WO2002042088A1 - Support d'enregistrement thermique polychrome - Google Patents

Support d'enregistrement thermique polychrome Download PDF

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Publication number
WO2002042088A1
WO2002042088A1 PCT/JP2001/009994 JP0109994W WO0242088A1 WO 2002042088 A1 WO2002042088 A1 WO 2002042088A1 JP 0109994 W JP0109994 W JP 0109994W WO 0242088 A1 WO0242088 A1 WO 0242088A1
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Prior art keywords
color
sensitive recording
electron
bis
heat
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PCT/JP2001/009994
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English (en)
Japanese (ja)
Inventor
Yasunori Ishii
Michihiko Sato
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Mitsubishi Paper Mills Limited
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Publication of WO2002042088A1 publication Critical patent/WO2002042088A1/fr

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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
    • B41M5/34—Multicolour thermography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/3275—Fluoran compounds

Definitions

  • the present invention relates to a multicolor heat-sensitive recording material that develops different colors depending on the heating conditions. More specifically, the present invention relates to a multicolor heat-sensitive recording material having a clear color tone, excellent color separation of two or more colors, and excellent image storability. Background art
  • the heat-sensitive recording material is generally provided with a heat-sensitive recording layer having, as a main component, an electron-donating, usually colorless or pale-colored dye precursor and an electron-accepting developer on a support. Heating with a thermal head, a hot pen, a laser beam, etc., allows the dye precursor and the developer to react instantaneously to produce a colored image.
  • Such a heat-sensitive recording material has the advantages that recording can be obtained with a relatively simple device, maintenance is easy, and there is no generation of noise.
  • Measurement recorders, fax machines, printers, computer terminals It is used in a wide range of fields such as vending machines, labels and ticket vending machines.
  • multicolor thermal recording materials capable of developing two or more colors depending on the heating temperature are desired.
  • a method for realizing such a multicolor thermal recording material
  • thermosensitive recording component is adjusted by changing the melting point, etc., of the compounds constituting the thermosensitive recording component.Only the thermosensitive recording component with a low coloring temperature develops color at low temperature heating, and the thermosensitive recording component with low coloring temperature at high temperature. A method in which a thermosensitive recording component having a higher coloring temperature develops color at the same time to develop a color tone different from that at the time of low-temperature heating;
  • thermosensitive recording component contained in a layer more distant from the surface is colored at a higher heating temperature
  • Etc. are known.
  • the coloring temperature is adjusted by changing the melting point of the compound constituting the heat-sensitive recording component
  • usable materials are limited, and there is a problem that a balance with other characteristics cannot be sufficiently obtained.
  • the method (2) in which different heat-sensitive recording components are contained in separate laminated layers has a problem that the layer structure of the multicolor heat-sensitive recording material is complicated and productivity is poor.
  • the compound that constitutes the thermal recording component is encapsulated in a microcapsule and the wall of the microcapsule has a role as a color control layer so that color development such as color temperature can be achieved.
  • Methods for adjusting the characteristics have been proposed.
  • a plurality of electron-donating dye precursors having different coloring colors are contained together with an electron-accepting compound in the same heat-sensitive recording layer.
  • a method has been proposed to enclose at least one of them in a microphone mouth capsule.
  • the temperature at which the electron-donating dye precursor contained in the microphone-capsule reacts with the electron-accepting compound to form a color can be increased, and the electron-donating dye contained in the microphone-capsule can be increased. Since the dye precursor and the non-encapsulated electrophilic dye precursor do not interact with each other, two or more types of color tones can be obtained with one heat-sensitive recording layer.
  • Various microencapsulation methods can be applied as a method of forming a color development control layer on the surface of the compound constituting the heat-sensitive recording component.
  • As a method of coating the color-forming component with a thermoplastic mic mouth capsule wall an interfacial polymerization method, a coacervation method, a spray dry method, a curing-in-liquid coating method, a melting dispersion cooling method, and the like are known.
  • thermosensitive recording component When encapsulating the compound constituting the thermosensitive recording component in a microphone mouth capsule, Since these compounds are usually solids, when using the interfacial polymerization method, the compounds constituting the heat-sensitive recording component are dissolved in a solvent, the raw material for the capsule wall is added, and this is emulsified in a medium such as water. After that, there is a method of evaporating the solvent in which the coloring component is dissolved and polymerizing the capsule membrane, but this method has a drawback that the process becomes complicated and productivity decreases.
  • the uniformity of the capsule film is poor, and the particle size of the capsule tends to increase.
  • the melting point of the capsule film is limited to a relatively low melting point, so that there is a disadvantage that the characteristics of the formed capsule wall are also limited.
  • Japanese Patent Application Laid-Open No. Hei 9-142025 discloses that an electron-donating dye precursor is used as a compound constituting a heat-sensitive recording component, and the electron-donating dye precursor is used as a composite particle with a polyurea or a polyurethane to develop color characteristics. It proposes a method of obtaining a multicolor heat-sensitive recording material by adjusting the particle size and incorporating the composite particles into the heat-sensitive recording material. According to this method, compared to the method using a microphone-mouth capsule, it is stated that the sensitivity is less reduced and that coloring due to pressure or friction is less likely to occur. However, this method requires a large amount of polyurea or polyurethane to completely cover the electron-donating dye precursor, so that sufficient sensitivity cannot be obtained. In addition, there is a disadvantage that the controllability of the coloring properties is also limited to some extent.
  • Hei 8-207441 a red-coloring dye precursor selected from 3-ethylamino-17-chlorofluorene and the like as an electron-donating dye precursor, and 1, 1, 3-
  • a method has been proposed in which two or more compounds selected from tris (2-methynole 4-hydroxy-5-cyclohexynolephenyl) butane and the like are used as a preservative improver. It is described that according to the above method, a two-color heat-sensitive recording material having excellent red color development and excellent storage stability of a red color image can be obtained. However, in this method, a clear red color image cannot be obtained because the red color tone is vermilion, and sticking between the thermal paper and the thermal head tends to occur during printing. It was not satisfactory. Disclosure of the invention
  • the problem to be solved by the present invention is to provide a multicolor heat-sensitive recording material having a clear color tone, excellent color separation of two or more colors, and excellent storage stability of a low-temperature color image.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, have come to invent the multicolor heat-sensitive recording material of the present invention.
  • a heat-sensitive recording layer is provided on a support, and the heat-sensitive recording layer comprises two or more kinds of usually colorless to light-colored electron-donating dye precursors that develop different colors and the electron-donating dye precursors.
  • a multicolor heat-sensitive recording material containing an electron-accepting compound capable of forming a dye, wherein one of the electron-donating dye precursors is 3-di-1-n-butylamino-6-methyl-17-bromofluorane This is a multicolor heat-sensitive recording material characterized in that:
  • the electron-accepting compound is a compound represented by the following general formula (I) and a bis (3-aryl-14-hydroxide).
  • Roxyphenyl) Sulfone is preferably at least one selected from the group consisting of sulfones.
  • X represents a hydrogen atom or a lower alkyl group
  • R ⁇ R 2 and R 3 may be the same or different and each represents a hydrogen atom, a halogen atom, a hydroxyl group, a lower alkyl group, or a cycloalkyl group;
  • R 4 , R 5 and R 6 may be the same or different and each represent a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group;
  • R 7 is a hydrogen atom or a general formula (II)
  • the compound represented by the general formula (I) is 2,4-bis (phenylsulfol) phenol. Is preferred.
  • At least one or more of the electron-donating dye precursors are particles having a color-developing layer obtained by polymerizing a compound having an unsaturated carbon bond on the surface. It preferably exists in the thermosensitive recording layer in a state.
  • the heat-sensitive recording layer comprises two or more kinds of usually colorless or light-colored electron-donating dye precursors that form different colors and an electron-accepting colorant that forms the electron-donating dye precursor. And a compound.
  • the first color tone is usually formed by a colorless or pale color electron-donating dye precursor and an electron-accepting compound, and at high temperature heating, the first color tone is added to the first color tone.
  • the second color tone is formed by the usually colorless or light-colored electron-donating dye precursor and the electron-accepting compound having a color tone different from that of the above.
  • At least one of the two or more usually colorless or light-colored electron-donating dye precursors that develops a different color tone is usually colorless that develops a red color tone.
  • 3-di-n-butylamino-16-methyl-7-bromofluoran which is a light-colored electron-donating dye precursor
  • a red-colored image with a clear color tone and excellent image storability can be produced at a low temperature. It can be obtained as a colored image.
  • 3-di-n-butylamino-6-methyl-7-bromofluorane as an electron-donating dye precursor, a colorless or pale-colored black-, green-, or blue-based color is developed.
  • a high-temperature color image formed by mixing with another electron-donating dye precursor can be made black, which is closer to true black.
  • the problem of the present invention cannot be solved using the above-mentioned conventionally known electron-donating dye precursor.
  • a dye precursor that develops a purple-red color tone represented by 3,3-bis (1-ethynoleic 2-methylindole-13-yl) phthalide
  • the body gives a dark color that is far from the original red color, so it is not enough to get a vivid red color.
  • a dye precursor that develops an orange color such as represented by 3-getylamino-6,8-dimethylfluoran, has a color tone of black after the color mixture is close to brown. Insufficient.
  • Dye precursors such as 3-Jetylamino-1 7-Mouth Fluoran give a red color from vermilion to orange, so that a clear red color can be obtained. Is insufficient, and the color of black is also close to brown, so not only is the color separation of red and black insufficient, but also the image storability is poor.
  • 3-di-n-butylamino-16-methyl-7-bromofluoran used in the present invention develops a clear and pure red color tone which cannot be realized by the above-mentioned electron-donating dye precursor, and It is also excellent in preservation of color images. Further, a high-temperature color image, which is usually colorless or light-colored and develops a black-based, green-based, or blue-based color tone by mixing with another electron-donating dye precursor, can be converted to a black color that is almost pure black.
  • a sufficiently clear red-colored image can be obtained by using 3-di-n-butylamino 6-methyl-7-bromofluorane as a dye precursor that develops a red color tone.
  • the object of the present invention is to further fine-tune the red color tone.
  • Other dye precursors that develop a red color can be selected from the electron-donating dye precursors listed above.
  • the multicolor heat-sensitive recording material of the present invention among the two or more kinds of the electron-donating dye precursors contained in the heat-sensitive layer, 3-d-n-butylamino 6-methyl-7-bromofur which develops a red color tone.
  • At least one of the dye precursors other than orane is an electron-donating dye precursor that develops a black, green, or blue color tone to obtain a black color tone by mixing with red that develops at low temperatures. Is used.
  • the dye precursor that develops a black, green, or blue color tone include electron donating compounds generally used in heat-sensitive recording paper and pressure-sensitive recording paper. Specific examples include the following, but are not limited thereto.
  • Black electron-donating dye precursors 3-dibutylamino 6-methyl-7-arinofluoran, 3-dibutylamino_6-methyl-7_phenylaminofluoran, 3-dibutylamino 7- (2-chloroamino- Reno) Phenoleorane, 3-dibutinoreaminol 7— (o—black mouth phenyl) amino fluoran, 3-getylamine 6—methyl-7-anilinol fluoran, 3-getylamino 6-methyl-7 phenylaminofluoran, 3-getyl Amino 6-methyl-7-xylidinofluoran, 3-diethylamino 7- (2-chloroanilino) fluoran, 3-getylamino-7- (o-chlorophenyl) aminofluoran, 3-getylamino-7 (o-phenyl phenyl) amino-fluoran, 3-methylamino 7-(2-phenol-phenylamino) fluoran
  • Green electron donating dye precursor 3- (N-ethyl-N-n-hexyl) amino-7-anilinofluorane, 3- (N-ethyl-N-p-tolyl) amino-7- (N-furyl N-methyl) aminofluoran, 3- (N-ethyl-N-n-propyl) amino-7-dibenzylaminobu Luoran, 3- (N-ethynole N-n-propynole) Amino-6-chloro-one 7-Dipendinoleaminophnoleolane, 3- (N-ethynole N-4-methylthiophene) amino-7- (N-methyl 1-N-phenyl) aminofluoran, 3 _ (N-ethynoleic 4-methinolephenyl) amino-7-dibenzylaminofluoran, 3- (N-ethyl-4-methylphenyl) amino-6-methyl-7-dibenzylamino Phen
  • Blue-based electron-donating dye precursors 3- (1-Ethyl-2-methylin-l-3-inole) -1,3- (4-ethylenaminophenyl) phthalide, 3- (1-ethynoley 2-methinolay) 1-3 (Isle) 1 3-(2-Methyl 4-Jetylaminophenol) 1-4-Azaphthalide, 3-(1-Ethyl 2-Methylindole 1-3-Innole) 1 3 — (2-Ethoxy 41-aminophenyl) 4-azaphthalide, 3 _ (1-Ethyl-2-methylindoleno-3-inole) 1-3— (2-Ethoxy-4-methinoleaminophenyl) 1-4 Azaphthalide, 3— (1-Ethyl-1-Methylindole—3-yl) 1-3— (2_Ethoxy-14-Ethylaminoamino) 1-4 Azaphthalide, 3 -— (1-Ethy
  • These black, green or blue dye precursors can be used alone or in combination of two or more.
  • the electron-accepting compound which forms two or more of usually colorless or light-colored electron-donating dye precursors that form different colors is generally a heat-sensitive recording material or a pressure-sensitive recording material.
  • the acidic substances used in the above are used. Specific examples include the following, but are not limited thereto.
  • Clay materials such as activated clay, zeolite, bentonite, 4-phenylphenol, 4-t butynolephen, 4-hydroxyacetophenone, 2,2,2-hydroxydiphenyl, 2,2 ' -Methylenebis (4-methyl-6-t-butylphenol), 4,4'-ethylenebis (2-methynolephenone), 1,1-bis (4-hydroxyphenol).
  • These electron accepting compounds can be used alone or in combination of two or more.
  • the electron accepting compound that causes the color of the electron-donating dye precursor 3-di-n-butylamino 6-methyl-7-bromofluoran
  • the electron accepting compound that causes the color of the electron-donating dye precursor 3-di-n-butylamino 6-methyl-7-bromofluoran
  • X represents a hydrogen atom or a lower alkyl group
  • R ⁇ R 2 and R 3 may be the same or different and each represents a hydrogen atom, a halogen atom, a hydroxyl group, a lower alkyl group, or a cycloalkyl group;
  • R 4 , R 5 and R 6 may be the same or different and each is a hydrogen atom Represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group,
  • R 7 is a hydrogen atom or a general formula (II)
  • Examples of the sulfol compound represented by the general formula (I) used in the multicolor heat-sensitive recording material of the present invention include compounds disclosed in JP-A-8-269,000. Specific examples include, but are not limited to, the following.
  • sulfonyl compounds represented by the general formula (I) used in the present invention when 2,4-bis (phenylsulfonyl) phenol is used, compared with the case where other sulfonyl compounds are used, Basic characteristics such as thermal responsiveness, saturation density of the color image, whiteness of the background, preservation of the image and background, and the amount of residue deposited on the thermal head of the thermal printer are all good. A multicolor heat-sensitive recording material having good and good quality balance without defects can be obtained.
  • the amount of at least one compound selected from the sulfonyl compound represented by the general formula (I) and bis (3-aryl-4-hydroxyphenyl) sulfone is 3-di-n-butylamino-6.
  • the amount is preferably 50 to 100 parts by weight, more preferably 100 to 600 parts by weight, based on 100 parts by weight of methyl-7-bromofluoran.
  • an electron-accepting compound which is generally used for a thermosensitive recording material or a pressure-sensitive recording material.
  • the heat-sensitive recording layer in the multicolor heat-sensitive recording material of the present invention is, for example, a black color by mixing a low-temperature color image with red and a high-temperature color image with a low-temperature color image and a color tone different from red.
  • a black color by mixing a low-temperature color image with red and a high-temperature color image with a low-temperature color image and a color tone different from red.
  • two color-forming layers are provided on the support, and a color tone of red is formed on the upper layer on the atmosphere side. It is preferable to contain -methyl-17-bromofluorane, and to contain, in the lower layer on the side of the support, a generally colorless or light-colored electron-donating dye precursor which develops a color tone different from red.
  • the heat-sensitive recording layer in the multicolor heat-sensitive recording material of the present invention may be composed of only one color-forming layer.
  • the colorless or pale-color electron-donating dye precursor which develops a red color tone at low temperature is used. It develops a color tone different from red, whose thermal response has been adjusted by providing a 3-di-n-butylamino 6-methyl-7-bromofluorane and a color-regulating layer on the surface.
  • the colorless or pale-colored electron-donating dye precursor is usually contained in the same color-forming layer.
  • the productivity of the multicolor heat-sensitive recording material can be improved, which is more preferable.
  • a colorless or light-colored electron-donating dye precursor that develops a color tone different from that of the low-temperature color-developed image is polymerized with a compound having an unsaturated carbon bond on the surface, and the color-controlling layer is provided on the particles. It is most preferable to include it in the heat-sensitive recording layer (color-forming layer) in the form because the color tone is clearer and the two-color separation is excellent.
  • the first color tone is generated by the reaction between the usually colorless or light-colored electron-donating dye precursor having no color-developing layer on its surface and the electron-accepting compound
  • Heating at a high temperature causes the first color tone to be mixed with the color tone due to the reaction between the usually colorless or light-colored electron-donating dye precursor provided with a color-regulating layer on the surface and the electron-accepting compound.
  • a second tone occurs.
  • the electron-donating dye precursor particles having a color control layer on the surface used in the multicolor heat-sensitive recording material of the present invention wherein the color control layer is obtained by polymerizing an unsaturated carbon bond-containing compound. By polymerizing the unsaturated carbon bond-containing compound, the productivity is better than when a color control layer is prepared using a conventional microcapsule manufacturing method, and the characteristics of the color control layer are improved. It can be controlled freely.
  • the color control layer is formed by adding an unsaturated carbon bond-containing compound to the dispersion of the dye precursor particles, adding a polymerization initiator, and then heating as necessary to allow the unsaturated carbon bond-containing compound to undergo addition polymerization.
  • Dye precursor particle surface coated with polymer It is formed by doing.
  • the unsaturated carbon bond-containing compound When the unsaturated carbon bond-containing compound is added to the dispersion of the dye precursor, (a) the unsaturated carbon bond-containing compound is emulsified in the dispersion of the dye precursor, and (b) the dye precursor is dispersed. The liquid dispersion and the majority of the unsaturated carbon bond-containing compound are phase-separated to form separate layers, but a trace amount of the unsaturated carbon bond-containing compound is dissolved in the dye precursor dispersion. And (c) a state in which the dispersion of the dye precursor and the unsaturated carbon bond-containing compound are completely insoluble and completely phase-separated.
  • state (b) force is particularly preferably used for forming a color control layer on the surface of the particles of the dye precursor. That is, when the unsaturated carbon bond-containing compound is polymerized in such a state (b), the surface of the dye precursor particles is more uniform and denser than when polymerized in the other states (a) and (c). This makes it possible to form a color control layer excellent in various properties, and has an advantage that the particles of the dye precursor are aggregated and coarse particles are hardly formed.
  • State (b) can be realized by appropriately selecting the type of dispersion medium for dispersing the dye precursor particles and the type of unsaturated carbon bond-containing compound.
  • Known polymerization initiators can be used for polymerizing the unsaturated carbon bond-containing compound.
  • the polymerization reaction is not particularly limited in the type of polymerization, such as radical polymerization, anionic polymerization, and cationic polymerization. It is particularly preferably used. Specific examples of the polymerization initiator for radical polymerization are shown below. Peroxides such as tamenodiperoxide, t-butinoleperoxide, dicumylperoxide, di-t-butylperoxide, benzoyl peroxide, lauroyl peroxide, etc., and persulfates such as potassium persulfate and ammonium persulfate.
  • Azo compounds such as azobisisobutyronitrile, a combination of hydrogen peroxide and ferrous salt, a combination of persulfate and sodium acid sulfite, a combination of tamene hydroxyperoxide and ferrous salt Combination, over Combination of benzoyl oxide and getylaurine, combination of peroxide and metal alkyl, combination of oxygen and organometallic alkyl, etc.
  • the dispersion of the dye precursor and the unsaturated carbon bond-containing compound are substantially insoluble, and most of the dye precursor dispersion and the unsaturated carbon bond-containing compound undergo phase separation to form separate layers.
  • a polymerization initiator is used. Particularly preferred is one which dissolves in a dispersion medium in which a dye precursor is dispersed. By using such a polymerization initiator, it is possible to prevent the particles of the dye precursor from aggregating to form coarse particles.
  • the unsaturated carbon bond-containing compound used to form the color control layer is a compound having a carbon-carbon double bond and a carbon or carbon-carbon triple bond as an unsaturated carbon bond.
  • -Ridene compounds, bielene compounds, cyclic olefins and acetylene compounds are examples of the unsaturated carbon bond-containing compound used to form the color control layer.
  • vinyl compound examples include styrene, isobutene, 3-methyl-1-butene, butynolebininoleether, methinolevinyl ketone, nitroethylene, vinylidene cyanide, ethylene, propylene, and vinyl chloride.
  • acetylene compound examples include, but are not limited to, acetylene and phenylacetylene. These vinyl compounds, vinylidene compounds, vinylene compounds, cyclic olefins, acetylene compounds and the like can be used alone or as a mixture of two or more.
  • the unsaturated carbon bond-containing compound is appropriately selected for the purpose of adjusting the properties of the color control layer.
  • an unsaturated carbon bond-containing compound By selecting an unsaturated carbon bond-containing compound, the thermal properties of the dye precursor during heating can be controlled.
  • a method for controlling the thermal properties of the dye precursor a compound containing two or more unsaturated carbon bonds in one molecule as an unsaturated carbon bond-containing compound is used, and the amount of the compound is adjusted. And the like.
  • the ratio of the unsaturated carbon bond-containing compound to the dye precursor is preferably 5 to 500% by weight.
  • the proportion of the unsaturated carbon bond-containing compound is less than 5% by weight, the function as a color control layer is insufficient, while when it exceeds 500% by weight, the color of the dye precursor is insufficient.
  • the dispersion of the dye precursor and the electron-accepting compound can be obtained by a method in which the dye precursor is dry-milled and dispersed in a dispersion medium, or a method in which the dye precursor is mixed in a dispersion medium and wet-milled.
  • An arbitrary method can be used as a method for pulverizing.
  • the particle size of the dye precursor particles in the dispersion is preferably 20 zm or less. If the particle size is larger than this, it is not preferable because uniform printing cannot be performed.
  • the particle size is particularly preferably 10 ⁇ m or less, and more uniform printing can be obtained.
  • the lower limit of the particle size of the dye precursor particles is not particularly limited, but is preferably 0.1 ⁇ or more from the viewpoint of easy production.
  • the electron-donating dye precursor used for forming a color-adjusting layer on the surface and obtaining a second color image at a higher temperature includes low-temperature coloring.
  • compounds used for heat-sensitive recording paper and pressure-sensitive recording paper must be used.
  • a pigment, a sensitizer, an antioxidant, an anti-sticking agent and the like are added to the heat-sensitive recording layer as needed.
  • binders include starches, hydroxyethyl cellulose, methylcellulose, ethylcellulose, canoleoxymethylcellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylic acid, and polyacrylic acid.
  • Methacrylic acid polyacrylate, polymethacrylate, sodium polyacrylate, polyethylene terephthalate, polybutylene terephthalate, chlorinated polyether, aryl resin, furan resin, ketone resin, oxybenzoyl Polyester, Polyacetal, Polyethenoleetherketone, Polyethersnolephone, Polyimide, Polyamide, Polyamidoimid, Polyaminobismaleimide, Polymethinolepentene, Polyphenylene oxide, Reference: phenylene sulfide, polyphenylene sulfone, polysulfone, polyarylate, polyallyl sulfone, polybutadiene, polycarbonate, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyvinyl acetate, polyvinyl urethane, phenolic resin, ⁇ Rare resin, melamine resin, melamine formalin resin, benzoguanamine resin, bismaleimi
  • Specific examples include stearic acid amide, N-hydroxymethylstearic acid amide, N-stearylstearic acid amide, ethylenebisstearic acid amide, oleic acid amide, and palmitic acid amide.
  • fatty acid amides such as methylenebis hydrogenated tallow fatty acid amide and ricinoleic acid amide, paraffin wax, microcrystalline tusta, polyethylene wax, carnauba wax, etc., and natural waxes, N-stearyl urea, etc.
  • Aliphatic urea compound 2-benzinoleoxynaphthalene, bis (4-methoxypheninole) ether, 2,2,1-bis (4-methoxyphenoxy) ethynoleether, 1,2-bis (3 —Methyl ⁇ phenoxy) ethane, 1,2-bis (phenoxymethyl) benzene, trinolebi Ether compounds such as phenylene ether, naphthino ether derivatives, anthryl ether derivatives, aliphatic ethers, diphenyl adipate, di (4-methylbenzyl) oxalate, di-benzinole oxalate, di-ammonate (4-chloronore) Benzenole) Estenole, diphen-oleate carbonate, dimethinole terephthalenolate, dibenzi / terephthalenolate, fenenoleestenole benzenesnolephonate, ethenorele
  • sensitizers are preferably used in an amount of 20 to 250% by weight based on the dye precursor in order to obtain a sufficient thermal response.
  • the support on which the heat-sensitive recording layer is provided may be any of transparent, translucent, and opaque paper, nonwoven fabric, woven fabric, synthetic resin film, synthetic resin laminate paper, Paper, metal foil, ceramic paper, glass plate, or the like, or a composite sheet combining these can be used arbitrarily according to the purpose, but is not limited thereto.
  • one or more protective layers may be provided on the heat-sensitive recording layer directly or via another layer.
  • the components of the protective layer are not particularly limited, but those having little effect on the coloring properties of the heat-sensitive recording composition are particularly preferably used.
  • the resin used for forming the protective layer include starches, hydrated kissinenoresenorelose, methinoresenololose, etinoresenorelose, carboxymethinoresenorelose, gelatin, and casein.
  • An intermediate layer may be provided between the heat-sensitive recording layer and the support.
  • the intermediate layer can contain various resins, organic pigments, inorganic pigments, various hollow particles, and the like.
  • the layer between the heat-sensitive recording layer and the support, and the surface on which the Z or heat-sensitive recording layer is provided or on the opposite surface a layer containing an ink jet-recordable material, It is also possible to provide a layer that eats a material capable of recording information electrically, magnetically or optically.
  • a back coat layer may be provided on the surface opposite to the surface on which the heat-sensitive recording layer is provided for the purpose of preventing curling and electrification, and may be subjected to adhesive processing or the like. Further, printing with UV ink or the like may be performed on the surface of the heat-sensitive recording layer or the protective layer.
  • any layer and support in the heat-sensitive recording material may contain a light-heat conversion material.
  • any layer of the multicolor heat-sensitive recording material of the present invention if necessary, diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, hydroxide Inorganic and organic pigments such as aluminum and urea-formalin resin, as well as higher fatty acid metal salts such as zinc stearate and calcium stearate, paraffin, oxidized paraffin, polyethylene, polyethylene oxide, stearic acid amide, caster wax, etc. These waxes may also contain a dispersant such as sodium octyl sulfosuccinate, and a surfactant and a fluorescent dye.
  • a dispersant such as sodium octyl sulfosuccinate, and a surfactant and a fluorescent dye.
  • an antioxidant and an ultraviolet absorber can be added for the purpose of improving light resistance.
  • the antioxidant include, but are not particularly limited to, hindered amine antioxidants, hindered phenol antioxidants, and sulfide antioxidants.
  • UV absorbers include organic UV absorbers such as benzotriazole UV absorbers, salicylic acid UV absorbers, benzophenone UV absorbers, and the like.
  • examples include inorganic ultraviolet absorbers such as lead, titanium oxide, and cerium oxide, but are not particularly limited.
  • part represents part by weight
  • % represents% by weight
  • compositions were individually pulverized using a ball mill so that the volume average particle diameter became 1.0 / im, to prepare Liquids A to G.
  • Electron acceptor compound dispersion 7% 2% polybutyl alcohol aqueous solution ⁇ Electron acceptor compound dispersion
  • Example 2 In the same manner as in Example 1 except that 10 parts of E liquid was used instead of 10 parts of D liquid in the high-temperature coloring coating liquid, and 30 parts of E liquid was used instead of 30 parts of D liquid in the low-temperature coloring coating liquid, A multicolor heat-sensitive recording material in which the heat-sensitive recording layer was composed of two coloring layers was prepared.
  • Example 2 In the same manner as in Example 1 except that 10 parts of the F liquid was used instead of 10 parts of the D liquid in the high-temperature coloring coating liquid, and 30 parts of the F liquid was used instead of 30 parts of the D liquid in the low-temperature coloring coating liquid, A multicolor heat-sensitive recording material in which the heat-sensitive recording layer was composed of two coloring layers was prepared.
  • thermosensitive recording layer consists of two color developing layers in the same manner as in Example 1 except that 10 parts of solution A was used instead of 10 parts of solution A in the low-temperature color forming coating solution used in Example 1. Materials were made.
  • thermosensitive recording layer consists of two color developing layers in the same manner as in Example 2 except that 40 parts of Solution A was used instead of 40 parts of Liquid A in the low-temperature coloring coating solution used in Example 2. Materials were made.
  • Table 1 shows the structures of the heat-sensitive recording layers in the multicolor heat-sensitive recording materials of Examples 1 to 3 and Comparative Examples 1 to 3.
  • H liquid a dispersion liquid of electron-donating dye precursor particles provided with a color-developing layer on the surface.
  • a multicolor heat-sensitive recording material was prepared in the same manner as in Example 4, except that 40 parts of solution E was used instead of 40 parts of solution D in the multicolor heat-sensitive coating liquid. did.
  • a multi-color heat-sensitive recording layer comprising a single color-developing layer in the same manner as in Example 4, except that 10 parts of solution B was used instead of 10 parts of solution A in the multi-color heat-sensitive coating liquid used in Example 4.
  • a recording material was produced.
  • Multicolor heat-sensitive recording layer comprising a single color developing layer in the same manner as in Example 5 except that 10 parts of solution B was used instead of 10 parts of solution A in the multicolor heat-sensitive coating liquid used in Example 5. A recording material was produced.
  • a multicolor heat-sensitive recording layer comprising a single color-developing layer in the same manner as in Example 6 except that 10 parts of solution B was used instead of 10 parts of solution A in the multicolor heat-sensitive coating liquid used in Example 6.
  • a recording material was produced.
  • Table 1 shows the structure of the multicolor thermosensitive coloring layer in the single-layer type multicolor thermosensitive recording materials obtained in Examples 4 to 6 and Comparative Examples 4 to 6.
  • High-temperature coloring dye precursor provided with a coloring control layer 3-Jetylamino-1
  • Electron-accepting compound 2,2-bis (4-hydroxyphenyl) propane (D solution)
  • High-temperature coloring dye precursor provided with a coloring control layer 3-Jetylamino-1
  • Electron-accepting compound Bis (3-arylu 4-hydroxy sulfide) sulfone (E solution)
  • High-temperature coloring dye precursor provided with a coloring control layer 3—Jetylamino—
  • Electron accepting compound 2,4-bis (phenylsulfonyl) phenol (Solution F)
  • Electron-accepting compound 2,2-bis (4-hydroxyphenyl) propane (Solution D)
  • Electron-accepting compound Bis (3-arylu-4-hydroxyphenyl) sunorehon (E solution)
  • High-temperature coloring dye precursor provided with a coloring control layer 3-Jetylamino-1
  • Electron-accepting compound 2,4-bis (phenylsulfonyl) phenol (F solution)
  • Thermal facsimile printing tester equipped with a thermal head (main scanning line density 8 dot / mm, resistance value 790 ⁇ ) to the multicolor thermal recording materials of Examples 1 to 6 and Comparative Examples 1 to 6
  • a PMD manufactured by Okura Electric Co., Ltd.
  • an applied voltage of 20 volts and an applied pulse of 0.6 milliseconds were used to print a low-temperature red image.
  • an applied pulse of 1.5 milliseconds printed a high-temperature black image. The color tone of each printed area was visually observed.
  • the density of the printed area was measured using a reflection densitometer (RD918, manufactured by Macbeth), and the filter hole position was measured with magenta for low-temperature coloring and black for high-temperature coloring.
  • the results are shown in Table 13. If the low-temperature color is a clear red color with a reflection density of 1.10 or more and the high-temperature color is a non-reddish black color with a reflection density of 1.20 or more, color separation is good and there is no practical problem. It is.
  • a red-colored image printed in the same manner as in Test 1 was obtained by using a soft bursit chloride (product name: soft card case, manufactured by KOKUYO Co., Ltd.). ) was compared with the color density difference before and after storage at 20 ° C. and 60% RH for 14 days in a state of contact with 4.0 g Z cm 2 .
  • the density was measured using a reflection densitometer (RD918, manufactured by Macbeth), and the position of the filter hole was measured with magenta in the red image.
  • the results are shown in Table 14 as the concentrations after the test. If the concentration after the test is 0.80 or more, there is no practical problem.
  • the multicolor heat-sensitive recording materials of Examples 1 to 3 give clearer red and black images, have excellent color separation, and have a red image. Had excellent storage stability.
  • a multicolor heat-sensitive recording material having a clearer red image and excellent storage stability was obtained as compared with Example 1.
  • the multicolor heat-sensitive recording materials of Examples 4 to 6 not only a vivid red image color and a black image were obtained, but also the red border around the black image portion was small and excellent in color separation.
  • a multicolor heat-sensitive recording material having excellent red image preservability was obtained.
  • Example 5 a multicolor heat-sensitive recording material having a clearer red image and excellent storability as compared with Example 4 was obtained.
  • the multicolor heat-sensitive recording materials of Comparative Examples 1 to 6 lack the sharpness of the low-temperature color image, and the high-temperature color image is also reddish. The peripheral red border was large and color separation was insufficient. Also, the preservability of the red image was not practically sufficient.
  • the multicolor heat-sensitive recording material of the present invention has a clear color tone, excellent color separation properties, and excellent image storability, and is extremely useful in practical use.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Abstract

La présente invention concerne un support d'enregistrement thermique polychrome qui contient au moins deux types de précurseurs de colorant libérant des électrons, qui en général sont incolores ou de couleur claire, produisent sur un support, des tons de différentes couleurs et comportent une couche d'enregistrement thermique contenant un composé accepteur d'électrons qui assure la transformation en couleurs de ces précurseurs de colorant libérant des électrons. Le composé utilisé en tant que précurseur de colorant libérant des électrons est le 3-di-n-butylamino-6-méthyl-7-bromofluorane qui a pour effet de révéler des couleurs vivaces, d'assurer une séparation chromatique élevée et une excellente conservation des images.
PCT/JP2001/009994 2000-11-21 2001-11-15 Support d'enregistrement thermique polychrome WO2002042088A1 (fr)

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JP2000-354747 2000-11-21
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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08197847A (ja) * 1995-01-27 1996-08-06 New Oji Paper Co Ltd 赤黒２色感熱記録材料
JPH08216510A (ja) * 1995-02-14 1996-08-27 New Oji Paper Co Ltd 赤黒２色感熱記録型ラベル
EP0774363A1 (fr) * 1995-11-20 1997-05-21 Oji Paper Co., Ltd. Matériau pour l'enregistrement thermosensible
JPH10147069A (ja) * 1996-11-15 1998-06-02 Oji Paper Co Ltd 感熱記録体
JPH11198540A (ja) * 1998-01-14 1999-07-27 Mitsubishi Paper Mills Ltd 感熱記録材料
JP2000079766A (ja) * 1998-07-03 2000-03-21 Oji Paper Co Ltd 感熱記録材料
JP2000158822A (ja) * 1997-11-27 2000-06-13 Mitsubishi Paper Mills Ltd 感熱記録材料
JP2000247031A (ja) * 1999-02-26 2000-09-12 Mitsubishi Paper Mills Ltd 感熱記録材料
JP2001018538A (ja) * 1999-07-12 2001-01-23 Oji Paper Co Ltd 二色感熱記録体
JP2001113836A (ja) * 1999-10-18 2001-04-24 Fuji Photo Film Co Ltd 感熱記録材料

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08197847A (ja) * 1995-01-27 1996-08-06 New Oji Paper Co Ltd 赤黒２色感熱記録材料
JPH08216510A (ja) * 1995-02-14 1996-08-27 New Oji Paper Co Ltd 赤黒２色感熱記録型ラベル
EP0774363A1 (fr) * 1995-11-20 1997-05-21 Oji Paper Co., Ltd. Matériau pour l'enregistrement thermosensible
JPH10147069A (ja) * 1996-11-15 1998-06-02 Oji Paper Co Ltd 感熱記録体
JP2000158822A (ja) * 1997-11-27 2000-06-13 Mitsubishi Paper Mills Ltd 感熱記録材料
JPH11198540A (ja) * 1998-01-14 1999-07-27 Mitsubishi Paper Mills Ltd 感熱記録材料
JP2000079766A (ja) * 1998-07-03 2000-03-21 Oji Paper Co Ltd 感熱記録材料
JP2000247031A (ja) * 1999-02-26 2000-09-12 Mitsubishi Paper Mills Ltd 感熱記録材料
JP2001018538A (ja) * 1999-07-12 2001-01-23 Oji Paper Co Ltd 二色感熱記録体
JP2001113836A (ja) * 1999-10-18 2001-04-24 Fuji Photo Film Co Ltd 感熱記録材料

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