EP0307836B1 - Matériau d'enregistrement thermosensible - Google Patents

Matériau d'enregistrement thermosensible Download PDF

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Publication number
EP0307836B1
EP0307836B1 EP88114852A EP88114852A EP0307836B1 EP 0307836 B1 EP0307836 B1 EP 0307836B1 EP 88114852 A EP88114852 A EP 88114852A EP 88114852 A EP88114852 A EP 88114852A EP 0307836 B1 EP0307836 B1 EP 0307836B1
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EP
European Patent Office
Prior art keywords
group
heat sensitive
bis
sensitive recording
alkyl
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EP88114852A
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German (de)
English (en)
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EP0307836A3 (en
EP0307836A2 (fr
Inventor
Toshimi Central Research Laboratory Satake
Tadakazu Central Research Laboratory Fukuchi
Toshiaki Central Research Laboratory Minami
Tomoaki Central Research Laboratory Nagai
Toshio Central Research Laboratory Kaneko
Fumio Central Research Laboratory Fujimura
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Jujo Paper Co Ltd
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Jujo Paper Co Ltd
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Priority claimed from JP62230774A external-priority patent/JPH068072B2/ja
Priority claimed from JP62333939A external-priority patent/JPH01171980A/ja
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Publication of EP0307836A2 publication Critical patent/EP0307836A2/fr
Publication of EP0307836A3 publication Critical patent/EP0307836A3/de
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/323—Organic colour formers, e.g. leuco dyes
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/337—Additives; Binders
    • B41M5/3377—Inorganic compounds, e.g. metal salts of organic acids
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/914—Transfer or decalcomania

Definitions

  • the invention relates to a heat-sensitive recording material which has superior resistance to the effects of light, climate and oils and has better optical readability in the near infrared range.
  • a heat-sensitive recording sheet is generally prepared by applying a coating composition to the surface of a support such as paper, synthetic paper, film, plastic, etc., which is obtained by finely grinding and dispersing a colorless chromogenic substance and a color developing material, mixing the dispersions obtained and Addition of a binder, filler, sensitizer, lubricant and other auxiliaries. Under the influence of heat from the thermal spring, thermal head, thermal stamp, laser beam, etc., an instantaneous chemical conversion takes place, which leads to the recording.
  • a coating composition to the surface of a support such as paper, synthetic paper, film, plastic, etc.
  • heat sensitive recording sheets include use in technical recording equipment, computer terminal printers, facsimile machine printers, ticket machines, bar code printer printers and the like. Recently, much higher and more diverse requirements have been placed on recording devices, which is why a high quality of the recording sheet is required.
  • the rapid recording of the heat-sensitive recording sheet is said to have a clear high-density recording image even with little heat input, and it is also said to have superior resistance to the effects of light, climate and oils, that is, good durability.
  • heat-sensitive recording sheets are used for heat-sensitive notes in which the color formation is restricted to the visible range. Therefore, when using a semiconductor laser as a bar code scanner of POS systems, etc., they were unsuitable for reading in the near infrared range.
  • JP-OS 59-199757 and JP-OS 60-226871 have proposed heat-sensitive recording sheets in which a known color developing agent (acid clay, phenolic resin, hydroxybenzoic acid ester, bisphenol-A) and a fluoranleuco dye are combined with superior color formation in the near IR range are.
  • a known color developing agent ascid clay, phenolic resin, hydroxybenzoic acid ester, bisphenol-A
  • a fluoranleuco dye are combined with superior color formation in the near IR range are.
  • JP-OS 62-243652, JP-OS 62-243653 and JP-OS 62-257970 describe heat-sensitive recording sheets in which a known color developing agent and a divinyl compound are combined with superior color formation in the near infrared region.
  • the invention has for its object to provide a heat-sensitive recording material which is improved in the resistance to the action of light, climate and oils, and in the optical readability in the near infrared range, especially in bar code recordings.
  • the dyes of the following general formula (IV) are preferred: wherein R1, R2, R3, R4, R5, R7, R8, R9, T1, T2, T3 and R4 have the meaning given above.
  • R1, R2, R3, R4, R5, R7, R8, R9, T1, T2, T3 and R4 have the meaning given above.
  • an alkyl group preferably has 1-8 carbon atoms and a cycloalkyl group 5-8 ring atoms.
  • Aryl is preferably phenyl and naphthyl.
  • fluorine leuco dyes is not particularly limited; you can use the following, for example: 2-methyl-6-p- (p-dimethylaminophenyl) aminoaniline fluoran, 2-methoxy-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-chloro-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, p-nitro-6-p- (p-di ethylaminophenyl) amino-anilinofluoran, 2- Amino-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-diethylamino-6-p- (p-dimethylaminophenyl) aminoanilinofluoran, 2-phenyl-6-p- (p-phenylaminophenyl) aminoanilinofluoran, 2-benzyl-6-p - (p-phenyl) aminoaniline flu
  • a C1-C12 alkyl group and a C1-C12 alkoxy group can be a straight or branched radical.
  • Typical examples of an alkyl group with 1-12 carbon atoms and an alkoxy group with 1-12 carbon atoms are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl -, hexyl, octyl, nonyl, dodecyl, methoxy, ethoxy, tert-butoxy group and the like.
  • Typical examples of a C3-C10 cycloalkyl group are a cyclohexyl, 2-ethylcyclohexyl, p-tert-butylcyclohexyl group and the like.
  • Halogen-substituted zinc benzoate derivatives which can be used according to the invention are colorless substances with high melting points and can be prepared by reacting a halogen-substituted sodium benzoate derivative with zinc sulfate.
  • the stabilizer that can be used according to the invention is selected from several organic carboxylic acid metal salts.
  • Benzoic acid zinc salts with 1 - 2 halogen atoms on the benzene ring show greater resistance to light, oils and climatic influences than organic carboxylic acids and their polyvalent metal salts.
  • Halogen-substituted zinc benzoate derivatives which can be used according to the invention are, for example:
  • Preferred examples of the organic color developing agent which can be used according to the invention are bisphenol A types, 4-hydroxybenzoic acid esters, 4-hydroxyphthalic diesters, phthalic acid monoesters, bis (hydroxyphenyl) sulfides, 4-hydroxyphenylarylsulfones, 4-hydroxyphenylarylsulfonates, 1,3-di- [2- (hydroxyphenyl) -2-propyl] benzene, 4-hydroxybenzoyloxybenzoic acid ester, bisphenolsulfones, etc.
  • suitable compounds of this type are as follows:
  • the above color developing agents can be used either alone or in combination.
  • the fluoranleuco dye according to the invention can be used to further improve the optical readability in the near infrared range in combination with at least one substance from the group of the fluorene leuco dyes, divinylphthalide derivatives [in addition to those of the general formula (II)], sulfonylmethane derivatives, etc.
  • the divinyl compounds according to the invention can of course also be used in combination with at least one substance from the group of the fluorene leuco dyes, fluoranleuco dyes [in addition to those of the general formula (I)], sulfonylmethane derivatives, etc.
  • Preferred fluorene leuco dyes are the following near infrared absorbing leuco dyes of the general formula (VII): wherein R21, R22, R23, R24, R25 and R26 are the same or different and each represents a hydrogen atom, a C1-C8 alkyl group, a C5-C8 cycloalkyl group, a C3-C8 alkoxyalkyl group, a C3-C9 unsaturated alkyl group, one Tetrahydrofurfuryl group, a tetrahydropyran-2-methyl group, an alkyl group which can be substituted by a halogen atom, a C1-C4-alkyl group and / or a C1-C4-alkoxy group, an aryl group which by a halogen atom, a C1-C4-alkyl group and / or a C1-C4 alkoxy group can be substituted, or a C2-C8 al
  • the selection of the leuco dye of the formula (VII) used according to the invention is not subject to any particular restrictions; you can use the following, for example: 3,6-bis (dimethylamino) fluorene-9-spiro-3 ′ - (6′-dimethylamino) phthalide and 3,6-bis (diethylamino) fluorene-9-spiro-3 ′ - (6 ′ -diethylamino) -phthalide.
  • Preferred divinylphthalide derivatives are the following leuco dyes of the general formula (VIII) which absorb in the near infrared range: wherein R27, R28, R29 and R30 are the same or different and each have a C1-C8 alkyl group, a C5-C8 cycloalkyl group, a C3-C8 alkoxyalkyl group, a halogen atom, an aryl group, which is replaced by a halogen atom, a C1-C4- Alkyl group and / or a C1-C4-alkoxy group may be substituted, or a C1-C8-alkyl group which may be substituted by a halogen atom, a C1-C4-alkyl group and / or a C1-C4-alkoxy group; R27 and R28 or R29 and R30 optionally together or with an adjacent benzene ring a heterocyclic Can form a ring; and R31 and
  • Preferred sulfonylmethane derivatives are the following leuco dyes of the general formula (IX) which absorb in the near infrared range: wherein R41, R42, R43 and R44 are the same or different and each represents a hydrogen atom or a substituted or unsubstituted alkyl group; R45 and R46 are the same or different and each represents a hydrogen atom or a substituted or unsubstituted one Represent phenyl group; and R47 represents a substituted or unsubstituted alkyl group, or a substituted or unsubstituted phenyl group.
  • R41, R42, R43 and R44 are the same or different and each represents a hydrogen atom or a substituted or unsubstituted alkyl group
  • R45 and R46 are the same or different and each represents a hydrogen atom or a substituted or unsubstituted one Represent phenyl group
  • R47 represents a substituted or un
  • sulfonylmethane derivatives which can be used according to the invention is not subject to any particular restrictions, for example the following can be used: Bis- (p-dimethylaminostyryl) -p-methylphenylsulfonylmethane, Bis- (p-diethylaminostyryl) -p-methylphenylsulfonylmethane, Bis (p-dimethylaminostyryl) benzenesulfonylmethane.
  • a sensitizer can be added to the color development layer according to the invention.
  • Typical examples of such sensitizers are fatty acid amides, such as stearic acid amide, palmitic acid amide, etc., ethylene bisamide, montan wax, polyethylene wax, dibenzyl ester of terephthalate, benzyl p-benzyloxybenzoate, di-p-tolyl carbonate, p-benzylbiphenyl, phenylnaphthoxynyl carbonate, 1,4-phenyl-1-phthalyl-1,4-phthalate -naphthoic acid phenyl ester etc.
  • Binders according to the invention are, for example, completely saponified polyvinyl alcohol, degree of polymerization: 200-1900, partially saponified polyvinyl alcohol, carboxylated polyvinyl alcohol, amide-modified polyvinyl alcohol, sulfonic acid-modified polyvinyl alcohol, butyral-modified polyvinyl alcohol, other modified polyvinyl alcohols, hydroxyethyl cellulose, methyl cellulose styrene, methyl cellulose acid, carboxy Copolymers, cellulose derivatives such as ethyl cellulose and acetyl cellulose, polyvinyl chloride, polyvinyl acetate, polyacrylamide, polyacrylic acid ester, polyvinyl butyral, polystyrene, copolymers of the above compounds, polyamide resin, silicone resin, petroleum resin, terpene resin, ketone resin and coumarone resin.
  • These high molecular weight Binders can be used after being dissolved in a solvent such
  • the type and amount of the organic color developing agent according to the invention, the basic colorless chromogenic dye, the other additives which are determined depending on the desired effect and the suitability for recording purposes are not restricted.
  • the heat-sensitive material according to the invention is produced by applying the coating composition to a base material such as paper, synthetic paper, film, plastic, etc.
  • the organic color developing agent according to the invention, iron salt of a saturated higher fatty acid, the basic colorless chromogenic dye and optionally the other additives are ground to a particle size of several microns or smaller by means of a grinding device such as a ball mill, attritor, sand grinder, etc., or by means of a suitable emulsifying machine .
  • a grinding device such as a ball mill, attritor, sand grinder, etc.
  • Various additives are added to produce the coating composition of the invention.
  • the additives which can be used according to the invention are, for example, the following: fillers; Release agents for preventing sheet sticking, such as metal salts of fatty acids; lubricant for mottling prevention such as fatty acid amide, ethylene bisamide, montan wax, polyethylene wax, etc .; Dispersants such as sodium dioctylsulfosuccinic acid, sodium dodecylbenzenesulfonate, sodium lauryl alcohol sulfate, sodium alginate, etc .; UV absorbers of the benzophenone and triazole series; Anti-foaming agents; Fluorescent dyes; water repellant, etc.
  • both inorganic and organic fillers which are used in the paper processing industry can be used as the fillers according to the invention.
  • the fillers according to the invention are alumina, talc, silicon dioxide, magnesium carbonate, aluminum hydroxide, magnesium hydroxide, barium sulfate, kaolin, titanium dioxide, zinc oxide, calcium carbonate, aluminum oxide, urea-formaldehyde resin, polystyrene resin, phenolic resin, etc.
  • a cover layer e.g. be applied from a polymer.
  • the reason for the superior optical readability of the heat-sensitive recording sheet according to the invention in the near infrared range is probably the following:
  • the colored image of the recording sheet when using conventional, electron-donating color developing agents, for example from the fluorine series do not take up any light in the near infrared range.
  • the fluoranleuco dyes of the general formula (I) according to the invention or the divinyl compounds of the general formula (II) according to the invention absorb during color development in the heat-melting reaction in the presence of an electron acceptor particularly strong in the near infrared range (especially in the range of 700 - 1500 nm).
  • a heat-sensitive recording sheet is composed of a basic colorless dye as an electron donor and an organic acidic substance such as a phenolic compound, aromatic carboxylic acid, organic sulfonic acid, etc.
  • the heat-melting reaction is a kind of acid-base reaction which affects electron donation and - Recording is based, whereby a metastable charge transfer complex is formed, which leads to the colored image.
  • each of the halogen atoms is bonded directly to a benzene nucleus and, because of its strong electron attraction, leads to a decrease in the electron density on the metal via the mediation of the ⁇ electrons of the benzene ring.
  • zinc is a transition metal atom with an empty d-orbital and, in contrast to other polyvalent metals (magnesium, aluminum, calcium, titanium, manganese, tin and nickel), takes up electrons more easily.
  • the halogen-substituted zinc benzoate derivative therefore leads to the strengthening of the chemical bond between an organic color developing agent and the fluoranleuco dye according to the invention or the divinyl compound according to the invention. Therefore, it is believed that the chemical bond even under the influence of light, heat Moisture etc. is not dissolved for a long time, so that the recording image is very stable and the optical readability in the near infrared region is not reduced.
  • the reason for the better thermal responsiveness is based on the fact that halogen-substituted zinc benzoate derivatives have a superior color development ability and, because of their synergism with another color development agent, lead to an increase in color development sensitivity.
  • Solution A (dye dispersion): Basic, colorless chromogenic dye (see Table I) 2.0 parts 10% aqueous solution of polyvinyl alcohol 4.6 parts water 2.6 parts
  • Solution B (color developer dispersion): 4,4'-isopropylidenediphenol 6.0 parts 10% aqueous solution of polyvinyl alcohol 18.8 parts water 11.2 parts
  • Solution C (stabilizer dispersion): Stabilizer (see Table I) 4.0 parts 10% aqueous solution of polyvinyl alcohol 9.2 parts water 5.2 parts
  • a heat-sensitive coating composition is obtained: Coating mass Solution A (dye dispersion) 9.2 parts Solution B (color developer dispersion) 36.0 parts Solution C (stabilizer dispersion) 18.4 parts Kaolin clay (50% aqueous dispersion) 12.0 parts.
  • Solution A (dye dispersion 1) Basic, colorless chromogenic dye 1 (see Table I) 1.0 part 10% aqueous solution of polyvinyl alcohol 2.3 parts water 1.3 parts
  • Solution D (dye dispersion 2) Basic, colorless chromogenic dye 2 (see Table I) 1.0 part 10% aqueous solution of polyvinyl alcohol 2.3 parts water 1.3 parts.
  • This coating composition was applied in a coating amount of 6.0 g / m2 on a base paper with a weight of 50 g / m2, dried and supercalendered to achieve a smoothness of 200-600 s.
  • a heat sensitive recording sheet was obtained.
  • a heat-sensitive recording sheet was obtained in the same manner as in Example 1, except that Solution C was not used.
  • Solution A Basic colorless chromogenic dye (see Table III) 2.0 parts 10% aqueous solution of polyvinyl alcohol 4.6 parts water 2.6 parts
  • Solution B color developer dispersion: Color developing agents (see Table III) 6.0 parts 10% aqueous solution of polyvinyl alcohol 18.8 parts water 11.2 parts
  • Solution C stabilizer dispersion: Stabilizer (see Table III) 4.0 parts 10% aqueous solution of polyvinyl alcohol 9.2 parts water 5.2 parts
  • This coating composition was applied in a coating amount of 6.0 g / m2 on a base paper with a weight of 50 g / m2, dried and supercalendered to achieve a smoothness of 200-600 s.
  • a heat sensitive recording sheet was obtained.
  • a heat-sensitive recording sheet was obtained in the same manner as in Example 3, except that Solution C was not used.

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

Claims (8)

  1. Matériau d'enregistrement thermosensible avec une couche révélatrice de couleur thermosensible sur un support, la couche révélatrice de couleur thermosensible contenant un colorant chromogène incolore ou légèrement coloré basique et un révélateur de couleur organique, caractérisé en ce que la couche révélatrice de couleur thermosensible contient au moins un colorant du groupe formé par :
    a) des leuco-colorants à base de fluoranne de la formule générale :
    Figure imgb0033
     où au moins l'un des radicaux de R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈ et R₉ représente un radical de formule générale :
    Figure imgb0034
     les autres radicaux parmi R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈ et R₉ sont identiques ou différents et représentent, chacun, un atome d'hydrogène ou d'halogène, un groupe alcoyle, alxoxy, cycloalcoyle, nitro, hydroxy, amino, amino substitué, aralkyle aralkyle substitué, aryle ou aryle substitué;
    T₁, T₂, T₃ sont identiques ou différents et représentent, chacun, un atome d'hydrogène, un groupe C₁-C₈-alcoyle, C₃-C₉-alkényle ou C₃-C₉-alkinyle;
    T₄ est un atome d'hydrogène, un groupe C₁-C₈-alcoyle, C₃-C₉ alkényle, C₃-C₉-alkinyle ou un groupe phényle; ou
    T₃ et T₄ peuvent être combinés avec un atome d'azote adjacent, composant ainsi un groupe morpholino, pyrrolidino, piperidino ou hexaméthylénimino; et
    n représente un nombre entier de 0 à 4;
    b) et/ou des composés divinyliques de formule générale (II) :
    Figure imgb0035
     où
    R₁₁ représente un groupe alcoyle à 8 atomes de C ou moins;
    R₁₂ représente un groupe alcoyle à 8 atomes de C ou moins, un groupe C₅-C₇-cycloalcoyie ou un groupe benzyle ou phényle qui peut éventuellement être substitué par un atome de chlore ou de brome ou un C₁-C₄-alcoyle;
    X¹ et X² sont identiques ou différents et représentent, chacun, un groupe alcoyle à 8 atomes de C ou moins, un groupe alkoxy à 8 atomes de C ou moins, un atome de fluor, chlore ou brome;
    m et n sont identiques ou différents et représentent, chacun, un nombre entier 0, 1, 2 ou 3;
    chacun des X¹ dans (X¹)m est identique ou différent;
    chacun des X² dans (X²)n est identique ou différent;
    et chacun des X³ dans (X³)₄ est identique ou différent et représente un atome de chlore ou de brome, au moins un X³ étant un atome de brome;
    et, comme stabilisateur, un benzoate de zinc substitué par un halogène de formule générale (III) :
    Figure imgb0036
     où
    X représente un atome d'halogène
    A représente un atome d'hydrogène, un groupe nitro, C₁-C₁₂-alcoyle, C₁-C₁₂-alkoxy, C₃-C₁₀-cycloalcoyle, cyano ou hydroxy ;
    l représente un nombre entier 1 ou 2; et
    m représente un nombre entier de 0 à 4.
  2. Matériau d'enregistrement thermosensible selon la revendication 1, caractérisé en ce que le leuco-colorant à base de fluoranne de la formule générale (I) est le 2-chloro-3-méthyl-6-p-(p-phénylaminophényl)-amino-anilinofluoranne ou le 2-méthyl-6-p-(p-diméthylaminophényl)-amino-anilinofluoranne.
  3. Matériau d'enregistrement thermosensible selon la revendication 1, caractérisé en ce que le composé divinylique de formule générale (II) est 3,3-bis-[2-p-diméthylaminophényl)-2-(p-méthoxyhényl)-éthényl)-4,5,6,7-tétrabromophtalide.
  4. Matériau d'enregistrement thermosensible selon l'une des revendications 1 à 3, caractérisé en ce que la couche révélatrice de couleur contient, en outre, au moins un dérivé de sulfonylméthane sélectionné parmi bis-(p-diméthylaminostyryl)-p-méthylphénylsulfonylméthane, bis-(p-diéthylaminostyryl)-p-méthylphénylsulfonylméthane et bis-(p-diméthylaminostyryl)-benzènesulfonylméthane.
  5. Matériau d'enregistrement thermosensible selon l'une des revendications 1 à 3, caractérisé en ce que la couche révélatrice de couleur contient, en outre, un leuco-colorant à base de fluorène sélectionné parmi le 3,6-bis-(diméthylamino)-fluorène-9-spiro-3'-(6'-diméthylamino)phtalide et le 3,6-bis-(diéthylamino)-fluorène-9-spiro-3'-(6'-diéthylamino)phtalide.
  6. Matériau d'enregistrement thermosensible selon l'une des revendications 1 à 3, caractérisé en ce que le révélateur de couleur contient au moins un composé du groupe : dérivés du bisphénol-A, 4-hydroxy-benzoate, 4-hydroxy-diphtalate, monophtalate, bis-(hydroxyphényl)-sulfure, 4-hydroxyphénylarylsulfone, 4-hydroxyphénylarylsulfonate, 1,3-di-[-2(hydroxyphényl)-2-propyl]-benzène, 4-hydroxybenzoyloxybenzoate et bisphénolsulfone.
  7. Matériau d'enregistrement thermosensible selon l'une des revendications 1 à 3, caractérisé en ce que la masse révélatrice de couleur contient de 1 à 8 parts en poids du révélateur de couleur organique suivant l'invention, de 0,1 à 5 parts en poids de stàbilisateur et de 1 à 20 parts en poids de charge pour 1 part en poids du colorant chromogène incolore basique, et de 10 à 25 parts en poids de liant par rapport à la teneur totale en matières solides.
  8. Matériau d'enregistrement thermosensible selon l'une des revendications 1 a 3, caractérisé en ce que la couche révélatrice de couleur contient, en outre, au moins un dérivé de phtalide de divinyle de formule générale (VIII) :
    Figure imgb0037
     où
    R₂₇, R₂₈, R₂₉ et R₃₀ sont identiques ou différents et représentent, chacun, un groupe C₁-C₈-alcoyle, un groupe C₅-C₈-cycloalcoyle, un groupe C₃-C₈-alkoxyalcoyle, un atome d'halogène, un groupe aryle qui peut être substitué par un atome d'halogène, un groupe C₁-C₄-alcoyle et/ou un groupe C₁-C₄-alkoxy ou un groupe alcoyle qui peut être substitué par un atome d'halogène, un groupe C₁-C₄-alcoyle et/ou un groupe C₁-C₄-alkoxy;
    R₂₇ et R₂₈ ou R₂₉ et R₃₀ peuvent également former un anneau hétérocycle l'un avec l'autre ou avec un noyau benzène adjacent, et R₃₁ et R₃₂ sont identiques ou différents et représentent, chacun, un atome d'hydrogène, un atome d'halogène, un groupe C₁-C₄-alcoyle, un groupe C₁-C₄-alkoxy ou un groupe acyloxy;
    R33 représente un atome d'hydrogène ou un groupe C₁-C₄-alcoyle;
    a, b, c et/ou d peuvent représenter, chacun, un atome de carbone, un ou deux des atomes de carbone pouvant être remplacés par un atome d'azote; chacun de ces atomes de carbone pouvant être lié avec un atome d'hydrogène, un atome d'halogène, un groupe C₁-C₈-alcoyle, un groupe C₁-C₄-alkoxy, un groupe C₂-C₁₆-dialkylamino ou un groupe nitro; une liaison de a-b, b-c ou c-d pouvant faire partie d'un autre noyau aromatique.
EP88114852A 1987-09-14 1988-09-12 Matériau d'enregistrement thermosensible Expired - Lifetime EP0307836B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP62230774A JPH068072B2 (ja) 1987-09-14 1987-09-14 感熱記録材料
JP230774/87 1987-09-14
JP62333939A JPH01171980A (ja) 1987-12-28 1987-12-28 感熱記録材料
JP333939/87 1987-12-28

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EP0307836A2 EP0307836A2 (fr) 1989-03-22
EP0307836A3 EP0307836A3 (en) 1990-09-19
EP0307836B1 true EP0307836B1 (fr) 1993-04-28

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Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1328171C (fr) * 1988-01-20 1994-04-05 Jujo Paper Co., Ltd. Materiau d'enregistrement thermosensible
US5200947A (en) * 1989-02-03 1993-04-06 Jujo Paper Co., Ltd. Optical recording medium, optical recording method, and optical recording device used in method
EP0381492B1 (fr) * 1989-02-03 1998-04-15 Nippon Paper Industries Co., Ltd. Matériau pour l'enregistrement optique, méthode pour l'enregistrement optique, et dispositif pour l'enregistrement optique utilisé dans cette méthode
JP2536917B2 (ja) * 1989-02-06 1996-09-25 日本製紙株式会社 光記録体
GB8911419D0 (en) * 1989-05-18 1989-07-05 Smith & Mclaurin Limited Heat-sensitive record material
US5146087A (en) * 1991-07-23 1992-09-08 Xerox Corporation Imaging process with infrared sensitive transparent receiver sheets
US5164356A (en) * 1991-11-12 1992-11-17 Appleton Papers Inc. Thermally-responsive record material
DE69316586T2 (de) * 1993-03-31 1998-04-30 Nicca Chemical Co Wärmeempfindliches Aufzeichnungsmaterial
US5441418A (en) * 1993-05-20 1995-08-15 Binney & Smith Inc. Thermochromic drawing device
US5514635A (en) * 1993-12-29 1996-05-07 Optum Corporation Thermal writing surface and method for making the same
US7993807B2 (en) * 2004-04-28 2011-08-09 Hewlett-Packard Development Company, L.P. Compositions, systems, and methods for imaging
US20060153608A1 (en) * 2005-01-10 2006-07-13 Xerox Corporation System and method for determining printing media is appropriate for use in a printer/copier
US7198834B2 (en) * 2005-03-22 2007-04-03 Hewlett-Packard Development Company, L.P. Imaging media including interference layer for generating human-readable marking on optical media
US20070065623A1 (en) * 2005-09-21 2007-03-22 Vladek Kasperchik Laser-imageable coating based on exothermic decomposition
US20070065749A1 (en) * 2005-09-21 2007-03-22 Vladek Kasperchik Radiation-markable coatings for printing and imaging
US20070086308A1 (en) * 2005-10-13 2007-04-19 Gore Makarand P Systems and methods for imaging
CN118834546B (zh) * 2024-06-25 2026-01-27 吉林大学 一种电致变色器件及其制备方法

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59199757A (ja) * 1983-04-28 1984-11-12 Yamamoto Kagaku Gosei Kk フルオレン化合物、その製造法およびそれを用いる記録材料
US4721701A (en) * 1985-01-09 1988-01-26 Jujo Paper Co., Ltd. Thermosensitive recording sheet
JPS62148287A (ja) * 1985-12-24 1987-07-02 Kanzaki Paper Mfg Co Ltd 記録体
US4761396A (en) * 1986-02-12 1988-08-02 Kanzaki Paper Manufacturing Co., Ltd. Heat-sensitive recording material
JPH0815813B2 (ja) * 1986-06-09 1996-02-21 山田化学工業株式会社 感熱記録材料
EP0242170B1 (fr) * 1986-04-16 1991-09-18 Yamada Chemical Co., Ltd. Composés divinyliques et matière chromogène d'enregistrement préparée en utilisant ces composés
US4826806A (en) * 1986-07-31 1989-05-02 Shin Nisso Kako Co., Ltd. Fluoran compounds and color forming recording materials using same
JPH066392B2 (ja) * 1987-04-09 1994-01-26 日本製紙株式会社 感熱記録体
JP2778701B2 (ja) * 1988-09-12 1998-07-23 マナック株式会社 ブリーチ加工用脱色促進剤

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US4853362A (en) 1989-08-01
EP0307836A3 (en) 1990-09-19
DE3880599D1 (de) 1993-06-03
EP0307836A2 (fr) 1989-03-22
CA1296896C (fr) 1992-03-10

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