EP0097493A1 - Feuilles de transfert à sec pour l'enregistrement thermosensible et appareil d'enregistrement thermosensible - Google Patents

Feuilles de transfert à sec pour l'enregistrement thermosensible et appareil d'enregistrement thermosensible Download PDF

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Publication number
EP0097493A1
EP0097493A1 EP83303487A EP83303487A EP0097493A1 EP 0097493 A1 EP0097493 A1 EP 0097493A1 EP 83303487 A EP83303487 A EP 83303487A EP 83303487 A EP83303487 A EP 83303487A EP 0097493 A1 EP0097493 A1 EP 0097493A1
Authority
EP
European Patent Office
Prior art keywords
group
dye
image
transfer sheet
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP83303487A
Other languages
German (de)
English (en)
Inventor
Nobuyoshi Taguchi
Tokihiko Shimizu
Shu Hotta
Wataru Shimotsuma
Shoji Arai
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Panasonic Holdings Corp
Original Assignee
Matsushita Electric Industrial Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP57104926A external-priority patent/JPS5916780A/ja
Priority claimed from JP57105927A external-priority patent/JPS58220788A/ja
Priority claimed from JP57107219A external-priority patent/JPS58222890A/ja
Priority claimed from JP57124640A external-priority patent/JPS5914994A/ja
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
Publication of EP0097493A1 publication Critical patent/EP0097493A1/fr
Withdrawn legal-status Critical Current

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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
    • B41M5/382—Contact thermal transfer or sublimation processes
    • B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
    • 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5227—Macromolecular coatings characterised by organic non-macromolecular additives, e.g. UV-absorbers, plasticisers, surfactants

Definitions

  • This invention relates to the heat-sensitive recording and more particularly, to a novel type of dye transfer sheet or medium for use in heat-sensitive recording. Also, it relates to a heat-sensitive recording apparatus which is adapted to make the best use of the dye transfer sheet of the just-mentioned type.
  • a dye transfer sheet for heat-sensitive recording which comprises a support and a layer of a sublimating basic dye formed on the support, whereby when heated in an imagewise pattern, the dye sublimates from from the dye layer and deposits on an image-receiving medium according to the imagewise pattern.
  • The- sublimating basic dyes are preferably aromatic tertiary amines.
  • a heat-sensitive recording apparatus which comprises a first heat source which is controlled according to an information signal of picture element, a platen placed in face-to-face relation with the first heat source and establishing a gap with the first heat source so as to permit a transfer sheet having a sublimating basic dye layer to be passed therebetween along with an image-receiving sheet whose image-receiving surface is in face-to-face relation with the basic dye layer of the transfer sheet, and a second heat source located downstream of the first heat source to fix an image formed on the image-receiving surface, whereby when the transfer sheet is heated according to the information signal, the dye moves by sublimation toward the image-rece-iving layer in portions where heated thereby forming an intended image on the image-receiving layer, and the intended image is fixed by application of heat from the second heat source.
  • the dye transfer sheet according to the present invention is characterized by a layer of a sublimating basic dye formed on a support.
  • a variety of basic dyes are known in the art and may be used in the practice of the invention provided that their melting point is not too high. Usually, basic dyes having about 100°C or below are used. Preferable basic dyes include aromatic tertiary amines.
  • basic dyes of the following general formulae (1) through (6) are used: in which R 1 and R 2 independently represent a hydrogen atom or a phenyl group with or without being substituted with a chlorine atom, R 3 represent a hydrogen atom, a lower alkyl group, or an alkoxy group, R 4 and R 5 independently represent a lower alkyl group which is optionally substituted with a cyano group, a chlorine atom or a lower alkoxy group, or a benzyl group, or a phenyl group; in which R 6 and R 7 independently represent a lower alkyl group which is optionally substituted with a cyano group, a chlorine atom or a lower alkoxy group, or a benzyl group, or a phenyl group, X 1 and Y 1 independently represent a hydrogen atom, a chlorine atom, a methyl group, or a lower alkoxy group, and Y 2 represents a hydrogen atom, a chlorine atom, a chlorine
  • lower alkyl group. or “lower alkoxy group” means a group having not larger than 8 carbon atoms.
  • the dyes represented by the general formulae (1) and (2), (3) and (4), and (5) and (6) are yellow, magenta and cyan in color, respectively.
  • Typical and preferable examples of the dyes include the following dyes of the formulas (1) through (6).
  • dyes should preferably sublimate at temperatures below 100°C.
  • the dyes may be applied to a support by a variety of techniques. For instance, dyes may be sublimated or vacuum evaporated onto support, or solutions of dyes may be applied to support by casting or gravure printing.
  • Solvents for the dyes are, for example, chlorinated compounds such as chloroform, dichloromethane, dichloroethane, monochlorobenzene, o-dichlorobenzene and the like, and ethylene glycol compounds such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve, acetate, ethyl cellosolve acetate and the like.
  • the support should preferably be thin enough to efficiently transmit heat to an applied dye therethrough, e.g. its thickness is generally in the range of 5 to.20 microns.
  • Useful supports are condenser papers, electrolytic capacitor papers, porous thin papers, polymer films, metallic foils, metal-evaporated papers and the like. Dyes are applied to support generally in an amount of 10 to 10 g/m 2 .
  • additives such as stabilizers for dyes may be added to dyes.
  • resin binders having melting or softening temperatures over 100°C along with the dyes.
  • the basic dyes used in the practice of the invention have sublimation temperatures below 100°C. Accordingly, when resin binders whose softening or melting temperatures exceed 100°C are used in combination, unfavorable phenomena such as softening of binders, simultaneous transfer of binders with dyes, and troubles in sublimation of dyes will be suppressed even when high temperatures are applied at the time of recording.
  • Resin binders useful for the purposes are, for example, phenolic resins, melamine resins, urethane resins, epoxy resins, silicone resins, urea resins, diallyl phthalate resins, alkyd resins, acetal resins, methacrylic resins such as polymethyl methacrylate, polyesters, starch and its derivatives, cellulose derivatives, polyethylene, polypropylene, polystyrene, polyvinyl acetals such as polyvinyl butyral, polyamides such as 6-nylon, 11-nylon, 12- nylon, 6,6-nylon, 6,10-nylon and the like, polyvinyl alcohol, polycarbonates, polysulfones, polyether sulfones, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfides, polyethylene naphthalate, polyimides, polyamide-imides, AS resins, ABS resins, and the like.
  • polymers which are soluble in solvents such as acrylic resins, methacrylic resins, polystyrene, polyvinyl acetals, polyamides, polyvinyl alcohol, polycarbonates, polysulfones, polyether sulfones, polyphenylene oxides, cellulose derivatives and the like, are preferably used because of easy handling thereof.
  • binder resins may be applied to substrate after mixing with dyes, or may be applied in the form of a layer intervening between a support and a dye layer. Better results are obtained in the latter case.
  • Dye transfer sheets for heat-sensitive recording using binder resins can yield images of almost the same reflection density as dye transfer sheets free of binder resins. Presumably, this is considered as follows.
  • a binder resin-containing dye transfer sheet is more uniform than a resin- free sheet in distribution of sublimating dyes over substrate.
  • heat transmission also becomes more uniform because irregularities and fine pores on the surface of substrate are filled with binder resins applied.
  • heat from a heating unit of, for example, a thermal head of a recording apparatus is not-consumed as latent heat for melting or softening of resin binder, so that not only sublimation of dye is not impeded, but also heat transmission becomes better because of filling of fine pores in substrate.
  • dyes and binder resins in solvents are applied to support by casting or the like techniques.
  • dyes are mixed in an amount of from 10 to 1000 parts by weight per 100 parts by weight of resin binder.
  • a resin binder layer is formed between a dye layer and a substrate
  • an intended resin is applied to the substrate, such as, for example, by lamination or baking, or by application of reactive monomer onto substrate and curing of the monomer.
  • dyes are applied by vacuum evaporation or sputtering.
  • the basic dye transfer sheet of the present invention has been described above.
  • This type of transfer sheet is particularly effective when used in combination with an image-receiving medium which comprises a layer of nonionic electron acceptor.
  • This type of medium can yield images which are resistant to environmental changes.
  • the electron acceptors useful for the purposes include halogenated polyethylenes such as polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, poiyvinylidene fluoride, or the like, cyanated polyethylenes such as polyacrylonitrile, aromatic nitro compounds such as 2,4,7-trinitrofluorenone, aromatic nitrile compounds such as phthalodinitrile, 1,3,6,8-tetracyanopyrene, and the like, tetracyanoethylene, 7,7,8,8-tetracyanoquinodimethane derivatives, 11,11,12,12-tetracyanonaphthaquinodimethane derivatives, benzoquinone derivatives such as p-benzoquinone, p-fluoranyl, dichlorodicyanoquinone, and the like, aluminium halides such as aluminium fluoride, aluminium chloride, and the like, gallium halides, antimony halides, and the like.
  • polyvinylidene fluoride is considered to serve as an electron acceptor for the reason that the carbon positively polarizes as shown in the following formula
  • the image-receiving medium using electron acceptors produces better results when used in combination with basic dye transfer sheets of the present invention.
  • the resultant image is excellent in image transparency, uniform quality of image and stable in color reproduction, and has an enlarged range of color reproduction.
  • electron acceptors should be supported on substrate in the form of a thin layer, by which images of good quality can be obtained.
  • Electron acceptors can be formed on the surface of a substrate by vacuum evaporation, sputtering, casting or gravure printing. Needless to say, electron acceptors may be admixed with ordinarily employed additives or binders.
  • the recording principle is described using a basic dye transfer sheet of the invention.
  • a recording apparatus 1 including a thermal head 2 having a heating unit 3, and a platen 4.
  • a space S is established between the thermal head 2 and the platen 4 to permit a sublimating basic dye transfer sheet 5 and an image-receiving medium 6 to pass therethrough.
  • the sheet 5 and medium 6 are moved in the direction of arrow A.
  • the apparatus 1 further includes a pair of rollers 7 at least one of which is a heat roller for thermally fixing an image transferred on the image-receiving medium 6.
  • the basic dye transfer sheet 5 having a substrate 8 and a layer 9 of a sublimating basic dye with or without a binder formed on the substrate 8.
  • the basic dye may be applied to the substrate 8 as impregnated therein. In this case, the dye may not form a discrete layer on the substrate 8.
  • the basic dye layer 9 is heated in an imagewise pattern by.means of the heating unit 3 which is electrically controlled according to an information signal from a control circuit not shown.
  • the substrate is usually made of a thin sheet of about 5 to 20 microns in thickness.
  • condenser papers, electrolytic capacitor papers, porous thin papers, polymer films, metallic foils, metal-vaporized papers and the like are used as the thin substrate.
  • the image-receiving sheet 6 has a substrate 10 and an image-receiving layer 11.
  • the transfer sheet 5 and the image-receiving sheet 6 are set between the thermal head 2 and the platen 4 so that the dye layer 9 and the image-receiving layer 11 are facing each other.
  • the sheets 5 and 6 are separately moved by suitable drive means not shown.
  • the basic dye of the dye layer 9 is transferred to the image-receiving sheet 6 by sublimation or melting in an amount corresponding to an amount of heat generated from the heating unit 3.
  • the transferred dye diffuses into the image-receiving layer 11 where it reacts with an electron acceptor to form a color.
  • the sublimated or melted basic dye is attracted toward the image-receiving layer 11 by chemical reaction with the electron acceptor and diffuses into the image-receiving layer 11.
  • the dye moves toward the image-receiving layer not only by sublimation, but also by chemical reaction, so that it shows a greater tendency of sublimation than in the case where no chemical reaction is involved.
  • the transferred dye is not only deposited merely on the image-receiving sheet, but also chemically combined with the image-receiving layer. Thus, the once combined dye suffers little changes when placed under varying environmental conditions.
  • the image formed on the image-receiving layer is then heated by the paired rollers 7 to a temperature of 100 to 170°C for thermal fixation.
  • This thermal fixation assists the transferred dye to satisfactorily diffuse into the image-receiving layer.
  • the temperature of the thermal fixation depends on the type of dye and is generally in the range of 100 to 170°C. Lower temperatures are less effective whereas higher temperatures may result in discoloration of dye.
  • Fig. 2 schematically shows an enlarged sectional view of the transfer sheet 5 and the image-receiving layer 6.
  • the dye layer 9 is made of a sublimating basic dye 12 dispersed in a binder 13 and the image-receiving layer 11 is made of an electron acceptor 14 dispersed in a binder 15.
  • electron-acceptive polymers such as polyvinylidene chloride or polyvinylidene fluoride are used, they may also serve as a substrate 10.
  • the transfer sheet 5 has been illustrated hereinbefore as forming thereon the continuous basic dye layer 9.
  • the transfer sheet 5' includes the substrate 8 and basic dye layers 9a, 9b and 9c which are formed on the substrate in spaced relation with one another.
  • the basic dye layers 9a, 9b and 9c are made, for example, of cyan, magenta and yellow dyes, respectively.
  • a full color image can be obtained by superposing images from the basic dye layers 9a, 9b and 9c on a single image-receiving sheet according to an information signal. This is schematically shown in Fig. 4.
  • the dyes 9a, 9b and 9c transferred from the transfer sheet 5 by sublimation or melting diffuse into the image-receiving layer 11. These dyes 9a, 9b and 9c are mixed in molecular state in the image-receiving layer.
  • the mixing of the dyes in the molecular state has an advantage in that the resulting color is much brighter than a color obtained by superposition of dye layers as in color printing.
  • Fig. 5 there is shown another type of basic dye transfer sheet in which a polymer resin layer 16 is formed between the substrate 8 and the dye layer 9 as discussed before.
  • Fig. 6 shows a CIE chromaticity diagram of single and mixed colors obtained by the use of basic dye transfer sheets according to the present invention in comparison with those colors obtained from the ordinary color printing by an ordinary sublimation transfer printing technique. From the graph, it will be seen that the dye transfer technique of the present invention is comparable in color reproduction to ordinary color printing techniques.
  • the basic dye transfer sheet of the present invention can yield full color hard copies by application of low recording energy.
  • the copies have a wide range of color reproduction, continuous graduation, and are resistant to environmental changes.
  • the present invention is more particularly described by way of examples.
  • Ink compositions which contained dyes and binders indicated in Table 1 were each applied onto a 12 microns thick condenser paper by the use of a wire bar and dried as usual. Thereafter, each basic dye transfer paper was used for recording by a recording apparatus as shown in Fig. 1, in which a clay-coated paper was used as a dye-receiving sheet.
  • the recording conditions were as follows. Line density of main and sub scannings: 8 dots/mm Recording power: 0.2 U/dot Heating time of thermal head: 2 - 8 m.s.
  • Fig. 6 The chromaticity diagram of single and mixed colors is shown in Fig. 6 in comparison with a diagram by ordinary color printing.
  • the color mixing is in the order of cyan, yellow and magenta.
  • Fig. 7 there is shown the relation between the reflection density and the head heating time for different colors.
  • Ink compositions containing dyes indicated in Table 2 were prepared by mixing 8 parts by weight of a lwt% dye solution in dichloroethane and 2 parts by weight of a 2 wt: polycarbonate solution in dichloroethane and treated in the same manner as in Example 1.
  • Ink compositions containing dyes of the same types as used in Example 2 and various polymer resins indicated in Table 3 were each applied to a 12 microns thick condenser paper by means of a wire bar and dried. Each basic dye transfer paper was used along with a clay-coated paper for recording by the use of a thermal head.
  • the ink compositions were prepared by mixing 8 parts by weight of a 1 wt% ink solution and 2 parts by weight of a 2 wt% polymer solution.
  • the recording conditions were as follows. Line density of main and sub scannings: 8 dots/mm Electric power for recording: 0.2 U/dot Heating time of head: 5 m.s.
  • the reflection densities of the respective color images are shown in Table 3 in relation to the type of polymer.
  • the values shown in the table are average reflection densities measured at five portions, each having a 1 x 1 mm area, by a micro densitometer. In each parenthesis, there is shown a difference between maximum and minimum reflection densities.
  • Example 3 Each of 2 wt% polymer solutions as used in Example 3 was applied to a condenser paper of the same type as used in Example 3 by means of a wire bar, and each of 1 wt% dye solutions as used in Example 2 was further applied to the condenser paper in such a state that the applied polymer solution did not dry fully, followed by drying to obtain a basic dye transfer sheet.
  • the image on the image-receiving sheet of the present invention has a wider range of color reproduction and suffers a less influence of the arc lamp than in the case of the phenolic resin-containing sheet. Moreover, saturation densities of the respective colors prior to and after the xenone arc lamp test were greater than 1.2.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
EP83303487A 1982-06-17 1983-06-16 Feuilles de transfert à sec pour l'enregistrement thermosensible et appareil d'enregistrement thermosensible Withdrawn EP0097493A1 (fr)

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP57104926A JPS5916780A (ja) 1982-06-17 1982-06-17 転写型感熱記録方法および装置
JP104926/82 1982-06-17
JP57105927A JPS58220788A (ja) 1982-06-18 1982-06-18 像転写体
JP105927/82 1982-06-18
JP57107219A JPS58222890A (ja) 1982-06-21 1982-06-21 像受容体
JP107219/82 1982-06-21
JP57124640A JPS5914994A (ja) 1982-07-16 1982-07-16 像転写体
JP124640/82 1982-07-16

Publications (1)

Publication Number Publication Date
EP0097493A1 true EP0097493A1 (fr) 1984-01-04

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EP83303487A Withdrawn EP0097493A1 (fr) 1982-06-17 1983-06-16 Feuilles de transfert à sec pour l'enregistrement thermosensible et appareil d'enregistrement thermosensible

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2159971A (en) * 1984-06-06 1985-12-11 Mitsubishi Chem Ind Transfer recording method
DE3602437A1 (de) * 1985-01-30 1986-07-31 Sharp K.K., Osaka Thermosensitives aufzeichnungsmaterial
GB2179169A (en) * 1985-07-11 1987-02-25 Fuji Xerox Co Ltd Heat sensitive recording material
EP0217036A2 (fr) * 1985-08-05 1987-04-08 Hitachi, Ltd. Feuille avec couche d'encre colorée pour transfert thermique
US4664671A (en) * 1984-10-16 1987-05-12 Imperial Chemical Industries Plc Thermal transfer printing cationic dye with soft anionic base
US4705521A (en) * 1986-08-22 1987-11-10 Eastman Kodak Company Process for reheating dye-receiving element containing stabilizer
US4716145A (en) * 1986-06-27 1987-12-29 Eastman Kodak Company Non-imagewise reheating of transferred dyes in thermal dye transfer elements
US4929592A (en) * 1987-12-17 1990-05-29 Dai Nippon Insatsu Kabushiki Kaisha Heat transfer sheet
EP0227092B1 (fr) 1985-12-24 1990-11-07 EASTMAN KODAK COMPANY (a New Jersey corporation) Agent de libération pour le transfert de colorant par la chaleur
US5071502A (en) * 1985-04-24 1991-12-10 Fuji Xerox Co., Ltd. Heat-sensitive recording material
US5278131A (en) * 1991-05-24 1994-01-11 Imperial Chemical Industries Plc Thermal transfer printing ink sheet

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3239366A (en) * 1961-11-21 1966-03-08 Ncr Co Thermotransfer sheet material and copying systems utilizing same
NL6500108A (fr) * 1965-01-06 1966-07-07

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3239366A (en) * 1961-11-21 1966-03-08 Ncr Co Thermotransfer sheet material and copying systems utilizing same
NL6500108A (fr) * 1965-01-06 1966-07-07

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2565528A1 (fr) * 1984-06-06 1985-12-13 Mitsubishi Chem Ind Procede d'impression par transfert thermique et jeu de feuilles d'impression
GB2159971A (en) * 1984-06-06 1985-12-11 Mitsubishi Chem Ind Transfer recording method
US4664671A (en) * 1984-10-16 1987-05-12 Imperial Chemical Industries Plc Thermal transfer printing cationic dye with soft anionic base
DE3602437A1 (de) * 1985-01-30 1986-07-31 Sharp K.K., Osaka Thermosensitives aufzeichnungsmaterial
US5071502A (en) * 1985-04-24 1991-12-10 Fuji Xerox Co., Ltd. Heat-sensitive recording material
GB2179169A (en) * 1985-07-11 1987-02-25 Fuji Xerox Co Ltd Heat sensitive recording material
GB2179169B (en) * 1985-07-11 1989-07-26 Fuji Xerox Co Ltd Heat sensitive recording material
US4783375A (en) * 1985-07-11 1988-11-08 Fuji Xerox Co., Ltd. Heat-sensitive recording material
EP0217036A2 (fr) * 1985-08-05 1987-04-08 Hitachi, Ltd. Feuille avec couche d'encre colorée pour transfert thermique
EP0217036A3 (en) * 1985-08-05 1988-08-17 Hitachi, Ltd. Color ink sheet for thermal transfer
US4812439A (en) * 1985-08-05 1989-03-14 Hitachi, Ltd. Color ink sheet for thermal transfer
EP0227092B1 (fr) 1985-12-24 1990-11-07 EASTMAN KODAK COMPANY (a New Jersey corporation) Agent de libération pour le transfert de colorant par la chaleur
US4716145A (en) * 1986-06-27 1987-12-29 Eastman Kodak Company Non-imagewise reheating of transferred dyes in thermal dye transfer elements
EP0257578A2 (fr) * 1986-08-22 1988-03-02 EASTMAN KODAK COMPANY (a New Jersey corporation) Procédé pour réchauffer un élément récepteur de couleur contenant du stabilisant
EP0257578A3 (en) * 1986-08-22 1989-06-07 Eastman Kodak Company Process for reheating dye-receiving element containing stabilizer
US4705521A (en) * 1986-08-22 1987-11-10 Eastman Kodak Company Process for reheating dye-receiving element containing stabilizer
US4929592A (en) * 1987-12-17 1990-05-29 Dai Nippon Insatsu Kabushiki Kaisha Heat transfer sheet
US5278131A (en) * 1991-05-24 1994-01-11 Imperial Chemical Industries Plc Thermal transfer printing ink sheet

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