the same manner as in Example 1-1.
- Example 1-1 In the preparation of the Ai solution of Example 1-1, a dye precursor that develops a yellowish color tone is 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethyl.
- Example 1-1 was used except that 3-di (n-butyl) amino-6-methyl-7-arininofluorane, which is a dye precursor that develops a black color tone, was used instead of benzeneamine.
- a heat-sensitive recording material was obtained in the same manner.
- thermosensitive recording material thus obtained was evaluated as follows. The results were as shown in Table 1.
- the color density is preferably 1.00 or more, more preferably 1.30 or more, and still more preferably 1.60 or more.
- the remaining ratio of the color density in the recording area was obtained.
- the remaining ratio of the color density is preferably 50% or more, more preferably 70% or more, still more preferably 80% or more, and particularly preferably 90% or more.
- Residual rate of color density (%) [(color density after treatment) / (color density before treatment)] ⁇ 100 (Light resistance of color images)
- a thermal recording simulator (trade name: TH-PMD, manufactured by Okura Electric Co., Ltd.)
- recording was performed under the condition of an applied energy of 0.968 mJ / dot, and a thermal recording body having a recording portion was recorded at 5000 lux under a fluorescent lamp.
- the Y density of the recording part is measured with an x-rite spectral densitometer (trade name: x-rite 528, manufactured by X-Rite, using color measurement), and the above-mentioned color image is preserved.
- the residual ratio of the color density in the recording area was obtained.
- the remaining ratio of the color density is preferably 50% or more, more preferably 70% or more, still more preferably 80% or more, and particularly preferably 90% or more.
- Example 2-1 Preparation of first dye precursor dispersion (Aii liquid) 4- [2- (2-octyloxy) phenyl-6-phenyl-4-pyridinyl] -N, as a dye precursor that develops a yellowish color tone 40 parts of N-dimethylbenzenamine, 40 parts of a 10% aqueous solution of polyvinyl alcohol (polymerization degree 500, saponification degree 88%), and 20 parts of water were mixed, and the average particle size was measured using a vertical sand mill (manufactured by IMEX). Was pulverized to be 0.7 ⁇ m to obtain a first dye precursor dispersion (hereinafter also referred to as Aii liquid) as solid dispersed fine particles.
- Aii liquid a first dye precursor dispersion
- ethylene oxide adduct of acetylene glycol as a surfactant (trade name: Orphin (registered trademark) E1010, JP
- the product was gradually added to 90 parts of an aqueous solution containing 2 parts (manufactured by Shin Chemical Co., Ltd.) and emulsified and dispersed by stirring at a rotational speed of 10,000 rpm using a homogenizer.
- an aqueous solution in which 50 parts of water and 1.5 parts of a polyvalent amine compound (trade name: Epomin SP-006, manufactured by Nippon Shokubai Co., Ltd.) were dissolved in 13.5 parts of water was added and homogenized.
- This emulsified dispersion is heated to 80 ° C. and subjected to a polymerization reaction for 6 hours to prepare composite fine particles having a volume average particle diameter of 0.8 ⁇ m, and diluted with water so that the solid content concentration becomes 25%.
- a composite fine particle dispersion (hereinafter also referred to as “Bii liquid”) containing a second dye precursor was obtained.
- Cii solution a developer dispersion (Cii solution) From 40 parts of 4-hydroxy-4'-isopropoxydiphenylsulfone, 40 parts of 10% aqueous solution of polyvinyl alcohol (polymerization degree 500, saponification degree 88%), and 20 parts of water The resulting composition was pulverized using a vertical sand mill (manufactured by Imex Co., Ltd.) until the volume average particle size became 1.5 ⁇ m to obtain a developer dispersion (hereinafter also referred to as Cii solution).
- sensitizer dispersion 40 parts of 1,2-di (3-methylphenoxy) ethane, 40 parts of a 10% aqueous solution of polyvinyl alcohol (polymerization degree 500, saponification degree 88%), and 20 parts water Were mixed using a vertical sand mill (manufactured by Imex Co., Ltd.) so as to have an average particle size of 1.0 ⁇ m to obtain a sensitizer dispersion (hereinafter also referred to as “Dii solution”).
- thermal recording layer coating liquid Aii liquid 18 parts, Bii liquid 45 parts, Cii liquid 90 parts, Dii liquid 45 parts, styrene-butadiene latex (trade name: L1571, manufactured by Asahi Kasei Corporation, solid content concentration 48 parts) 20 parts, 10% polyvinyl alcohol aqueous solution (trade name: Poval (registered trademark) PVA-110, manufactured by Kuraray) 100 parts, 5% surfactant aqueous solution (trade name: SN wet OT-70, manufactured by San Nopco) ) A composition comprising 10 parts and 69 parts of water was mixed to obtain a thermal recording layer coating liquid (I).
- kaolin dispersion (Eii liquid) Kaolin (trade name: UW-90 (registered trademark), manufactured by BASF) 80 parts, 40% aqueous solution of sodium polyacrylate (trade name: Aron T-50, Toagosei Co., Ltd.) 1 part) and 53 parts of water were mixed and pulverized with a sand mill until the volume average particle size became 1.6 ⁇ m to obtain a kaolin dispersion (hereinafter also referred to as Eii liquid).
- thermo-sensitive recording layer coating liquid (I) for thermal-sensitive recording layer coating liquid (I), for protective layer coating liquid as the coating amount after drying each becomes 7g / m 2, 3g / m 2, after sequential coating and drying at Mayer bar in this order, performs super calender treatment to obtain a heat-sensitive recording material .
- Example 2-2 4- [2- (2-Octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethyl as a dye precursor that develops a yellowish color tone in the preparation of the Aii solution of Example 2-1 Heat sensitive in the same manner as Example 2-1 except that 4- [2- (2-butoxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine was used instead of benzeneamine. A record was obtained.
- Example 2-3 In the preparation of the Bii solution of Example 2-1, 3- (N-ethyl-N-isoamylamino) -7,8-benzo, which is a dye precursor that develops a magenta color, is used as the second dye precursor.
- Example 2-1 except that 3-di (n-butyl) amino-6-methyl-7-anilinofluorane, which is a dye precursor that develops a black color tone, was used instead of fluorane.
- a heat-sensitive recording material was obtained in the same manner.
- thermal recording layer coating liquid (II) 63 parts of Aii liquid, 90 parts of Cii liquid, 45 parts of Dii liquid, 20 parts of styrene-butadiene latex (trade name: L1571, manufactured by Asahi Kasei Co., Ltd., solid content concentration 48%) 100 parts of 10% aqueous polyvinyl alcohol solution (trade name: Poval (registered trademark) PVA-110, manufactured by Kuraray Co., Ltd.), 10 parts of 5% aqueous surfactant solution (trade name: SN wet OT-70, manufactured by San Nopco), and A composition comprising 69 parts of water was mixed to obtain a thermal recording layer coating liquid (II).
- thermal recording layer coating liquid (III) 63 parts of Bii liquid, 90 parts of Cii liquid, 45 parts of Dii liquid, 20 parts of styrene-butadiene latex (trade name: L1571, manufactured by Asahi Kasei Co., Ltd., solid content concentration 48%) 100 parts of 10% aqueous polyvinyl alcohol solution (trade name: Poval (registered trademark) PVA-110, manufactured by Kuraray Co., Ltd.), 10 parts of 5% aqueous surfactant solution (trade name: SN wet OT-70, manufactured by San Nopco), and A composition comprising 69 parts of water was mixed to obtain a thermal recording layer coating liquid (III).
- aqueous polyvinyl alcohol solution trade name: Poval (registered trademark) PVA-110, manufactured by Kuraray Co., Ltd.
- SN wet OT-70 manufactured by San Nopco
- thermosensitive recording material was obtained in the same manner as in Example 2-1, except that the coating liquid (III) was applied and dried in this order with a Mayer bar so that the coating amount after drying was 5 g / m 2. It was.
- Example 2-5 In the production of the heat-sensitive recording material of Example 2-1, on the surface provided with the aluminum vapor-deposited layer of the aluminum vapor-deposited film (trade name: VM-PET, manufactured by Toray Industries, Inc., thickness: 50 ⁇ m) Instead of coating and drying (I) so that the coating amount after drying is 7 g / m 2 , the coating amount after drying the thermal recording layer coating liquid (III) is 5 g / m 2 and for the thermal recording layer.
- a thermal recording material was obtained in the same manner as in Example 2-1, except that the coating liquid (II) was applied and dried in this order with a Mayer bar so that the coating amount after drying was 2 g / m 2. It was.
- Example 2-6 Instead of 4- [2- (2-octyloxy) phenyl-6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine as the yellow chromogenic dye precursor in the preparation of the Aii solution of Example 2-1 Thus, a heat-sensitive recording material was obtained in the same manner as in Example 2-1, except that 4- (2,6-diphenyl-4-pyridinyl) -N, N-dimethylbenzenamine was used.
- Example 2-7 In the production of the heat-sensitive recording material of Example 2-1, the support was replaced with an aluminum vapor-deposited film, and aluminum vapor-deposited paper (trade name: Almic T, manufactured by Toppan Label Co., Ltd., thickness 50 ⁇ m) was used. A heat-sensitive recording material was obtained in the same manner as in 2-1.
- Example 2-8 In the preparation of heat-sensitive recording material of Example 2-1, instead of the heat-sensitive recording layer coating solution coated amount after drying of (I) to 7 g / m 2, except that the 10 g / m 2, the Example 2 In the same manner as in No. 1, a heat-sensitive recording material was obtained.
- Example 2-1 4- [2- (2-Octyloxy) phenyl-6-phenyl-4-pyridinyl] -N, N-dimethyl as a dye precursor that develops a yellowish color tone in the preparation of the Aii liquid of Example 2-1
- a thermal recording material was obtained in the same manner as in Example 2-1, except that 1- (4-n-dodecyloxy-3-methoxyphenyl) -2- (2-quinolyl) ethylene was used instead of benzeneamine. It was.
- thermal recording layer coating liquid (IV) 18 parts Aii liquid, 45 parts Fii liquid, 90 parts Cii liquid, 45 parts Dii liquid, styrene-butadiene latex (trade name: L1571, manufactured by Asahi Kasei Corporation, solid content concentration 48 parts) 20 parts, 10% polyvinyl alcohol aqueous solution (trade name: Poval (registered trademark) PVA-110, manufactured by Kuraray) 100 parts, 5% surfactant aqueous solution (trade name: SN wet OT-70, manufactured by San Nopco) ) A composition comprising 10 parts and 69 parts of water was mixed to obtain a thermal recording layer coating solution (IV).
- Example 2-1 In the production of the thermal recording material of Example 2-1, the same procedure as in Example 2-1 was performed except that the thermal recording layer coating liquid (IV) was used instead of the thermal recording layer coating liquid (I). A heat-sensitive recording material was obtained.
- the thermal recording material thus obtained was evaluated as follows. The results were as shown in Table 2.
- thermosensitive recording medium that exhibits a gold or red color tone with a densitometer (trade name: x-rite 528, manufactured by X-Rite, color measurement mode) has a Y (Yellow) and M (Magenta) density of gold or black.
- the two-color heat-sensitive recording material exhibiting the following color tone was measured for Y and V (Visual) concentrations. Moreover, the color tone was evaluated visually.
- Color separation The image developed under the application conditions at the above color density was visually observed, and the color separation was evaluated according to the following criteria.
- C Cannot be recognized as each color tone.
- Example 3-1 Preparation of first dye precursor dispersion (Aiii liquid) 4- [2- (2-octyloxy) phenyl-6-phenyl-4-pyridinyl] -N, as a dye precursor that develops a yellow color tone 40 parts of N-dimethylbenzenamine, 40 parts of a 10% aqueous solution of polyvinyl alcohol (polymerization degree 500, saponification degree 88%), and 20 parts of water were mixed, and the average particle size was measured using a vertical sand mill (manufactured by IMEX). Was pulverized to be 0.7 ⁇ m to obtain a first dye precursor dispersion (hereinafter also referred to as Aiii liquid) as solid dispersed fine particles.
- Aiii liquid a first dye precursor dispersion
- second liquid Biii containing second dye precursor 3- (N-ethyl-N-isoamylamino) -7,8-benzo as a dye precursor that develops a magenta color 20 parts of fluorane, 9.5 parts of dicyclohexylmethane-4,4′-diisocyanate (trade name: Desmodur W, manufactured by Sumika Bayer Urethane Co., Ltd.), m-tetramethylxylylene diisocyanate (trade name: TMXDI (registered trademark)) ), Nihon Cytec Industries, Ltd.) was dissolved in a mixed solvent consisting of 9.5 parts by heating (150 ° C.), and this solution was polyvinyl alcohol (trade name: Poval (registered trademark) PVA-217EE, manufactured by Kuraray Co., Ltd.) 8.8.
- PVA-217EE polyvinyl alcohol
- an ethylene oxide adduct of acetylene glycol (trade name: Olphine (registered trademark) E1010, Slowly added to the aqueous solution 90 parts including Nissin Chemical Industry Co., Ltd.) 2 parts, using a homogenizer, was emulsified and dispersed by agitation speed 10000 rpm.
- an aqueous solution in which 50 parts of water and 1.5 parts of a polyvalent amine compound (trade name: Epomin SP-006, manufactured by Nippon Shokubai Co., Ltd.) were dissolved in 13.5 parts of water was added and homogenized. This emulsified dispersion is heated to 80 ° C.
- a composite fine particle dispersion (hereinafter also referred to as Biii liquid) containing the second dye precursor was obtained.
- sensitizer dispersion liquid Diii
- 40 parts of 1,2-di (3-methylphenoxy) ethane 40 parts of 10% aqueous solution of polyvinyl alcohol (polymerization degree 500, saponification degree 88%), and water 20 parts
- a vertical sand mill manufactured by Imex Co., Ltd.
- coating liquid (I) for heat sensitive recording layer Aiii liquid 18 parts, Biii liquid 45 parts, Ciii liquid 90 parts, Diii liquid 45 parts, styrene-butadiene latex (trade name: L1571, manufactured by Asahi Kasei Corporation, solid content concentration 48 parts) 20 parts, 10% polyvinyl alcohol aqueous solution (trade name: Poval (registered trademark) PVA-110, manufactured by Kuraray) 100 parts, 5% surfactant aqueous solution (trade name: SN wet OT-70, manufactured by San Nopco) ) A composition comprising 10 parts and 69 parts of water was mixed to obtain a thermal recording layer coating liquid (I).
- kaolin dispersion (Eiii liquid) Kaolin (trade name: UW-90 (registered trademark), manufactured by BASF) 80 parts, 40% aqueous solution of sodium polyacrylate (trade name: Aron T-50, Toagosei Co., Ltd.) 1 part) and 53 parts of water were mixed and pulverized with a sand mill until the volume average particle diameter became 1.6 ⁇ m to obtain a kaolin dispersion (hereinafter also referred to as Eiii liquid).
- thermal recording material After drying the coating solution for thermal recording layer (I) and the coating solution for protective layer on one side of synthetic paper (trade name: FPG-80, manufactured by YUPO Corporation, thickness 80 ⁇ m), respectively. After sequentially applying and drying with a Mayer bar in this order so that the application amount of 7 g / m 2 and 3 g / m 2 , super calendering was performed to obtain a thermal recording material.
- synthetic paper trade name: FPG-80, manufactured by YUPO Corporation, thickness 80 ⁇ m
- Example 3-2 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethyl as a dye precursor that develops a yellowish color tone in the preparation of the liquid Aiii of Example 3-1 Heat sensitive in the same manner as in Example 3-1, except that 4- [2- (2-butoxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine was used instead of benzeneamine. A record was obtained.
- Example 3-3 In the preparation of the liquid Biii of Example 3-1, 3- (N-ethyl-N-isoamylamino) -7,8-benzo, which is a dye precursor that develops a magenta color, is used as the second dye precursor.
- Example 3-1 except that 3-di (n-butyl) amino-6-methyl-7-anilinofluorane, which is a dye precursor that develops a black color tone, was used instead of fluorane.
- a heat-sensitive recording material was obtained in the same manner.
- Example 3-4 Preparation of thermal recording layer coating liquid (II) 63 parts of Aiii liquid, 90 parts of Ciii liquid, 45 parts of Diii liquid, 20 parts of styrene-butadiene latex (trade name: L1571, manufactured by Asahi Kasei Corporation, solid content concentration 48%) 100 parts of 10% aqueous polyvinyl alcohol solution (trade name: Poval (registered trademark) PVA-110, manufactured by Kuraray Co., Ltd.), 10 parts of 5% aqueous surfactant solution (trade name: SN wet OT-70, manufactured by San Nopco), and A composition comprising 69 parts of water was mixed to obtain a thermal recording layer coating liquid (II).
- aqueous polyvinyl alcohol solution trade name: Poval (registered trademark) PVA-110, manufactured by Kuraray Co., Ltd.
- SN wet OT-70 manufactured by San Nopco
- thermal recording layer coating liquid (III) 63 parts of Biii liquid, 90 parts of Ciii liquid, 45 parts of Diii liquid, 20 parts of styrene-butadiene latex (trade name: L1571, manufactured by Asahi Kasei Corporation, solid content concentration 48%) 100 parts of 10% aqueous polyvinyl alcohol solution (trade name: Poval (registered trademark) PVA-110, manufactured by Kuraray Co., Ltd.), 10 parts of 5% aqueous surfactant solution (trade name: SN wet OT-70, manufactured by San Nopco), and A composition comprising 69 parts of water was mixed to obtain a thermal recording layer coating liquid (III).
- aqueous polyvinyl alcohol solution trade name: Poval (registered trademark) PVA-110, manufactured by Kuraray Co., Ltd.
- SN wet OT-70 manufactured by San Nopco
- thermosensitive recording material of Example 3-1 after the thermal recording layer coating liquid (I) was dried on one side of a synthetic paper (trade name: FPG-80, manufactured by YUPO Corporation, thickness: 80 ⁇ m) in place of the coating amount applied and dried so that 7 g / m 2, the heat-sensitive recording layer coating solution (II) the coating amount after drying 2 g / m 2, the heat-sensitive recording layer coating solution (III) A heat-sensitive recording material was obtained in the same manner as in Example 3-1, except that the coating amount after drying was successively applied and dried with a Mayer bar in this order so that the coating amount after drying was 5 g / m 2 .
- a synthetic paper trade name: FPG-80, manufactured by YUPO Corporation, thickness: 80 ⁇ m
- Example 3-5 In the production of the thermosensitive recording material of Example 3-1, after the thermal recording layer coating liquid (I) was dried on one side of a synthetic paper (trade name: FPG-80, manufactured by YUPO Corporation, thickness: 80 ⁇ m) in place of the coating amount applied and dried so that 7 g / m 2, the heat-sensitive recording layer coating solution (III) a coating amount after drying 5 g / m 2, the heat-sensitive recording layer coating solution (II) A thermal recording material was obtained in the same manner as in Example 3-1, except that the coating amount after drying was successively applied and dried with a Mayer bar in this order so that the coating amount after drying was 2 g / m 2 .
- a synthetic paper trade name: FPG-80, manufactured by YUPO Corporation, thickness: 80 ⁇ m
- Example 3-6 Instead of 4- [2- (2-octyloxy) phenyl-6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine as the yellow chromogenic dye precursor in the preparation of the liquid Aiii of Example 3-1 Thus, a heat-sensitive recording material was obtained in the same manner as in Example 3-1, except that 4- (2,6-diphenyl-4-pyridinyl) -N, N-dimethylbenzenamine was used.
- Example 3-1 4- [2- (2-octyloxy) phenyl-6-phenyl-4-pyridinyl] -N, N-dimethyl as a dye precursor that develops a yellowish color tone in the preparation of the liquid Aiii of Example 3-1
- a thermosensitive recording material was obtained in the same manner as in Example 3-1, except that 1- (4-n-dodecyloxy-3-methoxyphenyl) -2- (2-quinolyl) ethylene was used instead of benzeneamine. It was.
- coating solution (IV) for heat sensitive recording layer 18 parts Aiii liquid, 45 parts Fiii liquid, 90 parts Ciii liquid, 45 parts Diii liquid, styrene-butadiene latex (trade name: L1571, manufactured by Asahi Kasei Corporation, solid content concentration 48 parts) 20 parts, 10% polyvinyl alcohol aqueous solution (trade name: Poval (registered trademark) PVA-110, manufactured by Kuraray) 100 parts, 5% surfactant aqueous solution (trade name: SN wet OT-70, manufactured by San Nopco) ) A composition comprising 10 parts and 69 parts of water was mixed to obtain a thermal recording layer coating solution (IV).
- Example 3-1 In the production of the thermal recording material of Example 3-1, the same procedure as in Example 3-1 was performed except that the thermal recording layer coating liquid (IV) was used instead of the thermal recording layer coating liquid (I). A heat-sensitive recording material was obtained.
- the thermal recording material thus obtained was evaluated as follows. The results were as shown in Table 3.
- Color separation The image developed under the application conditions at the above color density was visually observed, and the color separation was evaluated according to the following criteria.
- C Cannot be recognized as each color tone.
- Example 4-1 Preparation of first dye precursor dispersion (Aiv liquid) 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N as a dye precursor that develops a yellowish color tone , N-dimethylbenzenamine 40 parts, polyvinyl alcohol (polymerization degree 500, saponification degree 88%) 10% aqueous solution 40 parts, and water 20 parts were mixed, and average particle size was measured using a vertical sand mill (manufactured by IMEX). The particles were pulverized so as to have a diameter of 0.7 ⁇ m to obtain solid dispersed fine particles of the first dye precursor.
- the obtained dispersion is also referred to as Aiv liquid.
- Biv liquid the obtained dispersion is also referred to as Biv liquid.
- Civ solution a developer dispersion (Civ solution) From 40 parts of 4-hydroxy-4'-isopropoxydiphenylsulfone, 40 parts of 10% aqueous solution of polyvinyl alcohol (polymerization degree 500, saponification degree 88%), and water 20 parts The resulting composition was pulverized using a vertical sand mill (manufactured by Imex Co., Ltd.) until the volume average particle diameter became 1.5 ⁇ m to obtain a developer dispersion (hereinafter also referred to as Civ liquid).
- sensitizer dispersion 40 parts of 1,2-di (3-methylphenoxy) ethane, 40 parts of 10% aqueous solution of polyvinyl alcohol (polymerization degree 500, saponification degree 88%), and water 20 parts Were mixed using a vertical sand mill (manufactured by Imex Co., Ltd.) to obtain an sensitizer dispersion (hereinafter also referred to as Div liquid).
- thermal recording layer coating liquid (I) 20 parts of Aiv liquid, 5 parts of styrene-butadiene latex (trade name: L1571, manufactured by Asahi Kasei Co., Ltd., solid content concentration 48%), 10% aqueous solution of polyvinyl alcohol (trade name: 25 parts of Poval (registered trademark) PVA-110 (manufactured by Kuraray), 23 parts of Civ liquid, 11 parts of Div liquid, 2 parts of 5% surfactant aqueous solution (trade name: SN Wet OT-70, manufactured by San Nopco), and A composition comprising 17 parts of water was mixed to obtain a thermal recording layer coating liquid (I).
- Aiv liquid 20 parts of Aiv liquid, 5 parts of styrene-butadiene latex (trade name: L1571, manufactured by Asahi Kasei Co., Ltd., solid content concentration 48%), 10% aqueous solution of polyvinyl alcohol (trade name: 25 parts of Poval (registere
- thermal recording layer coating liquid (II) 20 parts of Biv liquid, 5 parts of styrene-butadiene latex (trade name: L1571, manufactured by Asahi Kasei Co., Ltd., solid content concentration 48%), 10% polyvinyl alcohol aqueous solution (trade name: 25 parts of Poval (registered trademark) PVA-110 (manufactured by Kuraray), 23 parts of Civ liquid, 11 parts of Div liquid, 2 parts of 5% surfactant aqueous solution (trade name: SN Wet OT-70, manufactured by San Nopco), and A composition comprising 17 parts of water was mixed to obtain a thermal recording layer coating liquid (II).
- kaolin dispersion (Eiv liquid) Kaolin (trade name: UW-90 (registered trademark), manufactured by BASF) 80 parts, 40% aqueous solution of sodium polyacrylate (trade name: Aron T-50, Toagosei Co., Ltd.) 1 part) and 53 parts of water were mixed and pulverized using a sand mill until the volume average particle diameter became 1.6 ⁇ m to obtain a kaolin dispersion (hereinafter also referred to as Eiv liquid).
- Eiv liquid a kaolin dispersion
- acetoacetyl-modified polyvinyl alcohol (trade name: Gohsephimer (registered trademark) Z-200, manufactured by Nippon Synthetic Chemical Industry Co., Ltd., degree of polymerization: about 1000, degree of saponification: about 98 mol%) 15% aqueous solution, paraffin wax (trade name: Hydrin P-7, manufactured by Chukyo Yushi Co., Ltd., solid content concentration 30%) 7.5 parts, 5% surfactant aqueous solution (trade name: SN wet) OT-70 (manufactured by San Nopco) 5 parts, glyoxal (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., solid content 40%) 0.3 parts, and a composition comprising 12.5 parts of water and a coating solution for protective layer Got.
- acetoacetyl-modified polyvinyl alcohol (trade name: Gohsephimer (registered trademark) Z-200, manufactured by Nippon Synthetic Chemical Industry Co.,
- thermal recording material After drying the coating solution (I) for the thermal recording layer on one side of synthetic paper (trade name: FPG-80, manufactured by YUPO Corporation, thickness 80 ⁇ m) from the side close to the support.
- the coating amount is 2.5 g / m 2
- the coating amount after drying the thermal recording layer coating liquid (II) is 4.0 g / m 2
- the coating amount after drying the protective layer coating liquid is 3.0 g / m.
- Example 4-2 In the production of the thermal recording material of Example 4-1, instead of coating the thermal recording layer coating liquid (II) so that the coating amount after drying was 4.0 g / m 2 , the thermal recording layer coating liquid A thermal recording material was obtained in the same manner as in Example 4-1, except that (II) was applied so that the coating amount after drying was 2.5 g / m 2 .
- Example 4-3 In the production of the thermal recording material of Example 4-1, instead of coating the thermal recording layer coating liquid (I) so that the coating amount after drying was 2.5 g / m 2 , the thermal recording layer coating liquid (II) is applied so that the coating amount after drying is 4.0 g / m 2, and the thermal recording layer coating solution (II) is applied so that the coating amount after drying is 4.0 g / m 2. Instead of this, a thermal recording material was obtained in the same manner as in Example 4-1, except that the coating liquid (I) for thermal recording layer was applied so that the coating amount after drying was 2.5 g / m 2 . .
- Example 4-4 In the preparation of the Aiv solution of Example 4-1, instead of 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine as the first dye precursor, A heat-sensitive recording material was obtained in the same manner as in Example 4-1, except that 4- [2- (2-butoxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine was used.
- Example 4-5 In the production of the thermal recording material of Example 4-1, instead of coating the thermal recording layer coating liquid (II) so that the coating amount after drying was 4.0 g / m 2 , the thermal recording layer coating liquid A heat-sensitive recording material was obtained in the same manner as in Example 4-1, except that (II) was applied so that the coating amount after drying was 5.0 g / m 2 .
- Example 4-6 In the production of the thermal recording material of Example 4-1, instead of coating the thermal recording layer coating liquid (I) so that the coating amount after drying was 2.5 g / m 2 , the thermal recording layer coating liquid (I) is applied so that the coating amount after drying is 4.0 g / m 2, and the thermal recording layer coating solution (II) is applied so that the coating amount after drying is 4.0 g / m 2. Instead of this, a thermal recording material was obtained in the same manner as in Example 4-1, except that the coating liquid (II) for thermal recording layer was applied so that the coating amount after drying was 2.5 g / m 2 . .
- Example 4-7 In the production of the thermosensitive recording material of Example 4-1, instead of one side of synthetic paper (trade name: FPG-80, manufactured by YUPO Corporation, thickness 80 ⁇ m) as a support, an aluminum vapor-deposited film (trade name: VM) -A heat-sensitive recording material was obtained in the same manner as in Example 4-1, except that the surface provided with an aluminum vapor-deposited layer (PET, manufactured by Toray Industries, Inc., 50 ⁇ m thick) was used.
- synthetic paper trade name: FPG-80, manufactured by YUPO Corporation, thickness 80 ⁇ m
- VM aluminum vapor-deposited film
- Example 4-1 In the preparation of the Aiv solution of Example 4-1, instead of 4- [2- (2-octyloxyphenyl) -6-phenyl-4-pyridinyl] -N, N-dimethylbenzenamine as the first dye precursor, A heat-sensitive recording material was obtained in the same manner as in Example 4-1, except that 1- (4-n-dodecyloxy-3-methoxyphenyl) -2- (2-quinolyl) ethylene was used.
- thermosensitive recording material thus obtained was evaluated as follows. The results were as shown in Table 4.
- C Cannot be recognized as each color tone.
- the heat-sensitive recording material of the present invention has a metallic luster on the support, a colored image different in appearance from the color tone of the dye precursor contained in the heat-sensitive recording layer is obtained due to the metallic luster, and a clear image is obtained.
- a golden metal tone can be exhibited.
- variable information that takes advantage of the vivid golden metal color tone, such as various tickets such as gold vouchers, coupons, receipts, labels, bags, sample books, price tags, packing tags, direct mail, message cards, It is suitably used for displays such as advertisements and billboards, packaging and packaging materials, and other uses such as substitution of gold leaf.
- the heat-sensitive recording material of the present invention is a two-color heat-sensitive recording material, it exhibits a yellow color tone and a color tone different from this, and has a high color density in each color tone and has a recording portion.
- the color separation property is excellent, and the effect of color expansion is excellent.
- the yellow color image has fluorescence.
- it is suitably used as a warning display such as a tiger mark and a reflective material by selecting a color tone.
- the two-color heat-sensitive recording material of the present invention is used, and a metallic luster is imparted to the support so that, in particular, the first metallic color tone and the second different color tone are combined. Since variable information can be printed out, it is possible to use, for example, a combination of red, negative / positive selection, decoration, a welcome message according to the visitor, etc., as a banner or a banner.
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Abstract
Description
(a) 前記支持体が金属光沢を有し、金属光沢を有しない基材の表面に金属光沢を付与した支持体であり、
及び/又は
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、下記一般式(1):
で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b1) 第2染料前駆体と高分子化合物とを含む複合微粒子の形態、若しくは
(b2) 200℃以上の融点を有する染料前駆体
である
感熱記録体。
前記感熱記録体を0.97mJ/dotの印加エネルギーでサーマルヘッドにより印字して得られる動発色のイエロー濃度が1.00以上であり、且つ前記感熱記録体を40~220℃の熱板に9.8×104Paで5秒間接触させて得られる発色濃度が0.2となる静発色開始温度が50℃以上である、項1に記載の感熱記録体。
前記黄色系の色調に発色する染料前駆体の含有量が0.7g/m2以上である、項1又は2に記載の感熱記録体。
前記黄色系の色調に発色する染料前駆体が、下記一般式(1):
で表される分子構造にピリジン骨格を有する染料前駆体である、項1~3のいずれか1項に記載の感熱記録体。
(a) 前記支持体が金属光沢を有し、金属光沢を有しない基材の表面に金属光沢を付与した支持体であって、
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b1) 第2染料前駆体と高分子化合物とを含む複合微粒子の形態であって、
前記感熱記録層が少なくとも第1感熱記録層及び第2感熱記録層からなる多層構造を有しており、前記第1染料前駆体が第1感熱記録層に含有され、少なくとも前記第2染料前駆体が複合微粒子の形態で第2感熱記録層に含有される、項1に記載の感熱記録体。
(a) 前記支持体が金属光沢を有し、金属光沢を有しない基材の表面に金属光沢を付与した支持体であって、
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b1) 第2染料前駆体と高分子化合物とを含む複合微粒子の形態であって、
前記ピリジン骨格を有する第1染料前駆体が、4‐[2‐(2‐ブトキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐ペンチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐ヘキシルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐(2,6‐ジフェニル‐4‐ピリジニル)‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ブトキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ペンチルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ヘキシルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、及び4‐[2,6‐ビス(2‐オクチルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンからなる群から選ばれる少なくとも1種である、項1又は5に記載の感熱記録体。
(a) 前記支持体が金属光沢を有し、金属光沢を有しない基材の表面に金属光沢を付与した支持体であって、
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b1) 第2染料前駆体と高分子化合物とを含む複合微粒子の形態であって、
前記感熱記録体を0.66mJ/dotの印加エネルギーでサーマルヘッドにより印字して得られる動発色のイエロー濃度が1.00以上であり、且つ0.97mJ/dotの印加エネルギーでサーマルヘッドにより印字して得られる動発色のイエロー濃度が1.00以上である、項1、5又は6に記載の感熱記録体。
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b1) 第2染料前駆体と高分子化合物とを含む複合微粒子の形態である
感熱記録体であって、
前記感熱記録層が少なくとも第1感熱記録層及び第2感熱記録層からなる多層構造を有しており、前記第1染料前駆体が第1感熱記録層に含有され、少なくとも前記第2染料前駆体が複合微粒子の形態で第2感熱記録層に含有される、項1に記載の感熱記録体。
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b1) 第2染料前駆体と高分子化合物とを含む複合微粒子の形態である
感熱記録体であって、
前記ピリジン骨格を有する第1染料前駆体が、4‐[2‐(2‐ブトキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐ペンチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐ヘキシルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐(2,6‐ジフェニル‐4‐ピリジニル)‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ブトキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ペンチルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ヘキシルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、及び4‐[2,6‐ビス(2‐オクチルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンからなる群から選ばれる少なくとも1種である、項1又は8に記載の感熱記録体。
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b1) 第2染料前駆体と高分子化合物とを含む複合微粒子の形態である
感熱記録体であって、
前記2色感熱記録体を0.66mJ/dotの印加エネルギーでサーマルヘッドにより印字して得られる動発色のイエロー濃度が1.00以上であり、且つ0.97mJ/dotの印加エネルギーでサーマルヘッドにより印字して得られる動発色のイエロー濃度が1.00以上である、項1、8、又は9に記載の感熱記録体。
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b2) 200℃以上の融点を有する染料前駆体であって、
前記感熱記録層が少なくとも第1感熱記録層及び第2感熱記録層からなる多層構造を有しており、前記第1感熱記録層が第1染料前駆体を含有し、前記第2感熱記録層が第2染料前駆体を含有する、項1に記載の感熱記録体。
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b2) 200℃以上の融点を有する染料前駆体であって、
前記ピリジン骨格を有する第1染料前駆体が、4‐[2‐(2‐ブトキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐ペンチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐ヘキシルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ブトキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ペンチルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ヘキシルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、及び4‐[2,6‐ビス(2‐オクチルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンからなる群から選ばれる少なくとも1種である、項1又は11に記載の感熱記録体。
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b2) 200℃以上の融点を有する染料前駆体であって、
前記2色感熱記録体を0.66mJ/dotの印加エネルギーでサーマルヘッドにより印字して得られる動発色のイエロー濃度が1.00以上であり、且つ0.97mJ/dotの印加エネルギーでサーマルヘッドにより印字して得られる動発色のイエロー濃度が1.00以上である、項1、11、又は12に記載の感熱記録体。
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b2) 200℃以上の融点を有する染料前駆体であって、
前記支持体が金属光沢を有する、項1、及び11~13のいずれか1項に記載の感熱記録体。
で表される分子構造にピリジン骨格を有する染料前駆体である、項17~19のいずれか1項に記載の感熱記録体。
で表される分子構造にピリジン骨格を有する第1染料前駆体と、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、少なくとも前記第2染料前駆体が複合微粒子の形態で感熱記録層に含有されることを特徴とする2色感熱記録体。
で表される分子構造にピリジン骨格を有する第1染料前駆体と、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、第1の色が前記第1染料前駆体の発色に前記支持体の有する金属光沢を帯びるメタル調の色調であり、第2の色が前記第1染料前駆体と第2染料前駆体の発色による混色の色調であることを特徴とする2色感熱記録体。
で表される分子構造にピリジン骨格を有する第1染料前駆体と、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、少なくとも前記第2染料前駆体が複合微粒子の形態で感熱記録層に含有されることを特徴とする2色感熱記録体。
で表される分子構造にピリジン骨格を有する第1染料前駆体と、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、第1の色が前記第1染料前駆体の発色による色調であり、第2の色が前記第1染料前駆体と第2染料前駆体の発色による混色の色調であることを特徴とする2色感熱記録体。
で表される分子構造にピリジン骨格を有する第1染料前駆体と、黒色系の色調に発色する第2染料前駆体とを含有し、前記第2染料前駆体の融点が200℃以上であることを特徴とする2色感熱記録体。
(a) 前記支持体が金属光沢を有し、金属光沢を有しない基材の表面に金属光沢を付与した支持体であり、
及び/又は
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有する。
下記一般式(1):
(1)1種以上の染料前駆体を壁膜としての疎水性樹脂を用いてマイクロカプセル化した形態、
(2)1種以上の染料前駆体を多価イソシアネート等により得られた疎水性樹脂からなる母材中に含有せしめた形態、
(3)1種以上の染料前駆体の微粒子表面に不飽和炭素結合を有する化合物を重合せしめた形態、
等が挙げられる。
例えば、(1)の形態の粒子の作製方法としては、特開昭60‐244594号公報に記載された方法が挙げられる。(2)の形態の粒子の作製方法としては、特開平9‐263057号公報に記載された方法が挙げられる。(3)の形態の粒子の作製方法としては、特開2000‐158822号公報に記載された方法が挙げられる。
エポキシ系化合物、ポリアミド樹脂、メラミン樹脂、グリオキシル酸塩、ジメチロールウレア化合物、アジリジン化合物、ブロックイソシアネート化合物、並びに過硫酸アンモニウムや塩化第二鉄、及び塩化マグネシウム、四硼酸ソーダ、四硼酸カリウム等の無機化合物;又は硼酸、硼酸トリエステル、硼素系ポリマー、ヒドラジド化合物、グリオキシル酸塩等が挙げられる。これらは1種単独で用いてもよいし、2種以上を組合せて使用してもよい。架橋剤の使用量は、感熱記録層の全固形量100質量部に対し、1~10質量部程度の範囲が好ましい。これにより、感熱記録層の耐水性を向上することができる。
・染料前駆体分散液(Ai液)の調製
黄色系の色調に発色する染料前駆体として、4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン40部、ポリビニルアルコール(重合度500、鹸化度88%)の10%水溶液40部、及び水20部を混合し、縦型サンドミル(アイメックス社製、サンドグラインダー)を用いて、平均粒子径が0.7μmとなるように粉砕して、Ai液を得た。
4‐ヒドロキシ‐4’‐イソプロポキシジフェニルスルホン40部、ポリビニルアルコール(重合度500、鹸化度88%)の10%水溶液40部、及び水20部を混合し、ウルトラビスコミルを用いて体積平均粒子径が1.5μmとなるまで粉砕して、Bi液を得た。
1,2‐ジ(3‐メチルフェノキシ)エタン40部、ポリビニルアルコール(重合度500、鹸化度88%)の10%水溶液40部、及び水20部を混合し、縦型サンドミル(アイメックス社製、サンドグラインダー)を用いて、平均粒子径が1.0μmとなるように粉砕して、Ci液を得た。
Ai液20部、スチレン‐ブタジエン系ラテックス(商品名:L1571、旭化成社製、固形分濃度48%)5部、10%ポリビニルアルコール水溶液(商品名:ポバール(登録商標)PVA‐110、クラレ社製)25部、Bi液23部、Ci液11部、5%界面活性剤水溶液(商品名:SNウェットOT‐70、サンノプコ社製)2部、及び水17部からなる組成物を混合撹拌して感熱記録層用塗液を得た。
カオリン(商品名:UW‐90(登録商標)、BASF社製)80部、ポリアクリル酸ナトリウムの40%水溶液(商品名:アロンT‐50、東亞合成社製)1部、及び水53部を混合し、サンドミルを用いて体積平均粒子径が1.6μmとなるまで粉砕して、Di液を得た。
Di液25部、アセトアセチル変性ポリビニルアルコール(商品名:ゴーセファイマー(登録商標)Z‐200、日本合成化学工業社製、重合度:約1000、鹸化度:約98モル%)の15%水溶液50部、パラフィンワックス(商品名:ハイドリンP‐7、中京油脂社製、固形分濃度30%)7.5部、5%界面活性剤水溶液(商品名:SNウェットOT‐70、サンノプコ社製)5部、グリオキザール(日本合成化学工業社製、固形分濃度40%)0.3部、及び水12.5部からなる組成物を混合攪拌して保護層用塗液を得た。
支持体としてアルミ蒸着紙(商品名:アルミックT、トッパンレーベル社製、厚さ50μm)のアルミ蒸着層が設けられた面上に、感熱記録層用塗液、保護層用塗液をそれぞれ乾燥後の塗布量が乾燥後の塗布量が5.5g/m2(黄色系の色調に発色する染料前駆体の含有量1.5g/m2)、3.0g/m2となるようにメイヤーバーにて塗布及び乾燥した後、スーパーカレンダー処理を行い、感熱記録体を得た。
実施例1‐1のAi液の調製において、黄色系の色調に発色する染料前駆体を4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンに代えて、4‐[2‐(2‐ブトキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンを用いた以外は、実施例1‐1と同様にして感熱記録体を得た。
実施例1‐1のAi液の調製において、黄色系の色調に発色する染料前駆体を4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンに代えて、1‐(4‐n‐ドデシルオキシ‐3‐メトキシフェニル)‐2‐(2‐キノリル)エチレンを用いた以外は、実施例1‐1と同様にして感熱記録体を得た。
実施例1‐1のAi液の調製において、黄色系の色調に発色する染料前駆体として4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンに代えて、4‐[2‐(2‐ヘキシルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンを用いた以外は、実施例1‐1と同様にして感熱記録体を得た。
実施例1‐1のAi液の調製において、黄色系の色調に発色する染料前駆体として4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンに代えて、4‐[2‐(2‐ペンチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンを用いた以外は、実施例1‐1と同様にして感熱記録体を得た。
実施例1‐1のAi液の調製において、黄色系の色調に発色する染料前駆体として4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンに代えて、4‐[2,6‐ビス(2‐ブトシキフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンを用いた以外は、実施例1‐1と同様にして感熱記録体を得た。
実施例1‐1のAi液の調製において、黄色系の色調に発色する染料前駆体として4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンに代えて、4‐(2,6‐ジフェニル‐4‐ピリジニル)‐N,N‐ジメチルベンゼンアミンを用いた以外は、実施例1‐1と同様にして感熱記録体を得た。
実施例1‐1の感熱記録体の作製において、感熱記録層用塗液の乾燥後の塗布量を5.5g/m2に代えて、2.5g/m2(黄色系の色調に発色する染料前駆体の含有量0.7g/m2)とした以外は、実施例1‐1と同様にして感熱記録体を得た。
実施例1‐1の感熱記録体の作製において、感熱記録層用塗液の乾燥後の塗布量を5.5g/m2に代えて、4.0g/m2(黄色系の色調に発色する染料前駆体の含有量1.1g/m2)とした以外は、実施例1‐1と同様にして感熱記録体を得た。
実施例1‐1の感熱記録体の作製において、感熱記録層用塗液の乾燥後の塗布量を5.5g/m2に代えて、20.0g/m2(黄色系の色調に発色する染料前駆体の含有量5.6g/m2)とした以外は、実施例1‐1と同様にして感熱記録体を得た。
実施例1‐1の感熱記録体の作製において、支持体をアルミ蒸着紙に代えて、アルミ蒸着フィルム(商品名:VM‐PET、東レ社製、厚さ50μm)を用いた以外は、実施例1‐1と同様にして感熱記録体を得た。
実施例1‐1の感熱記録体の作製において、支持体としてアルミ蒸着紙に代えて、金属光沢を有しない合成紙(商品名:FPG‐80、ユポ・コーポレーション社製、厚さ80μm)に変更した以外は、実施例1‐1と同様にして感熱記録体を得た。
実施例1‐1のAi液の調製において、黄色系の色調に発色する染料前駆体を4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンに代えて、黒色系の色調に発色する染料前駆体である3‐ジ(n‐ブチル)アミノ‐6‐メチル‐7‐アリニノフルオランを用いた以外は、実施例1‐1と同様にして感熱記録体を得た。
感熱記録用シミュレーター(商品名:TH‐PMD、大倉電機社製)を用い、印加エネルギー0.968mJ/dot条件にて記録し、記録部の見た目の発色色調を目視にて評価した。
熱風乾燥機を用いて、乾燥機内の温度120℃条件にて発色させた焼き面を作成し、焼き面を目視にて観察し、下記の基準で評価した。
感熱記録用シミュレーター(商品名:TH‐PMD、大倉電機社製)を用い、印加エネルギー0.968mJ/dotの条件にて記録し、記録部の発色濃度としてx‐rite分光濃度計(商品名:x‐rite528、エックスライト社製、色彩測定使用)でY濃度を測定した。十分な金色を得るには、発色濃度が1.00以上であることが好ましく、より好ましくは1.30以上であり、更に好ましくは1.60以上である。
熱傾斜試験機(東洋精機社製)を用いて、押圧9.8×104Pa、接触時間5秒間の条件、40~220℃の範囲で、10℃毎に発色させ、記録部の発色濃度としてx‐rite分光濃度計(商品名:x‐rite528、エックスライト社製、色彩測定使用)でY濃度を測定し、発色濃度が0.2を挟む温度の間で、線形補間を行って、発色濃度0.2に相当する温度を求めた。十分な金色を得るには、発色濃度が0.2となる温度は、50℃以上であることが好ましく、60℃以上であることがより好ましい。
感熱記録用シミュレーター(商品名:TH‐PMD、大倉電機社製)を用い、印加エネルギー0.968mJ/dotの条件にて記録し、記録部を有する感熱記録体を用いて、50℃、80%RHの環境下で24時間放置する処理を施した後、x‐rite分光濃度計(商品名:x‐rite528、エックスライト社製、色彩測定使用)で記録部のY濃度を測定し、下記式により記録部の発色濃度の残存率を求めた。発色濃度の残存率は、50%以上が好ましく、70%以上がより好ましく、80%以上が更に好ましく、90%以上が特に好ましい。
(発色像の耐光性)
感熱記録用シミュレーター(商品名:TH‐PMD、大倉電機社製)を用い、印加エネルギー0.968mJ/dotの条件にて記録し、記録部を有する感熱記録体を、蛍光灯下で5000ルクス×100時間の照射処理を行った後、x‐rite分光濃度計(商品名:x‐rite528、エックスライト社製、色彩測定使用)で記録部のY濃度を測定し、上記の発色像の保存性と同様に記録部の発色濃度の残存率を求めた。発色濃度の残存率は、50%以上が好ましく、70%以上がより好ましく、80%以上が更に好ましく、90%以上が特に好ましい。
感熱記録用シミュレーター(商品名:TH‐PMD、大倉電機社製)を用い、印加エネルギー0.968mJ/dotの条件にて記録し、x‐rite分光濃度計(商品名:x‐rite528、エックスライト社製、色彩測定使用)で記録部の色度b*値を測定した。十分な金色を得るには、+50.0以上が好ましい。
・第1染料前駆体分散液(Aii液)の調製
黄色系の色調に発色する染料前駆体として、4‐[2‐(2‐オクチルオキシ)フェニル‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン40部、ポリビニルアルコール(重合度500、鹸化度88%)の10%水溶液40部、及び水20部を混合し、縦型サンドミル(アイメックス社製)を用いて、平均粒子径が0.7μmとなるように粉砕して、固体分散微粒子として第1染料前駆体分散液(以下、Aii液ともいう)を得た。
マゼンタ色系の色調に発色する染料前駆体として、3‐(N‐エチル‐N‐イソアミルアミノ)‐7,8‐ベンゾフルオラン20部を、ジシクロヘキシルメタン‐4,4’‐ジイソシアネート(商品名:デスモジュールW、住化バイエルウレタン社製)9.5部、m‐テトラメチルキシリレンジイソシアネート(商品名:TMXDI(登録商標)、日本サイテックインダストリーズ社製)9.5部からなる混合溶媒に加熱溶解(150℃)し、この溶液をポリビニルアルコール(商品名:ポバール(登録商標)PVA‐217EE、クラレ社製)8.8部と、界面活性剤としてアセチレングリコールのエチレンオキサイド付加物(商品名:オルフィン(登録商標)E1010、日信化学工業社製)2部を含む水溶液90部に徐々に添加し、ホモジナイザーを用いて、回転数10000rpmの攪拌によって乳化分散した。この乳化分散液に、水50部、多価アミン化合物(商品名:エポミンSP‐006、日本触媒社製)1.5部を水13.5部に溶解した水溶液を加えて均一化した。この乳化分散液を80℃に昇温して、6時間の重合反応を行い、体積平均粒子径0.8μmの複合微粒子を調製し、固形分濃度が25%となるように水で希釈して、第2染料前駆体を含有する複合微粒子分散液(以下、Bii液ともいう)を得た。
4‐ヒドロキシ‐4’‐イソプロポキシジフェニルスルホン40部、ポリビニルアルコール(重合度500、鹸化度88%)の10%水溶液40部、及び水20部からなる組成物を、縦型サンドミル(アイメックス社製)を用いて体積平均粒子径が1.5μmとなるまで粉砕して、顕色剤分散液(以下、Cii液ともいう)を得た。
1,2‐ジ(3‐メチルフェノキシ)エタン40部、ポリビニルアルコール(重合度500、鹸化度88%)の10%水溶液40部、及び水20部を混合し、縦型サンドミル(アイメックス社製)を用いて、平均粒子径が1.0μmとなるように粉砕して、増感剤分散液(以下、Dii液ともいう)を得た。
Aii液18部、Bii液45部、Cii液90部、Dii液45部、スチレン‐ブタジエン系ラテックス(商品名:L1571、旭化成社製、固形分濃度48%)20部、10%ポリビニルアルコール水溶液(商品名:ポバール(登録商標)PVA‐110、クラレ社製)100部、5%界面活性剤水溶液(商品名:SNウェットOT‐70、サンノプコ社製)10部、及び水69部からなる組成物を混合して感熱記録層用塗液(I)を得た。
カオリン(商品名:UW‐90(登録商標)、BASF社製)80部、ポリアクリル酸ナトリウムの40%水溶液(商品名:アロンT‐50、東亞合成社製)1部、及び水53部を混合し、サンドミルを用いて体積平均粒子径が1.6μmとなるまで粉砕して、カオリン分散液(以下、Eii液ともいう)を得た。
Eii液25部、アセトアセチル変性ポリビニルアルコール(商品名:ゴーセファイマー(登録商標)Z‐200、日本合成化学工業社製、重合度:約1000、鹸化度:約98モル%)の15%水溶液50部、パラフィンワックス(商品名:ハイドリンP‐7、中京油脂社製、固形分濃度30%)7.5部、5%界面活性剤水溶液(商品名:SNウェットOT‐70、サンノプコ社製)5部、グリオキザール(日本合成化学工業社製、固形分濃度40%)0.3部、及び水12.5部からなる組成物を混合して保護層用塗液を得た。
アルミ蒸着フィルム(商品名:VM‐PET、東レ社製、厚さ50μm)のアルミ蒸着層が設けられた面上に、感熱記録層用塗液(I)、保護層用塗液をそれぞれ乾燥後の塗布量が7g/m2、3g/m2となるように、この順にメイヤーバーにて遂次塗布及び乾燥した後、スーパーカレンダー処理を行い、感熱記録体を得た。
実施例2‐1のAii液の調製において、黄色系の色調に発色する染料前駆体として4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンに代えて、4‐[2‐(2‐ブトキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンを用いた以外は、実施例2‐1と同様にして感熱記録体を得た。
実施例2‐1のBii液の調製において、第2染料前駆体として、マゼンタ色系の色調に発色する染料前駆体である3‐(N‐エチル‐N‐イソアミルアミノ)‐7,8‐ベンゾフルオランに代えて、黒色系の色調に発色する染料前駆体である3‐ジ(n‐ブチル)アミノ‐6‐メチル‐7‐アニリノフルオランを用いた以外は、実施例2‐1と同様にして感熱記録体を得た。
・感熱記録層用塗液(II)の調製
Aii液63部、Cii液90部、Dii液45部、スチレン‐ブタジエン系ラテックス(商品名:L1571、旭化成社製、固形分濃度48%)20部、10%ポリビニルアルコール水溶液(商品名:ポバール(登録商標)PVA‐110、クラレ社製)100部、5%界面活性剤水溶液(商品名:SNウェットOT‐70、サンノプコ社製)10部、及び水69部からなる組成物を混合して感熱記録層用塗液(II)を得た。
Bii液63部、Cii液90部、Dii液45部、スチレン‐ブタジエン系ラテックス(商品名:L1571、旭化成社製、固形分濃度48%)20部、10%ポリビニルアルコール水溶液(商品名:ポバール(登録商標)PVA‐110、クラレ社製)100部、5%界面活性剤水溶液(商品名:SNウェットOT‐70、サンノプコ社製)10部、及び水69部からなる組成物を混合して感熱記録層用塗液(III)を得た。
実施例2‐1の感熱記録体の作製において、アルミ蒸着フィルム(商品名:VM‐PET、東レ社製、厚さ50μm)のアルミ蒸着層が設けられた面上に、感熱記録層用塗液(I)を乾燥後の塗布量が7g/m2となるように塗布及び乾燥する代わりに、感熱記録層用塗液(III)を乾燥後の塗布量が5g/m2、感熱記録層用塗液(II)を乾燥後の塗布量が2g/m2となるように、この順にメイヤーバーにて遂次塗布及び乾燥した以外は、実施例2‐1と同様にして感熱記録体を得た。
実施例2‐1のAii液の調製において、黄色発色性染料前駆体として4‐[2‐(2‐オクチルオキシ)フェニル‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンに代えて、4‐(2,6‐ジフェニル‐4‐ピリジニル)‐N,N‐ジメチルベンゼンアミン用いた以外は、実施例2‐1と同様にして感熱記録体を得た。
実施例2‐1の感熱記録体の作製において、支持体をアルミ蒸着フィルムに代えて、アルミ蒸着紙(商品名:アルミックT、トッパンレーベル社製、厚さ50μm)を用いた以外は、実施例2‐1と同様にして感熱記録体を得た。
実施例2‐1の感熱記録体の作製において、感熱記録層用塗液(I)の乾燥後の塗布量を7g/m2に代えて、10g/m2とした以外は、実施例2‐1と同様にして感熱記録体を得た。
実施例2‐1のAii液の調製において、黄色系の色調に発色する染料前駆体として4‐[2‐(2‐オクチルオキシ)フェニル‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンに代えて、1‐(4‐n‐ドデシルオキシ‐3‐メトキシフェニル)‐2‐(2‐キノリル)エチレンを用いた以外は、実施例2‐1と同様にして感熱記録体を得た。
・第2染料前駆体分散液(Fii液)の調製
マゼンタ色系の色調に発色する染料前駆体として、3‐(N‐エチル‐N‐イソアミルアミノ)‐7,8‐ベンゾフルオラン40部、ポリビニルアルコール(重合度500、鹸化度88%)の10%水溶液40部、及び水20部を混合し、縦型サンドミル(アイメックス社製)を用いて、平均粒子径が0.7μmとなるように粉砕して、固体分散微粒子として第2染料前駆体分散液(以下、Fii液ともいう)を得た。
Aii液18部、Fii液45部、Cii液90部、Dii液45部、スチレン‐ブタジエン系ラテックス(商品名:L1571、旭化成社製、固形分濃度48%)20部、10%ポリビニルアルコール水溶液(商品名:ポバール(登録商標)PVA‐110、クラレ社製)100部、5%界面活性剤水溶液(商品名:SNウェットOT‐70、サンノプコ社製)10部、及び水69部からなる組成物を混合して感熱記録層用塗液(IV)を得た。
感熱記録用シミュレーター(商品名:TH‐PMD、大倉電機社製)を用い、印加エネルギー0.660mJ/dot及び0.968mJ/dotの条件にて記録し、記録部の発色濃度としてx‐rite分光濃度計(商品名:x‐rite528、エックスライト社製、色彩測定モード)で、金又は赤の色調を呈する2色感熱記録体は、Y(Yellow)及びM(Magenta)濃度を、金又は黒の色調を呈する2色感熱記録体は、Y及びV(Visual)濃度を測定した。また、目視にて色調を評価した。
上記の発色濃度における印加条件により発色させた像を目視にて観察し、色分離性を下記の基準で評価した。
上記の発色濃度における印加条件により発色させた像を目視にて観察し、下記の基準で評価した。
・第1染料前駆体分散液(Aiii液)の調製
黄色系の色調に発色する染料前駆体として、4‐[2‐(2‐オクチルオキシ)フェニル‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン40部、ポリビニルアルコール(重合度500、鹸化度88%)の10%水溶液40部、及び水20部を混合し、縦型サンドミル(アイメックス社製)を用いて、平均粒子径が0.7μmとなるように粉砕して、固体分散微粒子として第1染料前駆体分散液(以下、Aiii液ともいう)を得た。
マゼンタ色系の色調に発色する染料前駆体として、3‐(N‐エチル‐N‐イソアミルアミノ)‐7,8‐ベンゾフルオラン20部を、ジシクロヘキシルメタン‐4,4’‐ジイソシアネート(商品名:デスモジュールW、住化バイエルウレタン社製)9.5部、m‐テトラメチルキシリレンジイソシアネート(商品名:TMXDI(登録商標)、日本サイテックインダストリーズ社製)9.5部からなる混合溶媒に加熱溶解(150℃)し、この溶液をポリビニルアルコール(商品名:ポバール(登録商標)PVA‐217EE、クラレ社製)8.8部と、界面活性剤としてアセチレングリコールのエチレンオキサイド付加物(商品名:オルフィン(登録商標)E1010、日信化学工業社製)2部を含む水溶液90部に徐々に添加し、ホモジナイザーを用いて、回転数10000rpmの攪拌によって乳化分散した。この乳化分散液に、水50部、多価アミン化合物(商品名:エポミンSP‐006、日本触媒社製)1.5部を水13.5部に溶解した水溶液を加えて均一化した。この乳化分散液を80℃に昇温して、6時間の重合反応を行い、体積平均粒子径0.8μmの複合微粒子を調製し、固形分濃度が25%となるように水で希釈して、第2染料前駆体を含有する複合微粒子分散液(以下、Biii液ともいう)を得た。
4‐ヒドロキシ‐4’‐イソプロポキシジフェニルスルホン40部、ポリビニルアルコール(重合度500、鹸化度88%)の10%水溶液40部、及び水20部からなる組成物を、縦型サンドミル(アイメックス社製)を用いて体積平均粒子径が1.5μmとなるまで粉砕して、顕色剤分散液(以下、Ciii液ともいう)を得た。
1,2‐ジ(3‐メチルフェノキシ)エタン40部、ポリビニルアルコール(重合度500、鹸化度88%)の10%水溶液40部、及び水20部を混合し、縦型サンドミル(アイメックス社製)を用いて、平均粒子径が1.0μmとなるように粉砕して、増感剤分散液(以下、Diii液ともいう)を得た。
Aiii液18部、Biii液45部、Ciii液90部、Diii液45部、スチレン‐ブタジエン系ラテックス(商品名:L1571、旭化成社製、固形分濃度48%)20部、10%ポリビニルアルコール水溶液(商品名:ポバール(登録商標)PVA‐110、クラレ社製)100部、5%界面活性剤水溶液(商品名:SNウェットOT‐70、サンノプコ社製)10部、及び水69部からなる組成物を混合して感熱記録層用塗液(I)を得た。
カオリン(商品名:UW‐90(登録商標)、BASF社製)80部、ポリアクリル酸ナトリウムの40%水溶液(商品名:アロンT‐50、東亞合成社製)1部、及び水53部を混合し、サンドミルを用いて体積平均粒子径が1.6μmとなるまで粉砕して、カオリン分散液(以下、Eiii液ともいう)を得た。
Eiii液25部、アセトアセチル変性ポリビニルアルコール(商品名:ゴーセファイマー(登録商標)Z‐200、日本合成化学工業社製、重合度:約1000、鹸化度:約98モル%)の15%水溶液50部、パラフィンワックス(商品名:ハイドリンP‐7、中京油脂社製、固形分濃度30%)7.5部、5%界面活性剤水溶液(商品名:SNウェットOT‐70、サンノプコ社製)5部、グリオキザール(日本合成化学工業社製、固形分濃度40%)0.3部、及び水12.5部からなる組成物を混合して保護層用塗液を得た。
合成紙(商品名:FPG‐80、ユポ・コーポレーション社製、厚さ80μm)の片面上に、感熱記録層用塗液(I)、保護層用塗液をそれぞれ乾燥後の塗布量が7g/m2、3g/m2となるように、この順にメイヤーバーにて遂次塗布及び乾燥した後、スーパーカレンダー処理を行い、感熱記録体を得た。
実施例3‐1のAiii液の調製において、黄色系の色調に発色する染料前駆体として4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンに代えて、4‐[2‐(2‐ブトキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンを用いた以外は、実施例3‐1と同様にして感熱記録体を得た。
実施例3‐1のBiii液の調製において、第2染料前駆体として、マゼンタ色系の色調に発色する染料前駆体である3‐(N‐エチル‐N‐イソアミルアミノ)‐7,8‐ベンゾフルオランに代えて、黒色系の色調に発色する染料前駆体である3‐ジ(n‐ブチル)アミノ‐6‐メチル‐7‐アニリノフルオランを用いた以外は、実施例3‐1と同様にして感熱記録体を得た。
・感熱記録層用塗液(II)の調製
Aiii液63部、Ciii液90部、Diii液45部、スチレン‐ブタジエン系ラテックス(商品名:L1571、旭化成社製、固形分濃度48%)20部、10%ポリビニルアルコール水溶液(商品名:ポバール(登録商標)PVA‐110、クラレ社製)100部、5%界面活性剤水溶液(商品名:SNウェットOT‐70、サンノプコ社製)10部、及び水69部からなる組成物を混合して感熱記録層用塗液(II)を得た。
Biii液63部、Ciii液90部、Diii液45部、スチレン‐ブタジエン系ラテックス(商品名:L1571、旭化成社製、固形分濃度48%)20部、10%ポリビニルアルコール水溶液(商品名:ポバール(登録商標)PVA‐110、クラレ社製)100部、5%界面活性剤水溶液(商品名:SNウェットOT‐70、サンノプコ社製)10部、及び水69部からなる組成物を混合して感熱記録層用塗液(III)を得た。
実施例3‐1の感熱記録体の作製において、合成紙(商品名:FPG‐80、ユポ・コーポレーション社製、厚さ80μm)の片面上に、感熱記録層用塗液(I)を乾燥後の塗布量が7g/m2となるように塗布及び乾燥する代わりに、感熱記録層用塗液(III)を乾燥後の塗布量が5g/m2、感熱記録層用塗液(II)を乾燥後の塗布量が2g/m2となるように、この順にメイヤーバーにて遂次塗布及び乾燥した以外は、実施例3‐1と同様にして感熱記録体を得た。
実施例3‐1のAiii液の調製において、黄色発色性染料前駆体として4‐[2‐(2‐オクチルオキシ)フェニル‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンに代えて、4‐(2,6‐ジフェニル‐4‐ピリジニル)‐N,N‐ジメチルベンゼンアミン用いた以外は、実施例3‐1と同様にして感熱記録体を得た。
実施例3‐1のAiii液の調製において、黄色系の色調に発色する染料前駆体として4‐[2‐(2‐オクチルオキシ)フェニル‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンに代えて、1‐(4‐n‐ドデシルオキシ‐3‐メトキシフェニル)‐2‐(2‐キノリル)エチレンを用いた以外は、実施例3‐1と同様にして感熱記録体を得た。
・第2染料前駆体分散液(Fiii液)の調製
マゼンタ色系の色調に発色する染料前駆体として、3‐(N‐エチル‐N‐イソアミルアミノ)‐7,8‐ベンゾフルオラン40部、ポリビニルアルコール(重合度500、鹸化度88%)の10%水溶液40部、及び水20部を混合し、縦型サンドミル(アイメックス社製)を用いて、平均粒子径が0.7μmとなるように粉砕して、固体分散微粒子として第2染料前駆体分散液(以下、Fiii液ともいう)を得た。
Aiii液18部、Fiii液45部、Ciii液90部、Diii液45部、スチレン‐ブタジエン系ラテックス(商品名:L1571、旭化成社製、固形分濃度48%)20部、10%ポリビニルアルコール水溶液(商品名:ポバール(登録商標)PVA‐110、クラレ社製)100部、5%界面活性剤水溶液(商品名:SNウェットOT‐70、サンノプコ社製)10部、及び水69部からなる組成物を混合して感熱記録層用塗液(IV)を得た。
感熱記録用シミュレーター(商品名:TH‐PMD、大倉電機社製)を用い、印加エネルギー0.660mJ/dot及び0.968mJ/dotの条件にて記録し、記録部の発色濃度としてx‐rite分光濃度計(商品名:x‐rite528、エックスライト社製、色彩測定モード)で、黄又は赤色系の色調を呈する2色感熱記録体は、Y(Yellow)及びM(Magenta)濃度を、黄又は黒色系の色調を呈する2色感熱記録体は、Y及びV(Visual)濃度を測定した。また、目視にて色調を評価した。
上記の発色濃度における印加条件により発色させた像を目視にて観察し、色分離性を下記の基準で評価した。
上記の発色濃度における印加条件により発色させた黄色系の色調と、これとは異なる色調の混在する図柄のネガ/ポジの発色像を目視にて観察し、黄色系の色調による色膨張性を下記の基準で評価した。
上記の発色濃度における印加条件により発色させた黄色系の色調の発色像にブラックライトの紫外線を照射して発色像が蛍光を発するか否か、その有無を目視にて評価した。
・第1染料前駆体の分散液(Aiv液)の調製
黄色系の色調に発色する染料前駆体として、4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン40部、ポリビニルアルコール(重合度500、鹸化度88%)の10%水溶液40部、及び水20部を混合し、縦型サンドミル(アイメックス社製)を用いて、平均粒子径が0.7μmとなるように粉砕して第1染料前駆体の固体分散微粒子を得た。得られた分散液を以下、Aiv液ともいう。
融点が200℃以上の黒色系の色調に発色する染料前駆体として、3‐(N‐エチル‐p‐トルイジノ)‐6‐メチル‐7‐アニリノフルオラン40部、ポリビニルアルコール(重合度500、鹸化度88%)の10%水溶液40部、及び水20部を混合し、縦型サンドミル(アイメックス社製)を用いて、平均粒子径が0.7μmとなるように粉砕して第2染料前駆体の固体分散微粒子を得た。得られた分散液を以下、Biv液ともいう。
4‐ヒドロキシ‐4’‐イソプロポキシジフェニルスルホン40部、ポリビニルアルコール(重合度500、鹸化度88%)の10%水溶液40部、及び水20部からなる組成物を、縦型サンドミル(アイメックス社製)を用いて体積平均粒子径が1.5μmとなるまで粉砕して顕色剤分散液(以下、Civ液ともいう)を得た。
1,2‐ジ(3‐メチルフェノキシ)エタン40部、ポリビニルアルコール(重合度500、鹸化度88%)の10%水溶液40部、及び水20部を混合し、縦型サンドミル(アイメックス社製)を用いて、平均粒子径が1.0μmとなるように粉砕して増感剤分散液(以下、Div液ともいう)を得た。
Aiv液20部、スチレン‐ブタジエン系ラテックス(商品名:L1571、旭化成社製、固形分濃度48%)5部、10%ポリビニルアルコール水溶液(商品名:ポバール(登録商標)PVA‐110、クラレ社製)25部、Civ液23部、Div液11部、5%界面活性剤水溶液(商品名:SNウェットOT‐70、サンノプコ社製)2部、及び水17部からなる組成物を混合して感熱記録層用塗液(I)を得た。
Biv液20部、スチレン‐ブタジエン系ラテックス(商品名:L1571、旭化成社製、固形分濃度48%)5部、10%ポリビニルアルコール水溶液(商品名:ポバール(登録商標)PVA‐110、クラレ社製)25部、Civ液23部、Div液11部、5%界面活性剤水溶液(商品名:SNウェットOT‐70、サンノプコ社製)2部、及び水17部からなる組成物を混合して感熱記録層用塗液(II)を得た。
カオリン(商品名:UW‐90(登録商標)、BASF社製)80部、ポリアクリル酸ナトリウムの40%水溶液(商品名:アロンT‐50、東亞合成社製)1部、及び水53部を混合し、サンドミルを用いて体積平均粒子径が1.6μmとなるまで粉砕してカオリン分散液(以下、Eiv液ともいう)を得た。
Eiv液25部、アセトアセチル変性ポリビニルアルコール(商品名:ゴーセファイマー(登録商標)Z‐200、日本合成化学工業社製、重合度:約1000、鹸化度:約98モル%)の15%水溶液50部、パラフィンワックス(商品名:ハイドリンP‐7、中京油脂社製、固形分濃度30%)7.5部、5%界面活性剤水溶液(商品名:SNウェットOT‐70、サンノプコ社製)5部、グリオキザール(日本合成化学工業社製、固形分濃度40%)0.3部、及び水12.5部からなる組成物を混合して保護層用塗液を得た。
合成紙(商品名:FPG‐80、ユポ・コーポレーション社製、厚さ80μm)の片面上に、支持体に近い側から感熱記録層用塗液(I)を乾燥後の塗布量が2.5g/m2、感熱記録層用塗液(II)を乾燥後の塗布量が4.0g/m2、保護層用塗液を乾燥後の塗布量が3.0g/m2となるように順次メイヤーバーにて塗布及び乾燥した後、スーパーカレンダー処理を行い、感熱記録体を得た。
実施例4‐1の感熱記録体の作製において、感熱記録層用塗液(II)を乾燥後の塗布量が4.0g/m2となるように塗布する代わりに、感熱記録層用塗液(II)を乾燥後の塗布量が2.5g/m2となるように塗布した以外は、実施例4‐1と同様にして感熱記録体を得た。
実施例4‐1の感熱記録体の作製において、感熱記録層用塗液(I)を乾燥後の塗布量が2.5g/m2となるように塗布する代わりに、感熱記録層用塗液(II)を乾燥後の塗布量が4.0g/m2となるように塗布し、感熱記録層用塗液(II)を乾燥後の塗布量が4.0g/m2となるように塗布する代わりに、感熱記録層用塗液(I)を乾燥後の塗布量が2.5g/m2となるように塗布した以外は、実施例4‐1と同様にして感熱記録体を得た。
実施例4‐1のAiv液調製において、第1染料前駆体として4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンに代えて、4‐[2‐(2‐ブトキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンを用いた以外は、実施例4‐1と同様にして感熱記録体を得た。
実施例4‐1の感熱記録体の作製において、感熱記録層用塗液(II)を乾燥後の塗布量が4.0g/m2となるように塗布する代わりに、感熱記録層用塗液(II)を乾燥後の塗布量が5.0g/m2となるように塗布した以外は、実施例4‐1と同様にして感熱記録体を得た。
実施例4‐1の感熱記録体の作製において、感熱記録層用塗液(I)を乾燥後の塗布量が2.5g/m2となるように塗布する代わりに、感熱記録層用塗液(I)を乾燥後の塗布量が4.0g/m2となるように塗布し、感熱記録層用塗液(II)を乾燥後の塗布量が4.0g/m2となるように塗布する代わりに、感熱記録層用塗液(II)を乾燥後の塗布量が2.5g/m2となるように塗布した以外は、実施例4‐1と同様にして感熱記録体を得た。
実施例4‐1の感熱記録体の作製において、支持体として合成紙(商品名:FPG‐80、ユポ・コーポレーション社製、厚さ80μm)の片面に代えて、アルミ蒸着フィルム(商品名:VM‐PET、東レ社製、厚さ50μm)のアルミ蒸着層が設けられた面を用いた以外は、実施例4‐1と同様にして感熱記録体を得た。
実施例4‐1のAiv液調製において、第1染料前駆体として4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンに代えて、1‐(4‐n‐ドデシルオキシ‐3‐メトキシフェニル)‐2‐(2‐キノリル)エチレンを用いた以外は、実施例4‐1と同様にして感熱記録体を得た。
実施例4‐1のBiv液調製において、第2染料前駆体として3‐(N‐エチル‐p‐トルイジノ)‐6‐メチル‐7‐アニリノフルオランに代えて、融点が182℃の3‐ジ(n‐ブチル)アミノ‐6‐メチル‐7‐アニリノフルオランを用いた以外は、実施例4‐1と同様にして感熱記録体を得た。
感熱記録用シミュレーター(商品名:TH‐PMD、大倉電機社製)を用い、印加エネルギー0.660mJ/dot及び0.968mJ/dotの条件にて記録し、記録部の発色濃度としてx‐rite分光濃度計(商品名:x‐rite528、エックスライト社製、色彩測定モード)で、Y(Yellow)及びV(Visual)濃度を測定した。また、目視にて色調を評価した。
上記の印加条件によって発色させた像を目視にて観察し、色分離性を下記の基準で評価した。
Claims (15)
- 支持体上に染料前駆体及び顕色剤を含有する感熱記録層を備え、前記染料前駆体が黄色系の色調に発色する染料前駆体である感熱記録体であって、
(a) 前記支持体が金属光沢を有し、金属光沢を有しない基材の表面に金属光沢を付与した支持体であり、
及び/又は
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、下記一般式(1):
で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b1) 第2染料前駆体と高分子化合物とを含む複合微粒子の形態、若しくは
(b2) 200℃以上の融点を有する染料前駆体
である
感熱記録体。 - (a) 前記支持体が金属光沢を有し、金属光沢を有しない基材の表面に金属光沢を付与した支持体であって、
前記感熱記録体を0.97mJ/dotの印加エネルギーでサーマルヘッドにより印字して得られる動発色のイエロー濃度が1.00以上であり、且つ前記感熱記録体を40~220℃の熱板に9.8×104Paで5秒間接触させて得られる発色濃度が0.2となる静発色開始温度が50℃以上である、請求項1に記載の感熱記録体。 - (a) 前記支持体が金属光沢を有し、金属光沢を有しない基材の表面に金属光沢を付与した支持体であって、
前記黄色系の色調に発色する染料前駆体の含有量が0.7g/m2以上である、請求項1又は2に記載の感熱記録体。 - 感熱記録体が2色感熱記録体であり、
(a) 前記支持体が金属光沢を有し、金属光沢を有しない基材の表面に金属光沢を付与した支持体であって、
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b1) 第2染料前駆体と高分子化合物とを含む複合微粒子の形態であって、
前記感熱記録層が少なくとも第1感熱記録層及び第2感熱記録層からなる多層構造を有しており、前記第1染料前駆体が第1感熱記録層に含有され、少なくとも前記第2染料前駆体が複合微粒子の形態で第2感熱記録層に含有される、請求項1に記載の感熱記録体。 - 感熱記録体が2色感熱記録体であり、
(a) 前記支持体が金属光沢を有し、金属光沢を有しない基材の表面に金属光沢を付与した支持体であって、
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b1) 第2染料前駆体と高分子化合物とを含む複合微粒子の形態であって、
前記ピリジン骨格を有する第1染料前駆体が、4‐[2‐(2‐ブトキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐ペンチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐ヘキシルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐(2,6‐ジフェニル‐4‐ピリジニル)‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ブトキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ペンチルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ヘキシルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、及び4‐[2,6‐ビス(2‐オクチルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンからなる群から選ばれる少なくとも1種である、請求項1又は5に記載の感熱記録体。 - 感熱記録体が2色感熱記録体であり、
(a) 前記支持体が金属光沢を有し、金属光沢を有しない基材の表面に金属光沢を付与した支持体であって、
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b1) 第2染料前駆体と高分子化合物とを含む複合微粒子の形態であって、
前記感熱記録体を0.66mJ/dotの印加エネルギーでサーマルヘッドにより印字して得られる動発色のイエロー濃度が1.00以上であり、且つ0.97mJ/dotの印加エネルギーでサーマルヘッドにより印字して得られる動発色のイエロー濃度が1.00以上である、請求項1、5又は6に記載の感熱記録体。 - 感熱記録体が2色感熱記録体であり、
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b1) 第2染料前駆体と高分子化合物とを含む複合微粒子の形態である
感熱記録体であって、
前記感熱記録層が少なくとも第1感熱記録層及び第2感熱記録層からなる多層構造を有しており、前記第1染料前駆体が第1感熱記録層に含有され、少なくとも前記第2染料前駆体が複合微粒子の形態で第2感熱記録層に含有される、請求項1に記載の感熱記録体。 - 感熱記録体が2色感熱記録体であり、
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b1) 第2染料前駆体と高分子化合物とを含む複合微粒子の形態である
感熱記録体であって、
前記ピリジン骨格を有する第1染料前駆体が、4‐[2‐(2‐ブトキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐ペンチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐ヘキシルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐(2,6‐ジフェニル‐4‐ピリジニル)‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ブトキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ペンチルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ヘキシルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、及び4‐[2,6‐ビス(2‐オクチルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンからなる群から選ばれる少なくとも1種である、請求項1又は8に記載の感熱記録体。 - 感熱記録体が2色感熱記録体であり、
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b1) 第2染料前駆体と高分子化合物とを含む複合微粒子の形態である
感熱記録体であって、
前記2色感熱記録体を0.66mJ/dotの印加エネルギーでサーマルヘッドにより印字して得られる動発色のイエロー濃度が1.00以上であり、且つ0.97mJ/dotの印加エネルギーでサーマルヘッドにより印字して得られる動発色のイエロー濃度が1.00以上である、請求項1、8、又は9に記載の感熱記録体。 - 感熱記録体が2色感熱記録体であり、
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b2) 200℃以上の融点を有する染料前駆体であって、
前記感熱記録層が少なくとも第1感熱記録層及び第2感熱記録層からなる多層構造を有しており、前記第1感熱記録層が第1染料前駆体を含有し、前記第2感熱記録層が第2染料前駆体を含有する、請求項1に記載の感熱記録体。 - 感熱記録体が2色感熱記録体であり、
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b2) 200℃以上の融点を有する染料前駆体であって、
前記ピリジン骨格を有する第1染料前駆体が、4‐[2‐(2‐ブトキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐ペンチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐ヘキシルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2‐(2‐オクチルオキシフェニル)‐6‐フェニル‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ブトキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ペンチルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、4‐[2,6‐ビス(2‐ヘキシルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミン、及び4‐[2,6‐ビス(2‐オクチルオキシフェニル)‐4‐ピリジニル]‐N,N‐ジメチルベンゼンアミンからなる群から選ばれる少なくとも1種である、請求項1又は11に記載の感熱記録体。 - 感熱記録体が2色感熱記録体であり、
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b2) 200℃以上の融点を有する染料前駆体であって、
前記2色感熱記録体を0.66mJ/dotの印加エネルギーでサーマルヘッドにより印字して得られる動発色のイエロー濃度が1.00以上であり、且つ0.97mJ/dotの印加エネルギーでサーマルヘッドにより印字して得られる動発色のイエロー濃度が1.00以上である、請求項1、11、又は12に記載の感熱記録体。 - 感熱記録体が2色感熱記録体であり、
(b) 黄色系の色調に発色する染料前駆体が第1染料前駆体であり、さらに、前記第1染料前駆体とは異なる色調に発色する第2染料前駆体を含有し、
前記第1染料前駆体が、前記一般式(1)で表される分子構造にピリジン骨格を有する化合物であり、
前記第2染料前駆体が、
(b2) 200℃以上の融点を有する染料前駆体であって、
前記支持体が金属光沢を有する、請求項1、11、12、又は13に記載の感熱記録体。 - 前記一般式(1)で表される分子構造にピリジン骨格を有する染料前駆体において、式中、R1及びR2は、同時に水素原子である場合を除く染料前駆体である、請求項1~14のいずれか1項に記載の感熱記録体。
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BR112015027959-7A BR112015027959B1 (pt) | 2013-05-10 | 2014-05-01 | Meio de gravação sensível ao calor exibindo tom de metal dourado |
US14/888,269 US9751352B2 (en) | 2013-05-10 | 2014-05-01 | Heat-sensitive recording medium displaying gold metal tone, and/or heat-sensitive recording medium displaying two different color tones |
EP14795257.6A EP2995466A4 (en) | 2013-05-10 | 2014-05-01 | Heat-sensitive recording medium displaying gold metal tone, and/or heat-sensitive recording medium displaying two different color tones |
CN201480026419.2A CN105189132B (zh) | 2013-05-10 | 2014-05-01 | 表现出金色金属色调的热敏记录介质和/或表现出两种不同色调的热敏记录介质 |
KR1020157034955A KR102313080B1 (ko) | 2013-05-10 | 2014-05-01 | 골드 메탈 색조를 나타내는 감열 기록체, 및/또는 상이한 2색의 색조를 나타내는 감열 기록체 |
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JP2013-101864 | 2013-05-14 | ||
JP2013101845A JP6011448B2 (ja) | 2013-05-14 | 2013-05-14 | 2色感熱記録体 |
JP2013101864A JP5942924B2 (ja) | 2013-05-14 | 2013-05-14 | 2色感熱記録体 |
JP2013-101845 | 2013-05-14 | ||
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EP (1) | EP2995466A4 (ja) |
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JP2014218055A (ja) * | 2013-05-10 | 2014-11-20 | 王子ホールディングス株式会社 | 感熱記録体及びその記録方法 |
JP2016165859A (ja) * | 2015-03-10 | 2016-09-15 | 王子ホールディングス株式会社 | 感熱記録体 |
WO2016142764A1 (ja) * | 2015-03-10 | 2016-09-15 | 王子ホールディングス株式会社 | 感熱記録体 |
JP2016182765A (ja) * | 2015-03-26 | 2016-10-20 | 王子ホールディングス株式会社 | 感熱記録体 |
CN106904014A (zh) * | 2017-01-22 | 2017-06-30 | 上海固尔建工贸有限公司 | 一种防伪票证热敏纸及其制备方法 |
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CN112431028A (zh) * | 2020-10-20 | 2021-03-02 | 上海永利输送系统有限公司 | 一种自控温轻型输送带的制备方法 |
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TW201504359A (zh) | 2015-02-01 |
BR112015027959B1 (pt) | 2022-08-30 |
KR102313080B1 (ko) | 2021-10-15 |
CN105189132B (zh) | 2018-06-26 |
EP2995466A4 (en) | 2017-07-19 |
TWI629317B (zh) | 2018-07-11 |
EP2995466A1 (en) | 2016-03-16 |
KR20160006216A (ko) | 2016-01-18 |
US20160059604A1 (en) | 2016-03-03 |
US9751352B2 (en) | 2017-09-05 |
BR112015027959A2 (ja) | 2017-09-05 |
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