EP0394460B1 - Support d'enregistrement sensible a la chaleur - Google Patents

Support d'enregistrement sensible a la chaleur Download PDF

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Publication number
EP0394460B1
EP0394460B1 EP89908881A EP89908881A EP0394460B1 EP 0394460 B1 EP0394460 B1 EP 0394460B1 EP 89908881 A EP89908881 A EP 89908881A EP 89908881 A EP89908881 A EP 89908881A EP 0394460 B1 EP0394460 B1 EP 0394460B1
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EP
European Patent Office
Prior art keywords
layer
dye
recording material
thermosensitive recording
resin
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EP89908881A
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German (de)
English (en)
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EP0394460A1 (fr
EP0394460A4 (en
Inventor
Hideo Dai Nippon Insatsu Fujimura
Haruo Dai Nippon Insatsu Takeuchi
Katsuyuki Dai Nippon Insatsu Oshima
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Publication of EP0394460A4 publication Critical patent/EP0394460A4/en
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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
    • B41M5/50—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/50—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
    • B41M5/5209—Coatings prepared by radiation-curing, e.g. using photopolymerisable compositions
    • 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
    • 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
    • B41M5/5263—Macromolecular coatings characterised by the use of polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B41M5/5272—Polyesters; Polycarbonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
    • B41M7/0027—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using protective coatings or layers by lamination or by fusion of the coatings or layers

Definitions

  • the present invention relates to a recording medium used with a thermosensitive transfer recording system for printing or imaging by thermal printing means such as a thermal head and, more particularly, to a thermosensitive recording medium used in combination with a heat transfer sheet having a dye carrying layer.
  • thermosensitive recording medium or material is used in combination with a heat transfer sheet having a heat transfer layer containing thermally transferable dyes. That material is superposed upon the heat transfer sheet while said heat transfer layer is in contact with an image receiving or imageable layer. Then, heat is applied by thermal printing means such as a thermal head which is controlled by an electrical signal corresponding to image information from the back side of the heat transfer sheet with a thermosensitive printer, etc. to generate heat, thereby transferring the dyes in the heat transfer sheet into the image receiving layer to form a gradient image like a natural color photograph. Typical of this is a thermosensitive image-receiving sheet.
  • thermosensitive recording material has a disadvantage of making it difficult to provide a satisfactory releasing of the heat transfer sheet from the recording material, because the heat transfer layer (a dye layer) is thermally fused to the image-receiving layer (a dye-receiving layer) by heating at the time of printing with a thermal printer.
  • a release agent in a resin for forming the dye-receiving layer by mixing.
  • the heat resistance of the dye-receiving layer per se is less than satisfactory with no achievement of sufficient releasability, partly because the release agent remains only mixed with said resin.
  • US-A-4 701 837 discloses a light-transmissive recording medium to be used suitable for ink jet recording, particularly to a light-transmissive recording medium satisfying both water resistance of recording image and ink absorption characteristic. This medium is not used for a thermosensitive recording material.
  • JP-A-61199997 discloses a thermal transfer sheet by providing a coating layer composed of a thermoplastic polyester resin having a crosslinkable reaction group, a silicon oil having a crosslinkable reaction group and a specific isocyanate compound as a layer to be thermally transfer-printed for the surface of a base sheet.
  • thermosensitive recording material for use in combination with a heat transfer sheet carried thereon with a thermally transferable dye
  • said heat transfer dye-receiving thermosensitive recording material comprising: a substrate, and a dye-receiving layer provided on the surface of said substrate, said dye-receiving layer being formed by crosslinking and curing a polyester, silicon oil having a crosslinkable reaction group and polyisocyanate, characterized in that the dye receiving layer is formed in the presence of a catalyst comprising an organometallic compound.
  • FIGS 1 to 8 are sectional views showing embodiments of the thermosensitive recording material according to the present invention.
  • thermosensitive material of the present invention comprises a substrate 1 and a dye-receiving layer 2 formed thereon.
  • a release agent containing a crosslinkable reaction group may be incorporated as a part of the material forming the dye-receiving layer in addition to the above additive.
  • the substrate 1 used as a support in the present invention serves to carry the dye-receiving layer 2, and may be formed of any suitable material depending upon the purposes.
  • any suitable material for instance, use may be made of films, sheets, sheetings, etc. formed of synthetic resins and various types of paper.
  • Synthetic resin films may be formed of polyester, polyvinyl chloride, polypropylene, polyethylene, polycarbonate, polyamide and the like.
  • Use may also be made of white substrates obtained by forming such synthetic resin films, etc. with fillers into films or foamed substrates obtained by microfoaming.
  • As the paper materials use may be made of slick paper, coated paper, cast coated paper, synthetic rubber latex or synthetic resin emulsion-impregnated paper and so on.
  • Use may also be made of paper obtained by mixing inorganic fillers with a resinous component such as polyolefinic resin or other synthetic resin and extruding the mixture, synthetic paper obtained by coating a pigment on the surface of a film formed of a resin such as polystyrene, polyester and polyolefin.
  • a resinous component such as polyolefinic resin or other synthetic resin
  • synthetic paper obtained by coating a pigment on the surface of a film formed of a resin such as polystyrene, polyester and polyolefin.
  • laminates comprising any combination of the above substrates may be used. Typical of such laminates are combinations of cellulosic fiber paper with synthetic paper or cellulose fiber paper with a plastic film or sheet. Such substrates may have any suitable thickness, generally of about 10 to 800 ⁇ m.
  • the substrate When the substrate is poor in the adhesion to the dye-receiving layer, it is desired that its surface be primer- or corona-treated.
  • the substrate may be dispensed with depending upon the structure of the dye-receiving layer.
  • the dye-receiving layer serves to form thereon a heat transfer image and basically comprises a resin capable of receiving a dye transferred from a heat transfer sheet at the time of heat transfer and containing a crosslinkable reaction group and an additive containing a crosslinkable reaction group.
  • an additional release agent again containing a crosslinkable reaction group may be added to the dye-receiving layer.
  • the crosslinkable reaction groups in the present invention refer to (1) a thermosetting reactive group (for instance, -OH, -NH 2 , -COOH, -CONH 2 , -CONH-, -NCO, etc.) and (2) an ultraviolet- or electron beam-curing reactive group (for instance, vinyl, acrylic, methacrylic, allyl and other groups).
  • a thermosetting reactive group for instance, -OH, -NH 2 , -COOH, -CONH 2 , -CONH-, -NCO, etc.
  • an ultraviolet- or electron beam-curing reactive group for instance, vinyl, acrylic, methacrylic, allyl and other groups.
  • the above resins containing crosslinkable reaction groups may include polyester resin, acrylic resin, vinyl resin, polyurethane resin, cellulosic resin, polysaccharide or other resins, which are modified by introducing into their molecular chains one or more such crosslinkable reaction groups as mentioned above (which may be identical with or different from each other). These resins may be used alone or in combination of two or more.
  • the above release agents may include silicone, fluorine, long-chain aliphatic hydrocarbon compounds, waxes and other like substances, which are modified by introducing into their molecular chains one or more such crosslinkable reaction groups as mentioned above (which may be identical with or different from each other).
  • the above additives may include heat-curing compounds such as polyisocyanates (containing at least two -NCO groups), polyols (containing at least two -OH groups), polyamines (containing at least two -NH 2 groups) and polycarboxylic acids (containing at least two -COOH groups) and ultraviolet- or electron radiation-curing monomers such as those containing in their molecular chains one or more such crosslinkable reaction groups as mentioned above (which may be identical with or different from each other).
  • heat-curing compounds such as polyisocyanates (containing at least two -NCO groups), polyols (containing at least two -OH groups), polyamines (containing at least two -NH 2 groups) and polycarboxylic acids (containing at least two -COOH groups) and ultraviolet- or electron radiation-curing monomers such as those containing in their molecular chains one or more such crosslinkable reaction groups as mentioned above (which may be identical with or different from each other).
  • the resin capable of receiving a resin and the additive or the resin capable of receiving a resin, the additive and the release agent are crosslinked and cured alone or in combination through the crosslinkable reaction groups into a three-dimensional crosslinked structure.
  • thermosensitive recording materials present a phenomenon that when the dye is transferred into the dye-receiving layer by heating, the concentration of reflection cannot exceed a certain level or, to put it another way, is saturated or reach the top, because the printed surface is embossed into a matte by the amount of heating exceeding a certain fixed value.
  • the present inventors have now found that the above problem, that is, degradation of the print face by the embossing of the print face, is successfully solved by using an isocyanate compound containing at least two isocyanate groups as the above additive and using the additive in an excessive amount with respect to the resin.
  • the ratio of the equivalent of the isocyanate groups of the above additive to that of the crosslinkable reaction group of the aforesaid resin be in a range of 2:1 to 10:1. If the equivalent ratio is below 2:1, then there arises a problem that when printing is carried out with high energy, the print face is embossed into a matte and so becomes foggy. On the other hand, an equivalent ratio exceeding 10:1 is unpreferred, since there is then a drop of printing sensibility with a drop of the storability of the print.
  • the amount of the release agent added is in a range of about 0.1 to 20 parts by weight relative to 100 parts by weight of the resin capable of receiving a dye.
  • the amount of the release agent is too small, it is so thermally fused to the heat transfer sheet that the storability of the printed image deteriorates.
  • the amount of the release agent is too large, on the other hand, the printed image is so poor in storability that it can be mottled.
  • a catalyst is added to the resin forming the receiving layer to accelerate its crosslinking or curing.
  • Catalysts heretofore used industrially to this end include tertiary amines and organic metal compounds.
  • such catalysts as mentioned above are not necessarily preferred for use with the receiving layers of such thermosensitive recording materials as contemplated in the present invention.
  • the storage properties (esp., heat resistance and weather resistance) of the printed image are poorer than when they are not used.
  • organometallic compounds as catalysts, esp., those based on dibutyltin or dioctyltin.
  • the catalysts based on dibutyltin include, for instance, dibutyltin dilaurate, dibutyltin oxide, dibutyltin dichloride, dibutyltin di-2-ethylhexyl thioglycolate, dibutyltin di(monobutyl) maleate, dibutyltin di(monononyl) maleate, dibutyltin diacetate, dibutyltin mercaptide, dibutyltin ⁇ -mercaptopropionate, dibutyltin thiocarboxylate and dibutyltin di-2-ethylhexoate.
  • dibutyltin dilaurate dibutyltin oxide, dibutyltin dichloride, dibutyltin di-2-ethylhexyl thioglycolate
  • dibutyltin di(monobutyl) maleate dibutylt
  • the catalysts based on dioctyltin preferably include dioctyltin dilaurate, dioctyltin thioglycolate, dioctyltin ⁇ -mercaptopropionate, dioctyltin-1,4-butanediol-bis(mercaptoacetate), dioctyltin ethylene glycol dithioglycolate, dioctyltin thiocarboxylate, dioctyltin maleate, dioctyltin maleate polymer, dioctyltin-(1,2-propylene glycol maleate), dioctyltin-di-(monobutyl) maleate, dioctyltin-bis-(2-ethylhexyl maleate), dioctyltin-bis-(lauryl thioglycolate), dioctyltin
  • organometallic compounds which are used in the present invention, include stannous octoate, lead octoate, cobalt naphthenate, stannous chloride, stannic chloride, tetra-n-butyltin, tetraphenyltin, trimethyltin hydroxide and dimethyl-2-tin chloride.
  • the amount of the catalyst added is in a range of 0.01 to 10 parts by weight, preferably 0.1 to 1 part by weight relative to 100 parts by weight of the resin containing functional groups reacting with the isocyanate groups. At less than 0.01 part by weight, the catalyst does not produce any effect upon accelerating the reaction or reducing the length of reaction time. At higher than 10 parts by weight, on the other hand, the catalyst is effective to promote the reaction, but reduces the pot life of ink.
  • the above catalysts is used alone or in combination.
  • the dye-receiving layer may be formed by providing a composition for forming the receiving layer by preparing the resin capable of receiving a dye and the additive (and the release agent) with a solvent, etc. and coating that composition on a support or substrate by suitable means such as gravure printing, screen printing and reverse roll coating with a gravure press, followed by drying.
  • suitable means such as gravure printing, screen printing and reverse roll coating with a gravure press, followed by drying.
  • the crosslinkable reaction groups applied are of the ultraviolet- or electron radiation-curable type, crosslinking and curing reactions may take place by exposure to ultraviolet rays or electron radiations.
  • the dye-receiving layer may have a thickness of about 1 to 20 ⁇ m, preferably about 2 to 10 ⁇ m.
  • thermosensitive recording materials of the present invention may have various applications in the form of heat transfer recordable image-receiving sheets, cards, transmission types of sheets for preparing MSS and the like.
  • thermosensitive recording materials of the present invention may be provided with additional layers, or otherwise be subjected to various treatments, as required.
  • the present recording material may be subjected on its one major side with antistatic treatment, which may be carried out by incorporating an antistat in, e.g., the dye-receiving layer providing the front major side or providing it on the surface of the dye-receiving layer in the form of an antistatic layer. Similar treatment may also be applied to other major or minor sides. This treatment provides a smooth feeding of the recording materials and is effective to prevent dust, etc. from being deposited onto the recording materials.
  • the cushioning layer may be made up of suitable resins such as urethane resin, acrylic resin, ethylenic resin, butadiene rubber and epoxy resin.
  • suitable resins such as urethane resin, acrylic resin, ethylenic resin, butadiene rubber and epoxy resin.
  • the cushioning layer may have a thickness of about 2 to 20 ⁇ m.
  • a lubricating layer may be provided on the back side of the substrate.
  • the lubricating layer may be made up of suitable resins such as methacrylate resin, e.g., methyl methacrylate or the corresponding acrylate resin and vinylic resin, e.g., vinyl chloride/vinyl acetate copolymers.
  • methacrylate resin e.g., methyl methacrylate or the corresponding acrylate resin
  • vinylic resin e.g., vinyl chloride/vinyl acetate copolymers.
  • organic or inorganic microparticles may be added to the lubricating layer.
  • the recording material may be provided with a detection mark, with which the positioning of the heat transfer sheet relative to the recording material, etc. can be carried out very conveniently.
  • a detection mark capable of being sensed by a phototube sensor may be provided on the back side, etc. of the substrate.
  • cards such as cash cards and credit cards have been used as information recording media in card forms.
  • the required information is imparted to the surfaces of card substrates formed of, e.g., synthetic resins.
  • the information has been imparted by various means such as printing and magnetic recording, but characters, patterns, etc. have been applied by printing.
  • the substrates such as polyester sheets are provided on their surfaces with magnetic recording layers having thereon colored or otherwise silvered layers for ornamental purposes or with a view to protecting the magnetic recording layers and on their opposite sides with prints for the purpose of ornamentation, publicity, advertisement and other purposes.
  • the aforesaid heat transfer systems have the advantages of making it possible to make blank cards (to be printed on their surfaces) and to make a printing on a few, or as small as dozens of, blank cards at low printing costs and for an individual's hobby.
  • the card substrates are locally heated at the time of heat transfer, resulting in the formation of fine irregularities on their surfaces. This is true particularly when the thermal head of a printer is heated to a temperature sufficiently high to increase the density of printing.
  • thermosensitive recording material is formed into a card, the substrate of which is then provided on the whole or a part of at least one major side with a magnetic recording layer to obtain a magnetic card which also serves as a thermosensitive recording material.
  • a magnetic card presents no or little problem of irregularities or curling, which are otherwise caused by heat at the time of printing, since the dye-receiving layer comprises a material obtained by the curing of such a specific crosslinkable resin as mentioned above.
  • a magnetic card having much improved heat resistance and free from any problem of irregularities or curling, which is otherwise caused by heating with a thermal head at the time of heat transfer, by separate provision of a backing layer consisting of a crosslinkable resin on the upper surface of the magnetic recording layer of the magnetic card.
  • Figures 2 and 3 are schematic views showing the sections of illustrative examples of magnetic cards to which the present invention is applied.
  • (fig 2) one magnetic card of the present invention comprising a substrate 11 including thereon a magnetic recording layer 12 and a magnetism-protecting layer 13 and on the opposite side a layer 14 for receiving a sublimable dye is characterized in that said backing layer 13 is formed by using a crosslinkable resin as a binder.
  • the backing layer 13 consists only of a colored concealing layer in which metal powders, pigments or dyes are used as a colorant and a crosslinkable resin is employed as a binder.
  • the backing layer 13 comprises a colorant-containing colored concealing layer 31 and a transparent back protecting layer 32.
  • the colored layer 31 and/or the back protecting layer 32 may be formed of a crosslinkable resin.
  • the above magnetic card of the present invention is substantially identical with a conventional magnetic card, except that the colored concealing layer and/or the back protecting layer are formed of a crosslinkable resin.
  • crosslinkable resin refers to a resin, the molecules of which, after the formation of a layer, form a crosslinked network structure directly or through a crosslinker or polymerization initiator, and which is well-known in itself in the art of paints or printing.
  • the resins forming a crosslinked structure may include, for instance, those containing in their molecules hydroxyl, amino, carboxyl, carboamide, acid amide, isocyanate, glycidyl, methylol, vinyl, acrylic, methacrylic, allyl or other groups or oligomers. More illustratively but not exclusively, use may be made of amino, urea, phenol, melamine, alkyd, cellulose, acrylic, vinyl, polyester, polyamide, polyurethane, acrylic polyol, acrylic urethane and unsaturated polyester resins as well as their modified resins, all containing such groups as mentioned above.
  • such resins are broken down into heat curing resins crosslinked by heating, two-part resins crosslinked by crosslinkers such as polyisocyanates, polyols, polyamines and polycarboxylic acids, cold curing resins crosslinked by catalysts and photo-curing resins crosslinked by ultraviolet rays or electron radiations.
  • crosslinkers such as polyisocyanates, polyols, polyamines and polycarboxylic acids
  • cold curing resins crosslinked by catalysts
  • photo-curing resins crosslinked by ultraviolet rays or electron radiations.
  • the colored layer When forming the colored layer with the above crosslinkable resin, it is mixed with a colorant such as metallic flake pigments, color pigments, white pigments and dyes and, if required, with a diluent such as organic solvents to impart printability or coatability thereto. Then, the mixture is coated on the surface of the aforesaid magnetic recording layer in conventional manners such as gravure printing, screen printing, gravure offset printing or gravure coating, followed by drying and curing.
  • a colored layer may have a thickness of about 1 ⁇ m to 20 ⁇ m.
  • the density of crosslinking of the layer to be formed can be freely varied by the type of binders used, the quantity of crosslinkers used or the dose of light applied.
  • the object of the present invention is unachievable at a low degree of crosslinking, whereas too high a degree of crosslinking is unpreferred, since the coat is so lacking in flexibility that it can foliate or crack.
  • the density of crosslinking is suitably such that the substrate is not deformed by the heat of a thermal head at the time when making a printing on the dye-receiving layer formed of the back side thereof. It is easy to determine such a degree of crosslinking experimentally.
  • the molecular weight per one point of crosslinking is preferably in a range of about 1,000 to about 50,000 in the present invention.
  • Crosslinking may be achieved by any one of heat-, cold- and photo-curing. When a relative high degree of crosslinking is required, however, preference is given to photo-curing.
  • the backing layer may consist only of the colored concealing layer, as illustrated in Fig. 2, or may be of a double layer structure comprising the colored concealing layer and the back protecting layer, as illustrated in Fig. 3. It is understood that when the backing layer comprises two parts, one or both thereof may be formed of the crosslinkable resin.
  • the back protecting layer may be formed in similar manners as the colored concealing layer, except that it is made transparent with no use of any colorant.
  • recording materials in card forms are prone to generating static electricity. For instance, when cards are inputted into transfer equipment by an autofeeder, there is a problem that they are inputted while overlapping each other. Another problem with static electricity is that dust remains deposited or the magnetic information recorded in the magnetic recording layer is destroyed.
  • an antistatic layer may be provided on the surface of the dye-receiving layer for the purpose of preventing the generation of static electricity.
  • a dye-receiving layer 43 is provided on one side of a card substrate 42, and an antistatic layer 44 is attached to the surface of the dye-receiving laye 43.
  • the antistatic layer 44 may be formed by the application of an anionic surface active agent such as alkyl sulfates or phosphates, a nonionic surfactant such as polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, polyoxyalkylene fatty acids ester, polyoxyalkylene sorbitan fatty acid ester and sorbitan fatty acid ester, a cationic surfactant such as alkylamine salts and quaternary ammonium salts and an amphoteric surfactant such as alkyl betaine; however, this has a disadvantage of being poor in durability.
  • an anionic surface active agent such as alkyl sulfates or phosphates
  • a nonionic surfactant such as polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenyl ether, polyoxyalkylene fatty acids ester, polyoxyalkylene sorbitan fatty acid ester and sorbitan fatty acid
  • Siloxane compounds or polymers with a quaternary ammonium salt in their side chains may also be used as antistats.
  • inks containing carbon black and metal powders may be applied; however, this has a disadvantage of reducing the transmissibility of an image transfer-recorded on the dye-receiving layer 43.
  • the antistatic layer 44 should have a thickness of 0.001 to 1 ⁇ m, particularly 0.01 to 0.1 ⁇ m.
  • Reliance may also be placed upon a technique for forming a metallized layer having a thickness sufficient to make it transparent by metallization, say, 100 to 500 angstroms.
  • the antistatic layer 44 has a surface resistivity of 10 8 to 10 9 ohms/cm 2 .
  • the above substrate for cards includes a substrate material 42 having a magnetic recording layer 45 on its back side.
  • Said magnetic recording layer 45 is provided on its back side with a silvered concealing layer 46 for concealing the color of the magnetic recording layer 45.
  • On the back side of the layer 46 there are further provided a backing protective layer 47 and an antistatic layer 48 in that order.
  • the silvered concealing layer 46 may be formed of a composition in which metal powders such as aluminium powders are dispersed in a binder such as polyurethane, polyester or acrylic resin.
  • the back protecting layer 47 may be formed of a vinylic resin such as acrylic resin, polyurethane and vinyl chloride/vinyl acetate copolymers.
  • the antistatic layer 48 on the back side may be formed in similar manners as applied for forming the antistatic layer 44 on the front side. Although the antistatic layer 48 on the back side may be dispensed with, yet it is preferred, since a further improved antistatic effect is obtained by the provision of the antistatic layer 48 on the back side.
  • reference numeral 49 stands for bar codes and 10 and 41 denote pre-provided printable layers.
  • the printable layer 10 located on the side of the dye-receiving layer 43 may be provided on the upper side of the layer 43, as illustrated, or alternatively on the lower side thereof.
  • intermediate layers 52 such as cushioning and porous layers may be arranged between the dye-receiving layer 43 and the card substrate material 42, as illustrated in Figure 5.
  • the intermediate layers 52 may be formed of, e.g., urethane resin, acrylic resin, ethylenic resin, butadiene rubber, epoxy resin or the like and have preferably a thickness of about 2 to 20 ⁇ m.
  • the dye-receiving layer 63 and card substrate material 62 are each provided on the surface with a covering film 64.
  • reference numeral 65 in Fig. 6 stands for an adhesive layer.
  • the covering film 64 provides a protection against the dye-receiving layer.
  • the covering films 64 may be formed of acrylics, polyvinyl chloride, polyester, vinyl chloride/vinyl acetate copolymers, vinylic resin and so on.
  • a dye-receiving layer 63 is formed on a part of the surface of a card substrate material 62.
  • a spacer 66 By providing the spacer 66 to locate the dye-receiving layer on a part of the card substrate, it is possible to eliminate irregularities on the covering films.
  • the spacer 66 may be formed of similar synthetic resins to those forming the above covering films.
  • a recess or dent 67 is provided in a part of the surface of a card substrate material 62 to receive therein a dye-receiving layer 63.
  • a recess or dent 67 is provided in a part of the surface of a card substrate material 62 to receive therein a dye-receiving layer 63.
  • a dye-receiving layer 63 As is the case with Fig. 7, it is possible to eliminate irregularities on covering films 64.
  • compositions for the formation of dye-receiving layers were prepared with such crosslinkable reaction group-containing reactive resins and release agents and additives as indicated in Tables 1 and 2.
  • Each ink composition was coated on a white polyethylene terephthalate film of 100 ⁇ m in thickness (Lumilar E-20, made by Toray Industries, Inc.) by gravure reverse roll coating to obtain a given coat thickness on dry basis. It is to be noted that the composition of Example 14 contains 0.5 parts by weight of benzophenone.
  • UV- or electron radiation-curing curing was performed in the following manners.
  • curing was carried out with ultraviolet rays emitting from three high-pressure mercury lamps (80 W/cm)
  • electron radiation curing curing was effected with electron beams emitting from an EB irradiator (made by ESI; Electocurtain Type 175 KV, 3 Mrad.).
  • ESI Electocurtain Type 175 KV, 3 Mrad.
  • a dye transfer layer forming composition composed of such ingredients as mentioned below, was printed on the surface side of a polyester film of 4.5 ⁇ m in thickness and having on its back side a heat-resistant lubricating layer by gravure printing to form a dye transfer layer in a coated amount of 1.1 g/m 2 on dry basis, thereby preparing a transfer sheet.
  • thermosensitive head Using the above Dye donor transfer sheet with the transfer layer overlying the dye-receiving layer of each imageable sheet, printing was carried out with a thermosensitive head under the following conditions.
  • Rate of thermal fading (%) (density-before) - (density-after) (density-before) ⁇ 100
  • the recording materials of the present invention include a dye-receiving layer obtained by crosslinking and curing the resin capable of receiving the dye transferred from the heat transfer sheet by heating and having a crosslinkable reaction group with the release agent having a crosslinkable reaction group and so excel in releasability and heat resistance.
  • the dye-receiving layer is formed by crosslinking and curing the above resin and release agent together with the additive having a crosslinkable reaction group, then the recording materials of the present invention are improved in terms of not only releasability and heat resistance but also various properties such as elongation, heat resistance, flexibility and surface activity.
  • high-sensitivity printing can be made at high concentrations because of the imageable layer being of a three-dimensional crosslinked structure.
  • the storability of the image after heat transfer recording is much more improved.
  • Example B2 Dibutyltin dimercaptide 8.8 10.3
  • Example B3 Dibutyltin diacetate 9.2 11.1
  • Example B4 Dibutyltin dilaurate 9.6
  • Example B5 Dibutyltin maleate 8.9 10.7
  • Example B6 Dibutyltin glycolate 9.1 11.6
  • Example B7 Stannous octoate 8.8 10.9 Comparative Example B1 No addition 9.3 10.4 10 min.
  • Comparative Example B2 Triethylenediamine 31.2 20.0 1 min.
  • Comparative Example B4 Triethylamine 30.7 19.9
  • Comparative Example B5 Tetramethyl guanidine 33.6 19.5
  • Comparative Example B6 Tetramethyl hexadiamine 28.7 25.6
  • a magnetic coating material was coated and dried on a polyethylene terephthalate film (of 250 ⁇ m in thickness) in conventional manners to form a magnetic recording layer of 5 ⁇ m in thickness.
  • a composition for each colored concealing layer composed of such ingredients as given below, was coated, dried and cured to a thickness of 5 ⁇ m on dry basis in gravure offset printing fashion to form a colored concealing layer.
  • an additional composition for the back protecting layers composed of such ingredients as given below, was coated, dried and cured to a thickness of 2 ⁇ m on dry basis in gravure offset printing fashion to form a back protecting layer.
  • composition used in Ex. 1 for the formation of the dye-receiving layer was coated and dried to a thickness of 5 ⁇ m on dry basis on the opposite sides of the substrates to prepare magnetic cards according to the examples and comparative examples.
  • Composition for the Formation of Receiving Layer (common) parts by weight Polyester resin 20 Amino modified silicone oil 1 Epoxy modified silicone oil 1 TDI modified polyisocyanate 1 Methyl ethyl ketone 40 Toluene 40
  • Composition for Colored Concealing Layer parts by weight Vinyl chloride/vinyl acetate copolymer resin 20 Pigment 10 Isocyanate curing agent 3 Methyl ethyl ketone 30 Toluene 40 Curing by heat
  • composition for Colored Concealing Layer parts by weight Acrylic polyol 20 Acrylic monomer 5 Benzophenone 0.1 Pigment 10 Toluene 70 Curing by ultraviolet rays
  • composition for Colored Concealing Layer Non-crosslinked parts by weight
  • Vinyl chloride/vinyl acetate copolymer resin 30 Pigment 10 Toluene 60
  • Composition for Back Protecting Layer Polyurethane resin
  • Isocyanate curing agent 2 Toluene 70 Curing by heat
  • composition for Colored Concealing Layer parts by weight Polyester resin 20 Pigment 10 Isocyanate curing agent 6 Toluene 40 Isopropyl alcohol 30 Curing by heating
  • composition for Colored Concealing Layer parts by weight Unsaturated polyester resin 20 Diallyl phthalate 20 Pigment 5 Benzophenone 0.1 Methyl ethyl ketone 10 Toluene 30 Curing by ultraviolet rays
  • composition for Colored Concealing Layer parts by weight Cellulose acetate 30
  • Isocyanate curing agent 3 Pigment 5 Toluene 40
  • Isopropyl alcohol 30 Curing by heating
  • Composition for Back Protecting Layer Rosin modified maleate resin 30
  • Composition for Colored Concealing Layer parts by weight Vinyl chloride/vinyl acetate copolymer resin 30 Pigment 10 Methyl ethyl ketone 30 Toluene 30
  • composition for Colored Concealing Layer parts by weight Acrylic polyol 20 Pigment 10 Toluene 60
  • composition for Colored Concealing Layer parts by weight Ethyl polyacrylate resin 40 Pigment 5 Toluene 50
  • composition for Colored Concealing Layer parts by weight Polyurethane resin 30 Pigment 5 Toluene 60
  • composition for Colored Concealing Layer parts by weight Polyamide resin 30 Pigment 10 Toluene 30 Isopropyl alcohol 30
  • the magnetic cards of the present invention can be printed at high density with neither irregularities nor curling, so that they can be easily fed into equipment with accurate reading-out or writing-in.
  • thermosensitive recording materials of the present invention have wide application in the form of recording media for heat transfer recording systems designed to make printing or form images by thermal printing means such as thermal heads.
  • the thermosensitive recording materials of the present invention can also be used as card-form media, e.g., magnetic cards having thermosensitive recording means.

Landscapes

  • Thermal Transfer Or Thermal Recording In General (AREA)

Abstract

Le support d'enregistrement thermosensible ci-décrit est utilisé en combinaison avec une feuille de transfert de chaleur comportant des colorants susceptibles de migrer lorsqu'ils sont chauffés. Ledit support d'enregistrement thermosensible se compose d'un substrat (1) et d'une couche d'acceptation de colorant (2) formée sur au moins l'une des surfaces du substrat (1) et cette couche d'acceptation de colorant (2) se compose du produit réticulé et polymérisé d'une résine possédant un groupe de réaction réticulable, par l'utilisation d'un additif comportant un groupe de réaction réticulable.

Claims (14)

  1. Un matériau d'enregistrement thermosensible récepteur de colorant par transfert thermique comprenant
    - un substrat (1,11,42) et
    - une couche réceptrice de colorant (2,14,43,63) appliquée sur la surface dudit substrat (1,11,42), ladite couche réceptrice de colorant étant constituée par réticulation et durcissement d'une résine de polyester comportant un groupe réactif réticulable, une huile silicone présentant un groupe réactif réticulable et un polyisocyanate caractérisé en ce que la couche réceptrice de colorant est formée en présence d'un catalyseur comprenant un dérivé organométallique.
  2. Le matériau d'enregistrement thermosensible selon la revendication 1, dans lequel le rapport du nombre d'équivalents de groupes isocyanate du polyisocyanate au nombre de groupes réticulables de la résine de polyester est compris entre 2:1 et 10:1.
  3. Le matériau d'enregistrement thermosensible selon la revendication 1 ou 2, dans lequel le catalyseur est à base de dibutylétain ou de dioctylétain.
  4. Le matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 3, dans lequel ledit substrat (11) est appliqué en tout ou en partie sur au moins une face principale avec une couche d'enregistrement magnétique (12).
  5. Le matériau d'enregistrement thermosensible selon la revendication 4, dans lequel ladite couche d'enregistrement magnétique (12) est en outre munie sur sa surface d'une couche de support (13).
  6. Le matériau d'enregistrement thermosensible selon la revendication 5 dans lequel ladite couche (13) est formée en utilisant une résine réticulable en tant que liant.
  7. Le matériau d'enregistrement thermosensible selon la revendication 5 dans lequel ladite couche de support (13) comprend une couche masquante colorée (31) et une couche protectrice inférieure (32) l'une au moins de celles-ci étant formée en utilisant une résine réticulable en tant que liant.
  8. Le matériau d'enregistrement thermosensible selon l'une quelconque des revendications 1 à 7, se présentant sous la forme d'une carte.
  9. Le matériau d'enregistrement thermosensible selon la revendication 8, dans lequel ladite couche réceptrice (43) comporte à sa surface une couche antistatique (44, 48).
  10. Le matériau d'enregistrement thermosensible selon l'une quelconque des revendications 8 ou 9, dans lequel ladite couche réceptrice (43) présente une résistivité superficielle comprise 108 et 109 ohms/cm2.
  11. Le matériau d'enregistrement thermosensible de l'une quelconque des revendications 1 à 10, présentant une surface plane.
  12. Le matériau d'enregistrement thermosensible selon la revendication 11, dans lequel on a stratifié une couche de protection (64) sur la surface de ladite couche réceptrice de colorant (63).
  13. Le matériau d'enregistrement thermosensible selon la revendication 11, dans lequel ladite couche réceptrice de colorant (63) est placée sur une partie dudit substrat et dans lequel un espaceur (66) est formée sur une autre partie dudit substrat.
  14. Le matériau d'enregistrement thermosensible selon la revendication 11, dans lequel une partie dudit substrat fourni comporte un évidement (67) destiné à recevoir ladite couche réceptrice de colorants (63).
EP89908881A 1988-08-13 1989-08-01 Support d'enregistrement sensible a la chaleur Expired - Lifetime EP0394460B1 (fr)

Applications Claiming Priority (9)

Application Number Priority Date Filing Date Title
JP202125/88 1988-08-13
JP20212588 1988-08-13
JP204132/88 1988-08-17
JP20413288 1988-08-17
JP22642788 1988-09-12
JP226427/88 1988-09-12
JP246143/88 1988-09-30
JP24614388 1988-09-30
PCT/JP1989/000788 WO1990001419A1 (fr) 1988-08-13 1989-08-01 Support d'enregistrement sensible a la chaleur

Publications (3)

Publication Number Publication Date
EP0394460A1 EP0394460A1 (fr) 1990-10-31
EP0394460A4 EP0394460A4 (en) 1991-08-28
EP0394460B1 true EP0394460B1 (fr) 1997-12-29

Family

ID=27476091

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89908881A Expired - Lifetime EP0394460B1 (fr) 1988-08-13 1989-08-01 Support d'enregistrement sensible a la chaleur

Country Status (3)

Country Link
EP (1) EP0394460B1 (fr)
DE (1) DE68928514T2 (fr)
WO (1) WO1990001419A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0503439B1 (fr) * 1991-03-15 1994-11-09 Agfa-Gevaert AG Récepteur de colorant pour l'impression par thermosublimation
WO1993010978A1 (fr) * 1991-11-25 1993-06-10 Agfa-Gevaert Naamloze Vennootschap Procede de fabrication d'une image coloree monochrome, teintee thermiquement
US5266551A (en) * 1992-08-03 1993-11-30 Eastman Kodak Company Thermal dye transfer receiving element with polycarbonate polyol crosslinked polymer dye-image receiving layer
US5411931A (en) 1994-06-24 1995-05-02 Eastman Kodak Company Thermal dye transfer receiving element with polycarbonate polyol crosslinked polymer
DE69931955T2 (de) * 1998-10-08 2007-02-08 Matsushita Electric Industrial Co., Ltd., Kadoma Bildempfangsschicht und bildempfangselement für aufzeichnung durch thermische übertragung
JP5844010B2 (ja) * 2013-10-07 2016-01-13 リンテック株式会社 印刷用コート剤及び印刷用コートフィルムの製造方法

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JPS58215398A (ja) * 1982-06-08 1983-12-14 Sony Corp 被印刷紙
JPS61199997A (ja) * 1985-02-28 1986-09-04 Dainippon Printing Co Ltd 熱転写受像シート
JPS627594A (ja) * 1985-07-04 1987-01-14 Sony Chem Kk 昇華転写用透明被転写体
EP0209359A2 (fr) * 1985-07-15 1987-01-21 Matsushita Electric Industrial Co., Ltd. Couche réceptrice pour le colorant, pour l'enregistrement par transfert thermique
JPS6223790A (ja) * 1985-07-24 1987-01-31 Matsushita Electric Ind Co Ltd 感熱転写記録用受像体
JPS6246689A (ja) * 1985-08-27 1987-02-28 Mitsubishi Rayon Co Ltd 昇華型感熱転写記録方式の被記録体用コ−テイング組成物
JPS62222895A (ja) * 1986-03-25 1987-09-30 Nitto Electric Ind Co Ltd 昇華型感熱記録用受像体
JPS6319295A (ja) * 1986-07-12 1988-01-27 Nippon Telegr & Teleph Corp <Ntt> 昇華型熱転写受像体
JPS6327367U (fr) * 1986-08-08 1988-02-23
JPS6367188A (ja) * 1986-09-10 1988-03-25 Mitsubishi Rayon Co Ltd 昇華性分散染料易染性樹脂組成物
EP0292109A1 (fr) * 1987-04-24 1988-11-23 Imperial Chemical Industries Plc Récepteur de transfert thermique

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CH651854A5 (en) * 1981-03-10 1985-10-15 Peter Mueser Use of polyisocyanate-crosslinkable methacrylates for providing sheet metals that are to be printed by the sublimation transfer printing process with a coating that has an affinity for dyes
JPS6174879A (ja) * 1984-09-19 1986-04-17 Jujo Paper Co Ltd インクジエツト記録用シ−ト
JPS61132387A (ja) * 1984-11-30 1986-06-19 Dainippon Printing Co Ltd 被熱転写シ−ト
JPH0669754B2 (ja) * 1985-03-04 1994-09-07 キヤノン株式会社 インクジェット用透光性被記録材
JPS6287389A (ja) * 1985-10-15 1987-04-21 Matsushita Electric Ind Co Ltd 熱転写記録用受像体
JPS62233294A (ja) * 1986-04-02 1987-10-13 Nikon Corp 昇華転写記録用受像シ−ト及びそれを用いた昇華転写記録方法
JP2625418B2 (ja) * 1986-09-10 1997-07-02 松下電器産業株式会社 昇華型感熱転写記録方式の被記録体
JPS6387285A (ja) * 1986-09-30 1988-04-18 Dainippon Printing Co Ltd 粘着剤層付き被熱転写シ−ト

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58215398A (ja) * 1982-06-08 1983-12-14 Sony Corp 被印刷紙
JPS61199997A (ja) * 1985-02-28 1986-09-04 Dainippon Printing Co Ltd 熱転写受像シート
JPS627594A (ja) * 1985-07-04 1987-01-14 Sony Chem Kk 昇華転写用透明被転写体
EP0209359A2 (fr) * 1985-07-15 1987-01-21 Matsushita Electric Industrial Co., Ltd. Couche réceptrice pour le colorant, pour l'enregistrement par transfert thermique
JPS6223790A (ja) * 1985-07-24 1987-01-31 Matsushita Electric Ind Co Ltd 感熱転写記録用受像体
JPS6246689A (ja) * 1985-08-27 1987-02-28 Mitsubishi Rayon Co Ltd 昇華型感熱転写記録方式の被記録体用コ−テイング組成物
JPS62222895A (ja) * 1986-03-25 1987-09-30 Nitto Electric Ind Co Ltd 昇華型感熱記録用受像体
JPS6319295A (ja) * 1986-07-12 1988-01-27 Nippon Telegr & Teleph Corp <Ntt> 昇華型熱転写受像体
JPS6327367U (fr) * 1986-08-08 1988-02-23
JPS6367188A (ja) * 1986-09-10 1988-03-25 Mitsubishi Rayon Co Ltd 昇華性分散染料易染性樹脂組成物
EP0292109A1 (fr) * 1987-04-24 1988-11-23 Imperial Chemical Industries Plc Récepteur de transfert thermique

Also Published As

Publication number Publication date
EP0394460A1 (fr) 1990-10-31
EP0394460A4 (en) 1991-08-28
WO1990001419A1 (fr) 1990-02-22
DE68928514D1 (de) 1998-02-05
DE68928514T2 (de) 1998-08-20

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