EP0820875A1 - Thermisches Übertragungsblatt, das eine spezielle Schmierstoffgleitschicht verwendet - Google Patents

Thermisches Übertragungsblatt, das eine spezielle Schmierstoffgleitschicht verwendet Download PDF

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Publication number
EP0820875A1
EP0820875A1 EP97305483A EP97305483A EP0820875A1 EP 0820875 A1 EP0820875 A1 EP 0820875A1 EP 97305483 A EP97305483 A EP 97305483A EP 97305483 A EP97305483 A EP 97305483A EP 0820875 A1 EP0820875 A1 EP 0820875A1
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EP
European Patent Office
Prior art keywords
thermal transfer
heat resistant
transfer sheet
parts
resistant slip
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.)
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Application number
EP97305483A
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English (en)
French (fr)
Inventor
Junichi C/O Dai Nippon Printing Co. Ltd. Hiroi
Nobuyuki C/O Dai Nippon Printing Co. Ltd. Harada
Shigeki C/O Dai Nippon Printing Co. Ltd. Chujo
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Priority claimed from JP8212186A external-priority patent/JPH1035122A/ja
Priority claimed from JP8212185A external-priority patent/JPH1035121A/ja
Application filed by Dai Nippon Printing Co Ltd filed Critical Dai Nippon Printing Co Ltd
Publication of EP0820875A1 publication Critical patent/EP0820875A1/de
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/423—Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes

Definitions

  • the present invention relates to a thermal transfer sheet, and particularly relates to a thermal transfer sheet provided with a heat resistant slip layer comprising a specific material, which can prevent dropping out or misregistration of print to be caused by crumples of the thermal transfer sheet or an image-receiving material in a printing process, sticking of a thermal head to the thermal transfer sheet, and formation of head grime to be caused by a heating operation with the use of the thermal head and a cooling process thereafter.
  • a typical sublimation thermal transfer sheet is composed of a substrate film made of plastic such as polyester and a dye layer as a thermally transferable coloring material layer which is disposed on one surface of the substrate film and made of sublimation dye and binder resin.
  • the heat fusion thermal transfer sheet has a heat fusible ink layer made of a heat fusible composition containing coloring material instead of the dye layer.
  • Such a thermal transfer sheet is image-wise heated from its back surface side by a heating means such as the thermal head to transfer the dye of the dye layer or the heat fusible composition of the heat fusible ink layer to the image-receiving material, thus forming an image.
  • a heating means such as the thermal head to transfer the dye of the dye layer or the heat fusible composition of the heat fusible ink layer to the image-receiving material, thus forming an image.
  • the conventional thermal transfer sheet having a substrate film made of relatively heat fusible material such as plastic has caused problem in a process for formation of the image, such as deterioration of a peeling ability and a slipping ability against the thermal head and breakage of the substrate film.
  • a heat resistant slip layer has been formed on a surface of the substrate film opposite to the surface on which the coloring material layer is disposed by using modified resin such as thermosetting resin and silicone resin solely or in combination with cross linking agent.
  • modified resin such as thermosetting resin and silicone resin solely or in combination with cross linking agent.
  • a lubricant such as surface active agent, oil, organometallic salt and wax any one of which has the good slipping ability and the good releasing (or peeling) ability in a heated condition into the heat resistant slip layer.
  • the lubricant to be added is liquid, it may have a poor compatibility to the binder resin for the heat resistant slip layer. Furthermore, when the liquid lubricant has a low viscosity, the lubricant may transfer to the opposite surface of the substrate film or a surface of a conveying roll in the manufacturing or working process to cause a shortage of the lubricant in the heat resistant slip layer of the thermal transfer sheet as an end product. Accordingly, the use of the liquid lubricant may cause a deterioration of the slipping ability. Furthermore, when the thermal transfer sheet is rolled up, the use of the liquid lubricant may cause the transferring of the coloring material from the coloring material layer to the adjacent heat resistant slip layer, resulting in a contamination of the heat resistant slip layer.
  • the slipping ability and the releasing ability may be insufficient because of its low responsiveness to a momentary heating, and further, the lubricant may be deposited on the surface of the thermal element such as the thermal head to become the head grime in a cooling process after the heating with the use of the thermal head, thus causing a bad influence to the printed surface.
  • the thermal head 7 is sliding along the back surface 8 of the thermal transfer sheet, the head grime 10 is liable to be deposited on a surface of an advance direction (9) side of the thermal head 7.
  • an object of the present invention is to provide a thermal transfer sheet in which properties of the heat resistant slip layer such as the slipping ability and the releasing ability are excellent in the heat responsiveness, and the formation of the head grim to be caused in the heating operation with the use of the thermal head and the cooling process thereafter is prevented.
  • a thermal transfer sheet provided by the present invention comprises a substrate film, at least one transferable layer disposed on one surface side of said substrate film and a heat resistant slip layer disposed on another surface side of said substrate film, said heat resistant slip layer comprising organic phosphoric ester derivative represented by the following formula (1) or formula (2) as a lubricant;
  • each of R 1 , R 2 , R 3 and R 4 denotes OC k H 2k+1 , (OCH 2 CH 2 ) m OC n H 2n+1 , (OCH 2 CH 2 ) m OCOC n H 2n+1 or OH;
  • "k” denotes integer of 8 to 20;
  • "m” denotes integer of 1 to 10; and
  • n denotes integer of 1 to 20
  • each of R 5 and R 6 denotes OC k H 2k+1 , (OCH 2 CH 2 ) m OC n H 2n+1 , (OCH 2 CH 2 ) m OCOC n
  • the organic phosphoric ester derivative represented by the formula (1) or the formula (2) is used as the lubricant for the heat resistant slip layer of the thermal transfer sheet, the organic phosphoric ester derivative is compatible very well with the binder resin for the heat resistant slip layer and hardly transfers to another surface or object, and it becomes possible to prevent a contamination of the heat resistant slip layer to be caused by the transferring of the coloring material, to improve the slipping ability, the releasing ability and the like with respect to their responsiveness against the heating, and to prevent a formation of the head grime to be caused in the heating operation with the use of the heating element and the cooling process thereafter.
  • the heat resistant slip layer may contain: an organic or inorganic filler; a hardening agent such as isocyanate hardening agent, polyisocyanate, monomer containing unsaturated bond, polymer containing unsaturated bond, chelate compound and epoxy hardening agent; and another lubricant other than the organic phosphoric ester derivative described above.
  • a hardening agent such as isocyanate hardening agent, polyisocyanate, monomer containing unsaturated bond, polymer containing unsaturated bond, chelate compound and epoxy hardening agent
  • another lubricant other than the organic phosphoric ester derivative described above.
  • the heat resistant slip layer usually comprises 100 weight parts of a binder resin and 1 to 100 weight parts of the organic phosphoric ester derivative.
  • the heat resistant slip layer usually comprises 100 weight parts of the binder resin in a total amount including the filler and the hardening agent and 1 to 150 weight parts of the organic phosphoric ester derivative.
  • the heat resistant slip layer usually has an applied amount up to 3.0 g/m 2 in a solid component.
  • the transferable layer of the thermal transfer sheet may be a coloring material layer selected from the group consisting of a dye layer and a heat fusible ink layer.
  • FIG. 1 is a schematic sectional view of one example of a thermal transfer sheet according to the present invention.
  • FIG. 2 is an explanatory view indicating a formation process of a head grime.
  • FIG. 1 shows a schematic sectional view of one example of the thermal transfer sheet according to the present invention.
  • the thermal transfer sheet 1 has a substrate film 2, and plural kinds of transferable layers, i.e., coloring material layers of Yellow (3Y), Magenta (3M), Cyan (3C) and Black (3K), a transferable receptor layer 4 and a transferable protect layer 5 are formed on a front surface of the substrate film 2 side by side in this order. Furthermore, a heat resistant slip layer 6 is formed on a back surface of the substrate film 2.
  • transferable layers i.e., coloring material layers of Yellow (3Y), Magenta (3M), Cyan (3C) and Black (3K
  • a transferable receptor layer 4 and a transferable protect layer 5 are formed on a front surface of the substrate film 2 side by side in this order.
  • a heat resistant slip layer 6 is formed on a back surface of the substrate film 2.
  • a thermal element such as a thermal head 7 is brought into contact with the back surface of the thermal transfer sheet 1, and the thermal transfer sheet 1 is heated from its back surface side.
  • the transferable receptor layer 4 is first transferred onto an area to be printed of an image receiving material, and next, at least one color of the coloring material such as the dye or the heat fusible ink is transferred from any coloring material layer 3Y, 3M, 3C or 3K to the area provided with the receptor layer to form the image, and the transferable protect layer 5 is transferred onto the area having the formed image, thus obtaining a printed matter.
  • one or more kinds of transferable layer optionally selected are disposed on the front surface side of the substrate film side by side, and the heat resistant slip layer containing the organic phosphoric ester derivative represented by the formula (1) or the formula (2) as a lubricant is disposed on the back surface side of the substrate film.
  • the transferable layer to be disposed on the front surface side may be thermally transferable itself or contain a thermally transferable component.
  • the transferable layer capable of transferring itself includes the heat fusible ink layer, the transferable receptor layer, the transferable protect layer and the like.
  • the transferable layer enabling the component therein to transfer includes the sublimation dye layer.
  • the substrate film for the thermal transfer sheet is not limited to a specific one as far as the film has a desired heat resistance and strength, and a known substrate film conventionally used for a general thermal transfer sheet may be used.
  • An example for the substrate film includes the following films which usually have a thickness of 0.5 to 50 ⁇ m, and preferably 3 to 10 ⁇ m: a resin film such as a polyethylene terephthalate film, a poly 1,4-cyclohexylenedimethylene terephthalate film, a polyethylene naphthalate film, polyphenylene sulfide film, a polystyrene film, a polypropylene film, a polysulfone film, an aramid film, a polycarbonate film, a polyvinyl alcohol film, cellophane, a film of cellulose acetate or another cellulose derivative, a polyethylene film, a polyvinyl chloride film, a nylon film, a polyimide film and an ionomer film
  • the heat resistant slip layer on one surface of the substrate is formed of at least the binder resin and the organic phosphoric ester derivative represented by the following formula (1) or formula (2) as the lubricant, and it may contain various kind of additives as the occasion demands.
  • each of R 1 , R 2 , R 3 and R 4 denotes OC k H 2k+1 , (OCH 2 CH 2 ) m OC n H 2n+1 , (OCH 2 CH 2 ) m OCOC n H 2n+1 or OH; "k” denotes integer of 8 to 20; "m” denotes integer of 1 to 10; and "n” denotes integer of 1 to 20; and R 1 , R 2 , R 3 and R 4 may be the same or different from each other]
  • each of R 5 and R 6 denotes OC k H 2k+1 , (OCH 2 CH 2 ) m OC n H 2n+1 , (OCH 2 CH 2 ) m OCOC
  • the binder resin for the heat resistant slip layer is not limited to a specific one, and any one of thermoplastic resin and thermosetting resin may be used solely or in combination with each other as the binder resin.
  • a reaction product obtained by reacting a resin having a reactive group with a hardening agent such as an isocyanate hardening agent, a monomer or oligomer or high polymer containing unsaturated bond, a chelate compound and an epoxy hardening agent may also be used as the binder resin having an improved heat resistance.
  • a method for the hardening is not limited to a specific one, and the reaction product may be hardened by, for example, the heating or the ionizing radiation.
  • each kind of modified resin obtained by modifying the binder resin with silicone, long chain alkyl or the like may be used as the binder resin for the heat resistant slip layer.
  • the binder resin for the heat resistant slip layer there may preferably be used, for example, polyester resin, polyacrylic ester resin, polyvinyl acetate resin, styrene acrylate resin, polyurethane resin, polyolefine resin, polystyrene resin, polyvinyl chloride resin, polyether resin, polyamide resin, polycarbonate resin, polyethylene resin polypropylene resin, polyacrylate resin, polyacrylamide resin, polyvinyl butyral resin, polyvinyl acetoacetal resin, and oily polyol, and more preferably used polyvinyl acetal resin such as polyvinyl acetoacetal resin.
  • the modified resin there may be used various kinds of the silicone modified resin supplied on the market, acrylic polyol, acetal resin and a reaction product obtained by reacting a resin having hydroxyl group with monohydric higher alcohol derivative modified with isocyanate.
  • polyisocyanate which is to act as a cross linking agent may be added into the heat resistant slip layer.
  • polyisocyanate there may be any polyisocyanate compound conventionally used for paint, adhesive or bonding agent and synthesis of polyurethane.
  • a concrete example of such a polyisocyanate includes the following manufactured products: TAKENATE (manufactured by TAKEDA YAKUHIN KOGYO Co. Ltd.), BARNOCK (manufactured by Dainippon Ink Kagaku Kogyo Co. Ltd.), COLONATE (manufactured by Nihon Polyurethane Kogyo Co. Ltd.), DURANATE (manufactured by Asahikasei Kogyo Co. Ltd.)and DESMODUR (manufactured by Bayer Co. Ltd.).
  • An amount of polyisocyanate is usually within a range of 5 to 280 weight parts to 100 weight parts of the binder resin for the heat resistant slip layer.
  • a ratio of " -NCO/-OH " is preferably within a range of 0.6 to 2.0.
  • an excessively large amount of polyisocyanate causes difficulty in controlling shrinkage of a freshly-coated heat resistant slip layer and delay of the hardening time, and further, when an unreacted -NCO group still remains in the heat resistant slip layer, the remaining -NCO group reacts with moisture in the air and the binder resin or the dye in the coloring material layer, resulting in degradation of the property of the thermal transfer sheet.
  • the monomer or polymer (oligomer or high polymer) containing the unsaturated bond may also be used as the cross linking agent for the purpose of improving the heat resistant slip layer in its heat resistance, its coating workability and its adhesiveness to the substrate film.
  • the monomer or polymer containing the unsaturated bond may be used solely in place of the isocyanate described above or in combination therewith.
  • As a typical hardening method for those monomer and polymer there may be used irradiation of an electron ray or an ultraviolet ray, and in a case of a large amount of the filler to be used, the irradiation of the electron ray is preferably carried out.
  • an example of the monomer or polymer containing the unsaturated bond includes the following compounds, and a wording "(metha)acrylate” described below means as acrylate and methacrylate: a bi-functional monomer such as tetraethyleneglycol di(metha)acrylate, divinylbenzene and diallyl phthalate; a ter-functional monomer such as triallyl isocyanate and trimethylolpropane tri(metha)acrylate; tetramethylolmethane tetra(metha)acrylate; trimethoxyethoxy vinylsilane; a quinque or more functional monomer; and an oligomer or high polymer made from the above described monomer.
  • a bi-functional monomer such as tetraethyleneglycol di(metha)acrylate, divinylbenzene and diallyl phthalate
  • a ter-functional monomer such as triallyl isocyanate and trimethylolpropane tri(metha)acryl
  • the organic phosphoric ester derivative represented by the formula (1) which is used as the lubricant in the present invention is a reaction product obtained by reacting an organic phosphoric ester with a titanium chelate, and its reaction process can be expressed by the following reaction formula (3): [ in the formula (3), each of R 1 , R 2 , R 3 and R 4 denotes OC k H 2k+1 , (OCH 2 CH 2 ) m OC n H 2n+1 , (OCH 2 CH 2 ) m OCOC n H 2n+1 1 or OH; R 8 denotes OC z H 2z+1 or NO z/2 C z H 2z+1 ; "k” denotes integer of 8 to 20; “m” denotes integer of 1 to 10; “n” denotes integer of 1 to 20, “y” denotes integer of 2 to 4; and “z” denotes integer of 1 to 8; and R 1 , R 2 , R 3 and R 4 may be the same or different from each other; and
  • the organic phosphoric ester there may be used various kinds of the organic phosphoric ester, and a concrete example thereof includes: a series of PLYSURF (manufactured by Daiichi Kogyo Seiyaku Co. Ltd.); a series of JP (manufactured by Johoku Kagaku Kogyo Co. Ltd.); and a series of NIKKOL DDP (manufactured by Nikko Chemical Co. Ltd.).
  • a concrete example of the titanium chelate agent includes: a series of ORGATIX TC (manufactured by Matsumoto Kosyo Co. Ltd.); TAA, TLA, TEAA, TEAT, TAT, TBSTA (manufactured by Nihon Soda Co. Ltd. or Mitsubishi Gas Chemical Co. Ltd.)
  • the organic phosphoric ester derivative represented by the formula (2) can be used as the lubricant in the present invention in place of the organic phosphoric ester derivative represented by the formula (1) or in combination with the same.
  • the organic phosphoric ester derivative represented by the formula (2) is a reaction product obtained by reacting an organic phosphoric ester with a isocyanate, and its reaction process can be expressed by the following reaction formula (4): [ in the formula (4), each of R 5 and R 6 denotes OC k H 2k+1 , (OCH 2 CH 2 ) m OC n H 2n+1 , (OCH 2 CH 2 ) m OCOC n H 2n+1 or OH; R 7 denotes saturated aliphatic chain, unsaturated aliphatic chain or aromatic chain; "k” denotes integer of 8 to 20; “m” denotes integer of 1 to 10; “n” denotes integer of 1 to 20; and “x” denotes integer of 1 or more; and R 5 and R 6 may be
  • the isocyanate for the reaction formula (4) is not limited to a specific one as far as it contains isocyanate group, and there may be used: for example, toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), tolidine diisocyanate (TODI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), p-phenylene diisocyanate, xylylene diisocyanate (XDI), hydrogenated HDI (H 6 HDI), hydrogenated MDI (H 12 HDI), lysine diisocyanate (LDI), tetramethylxylene diisocyanate (TMXDI), lys
  • TDI toluene diisocyanate
  • MDI diphenylmethane diisocyanate
  • NDI 1,5-naphthalene diiso
  • an added amount of the organic phosphoric ester derivatives is usually within a range of 1 to 100 weight parts, and preferably 2 to 50 weight parts, with respect to 100 weight parts of the binder resin for the heat resistant slip layer.
  • an added amount of the organic phosphoric ester derivatives is usually within a range of 1 to 150 weight parts, and preferably 50 to 120 weight parts, with respect to 100 weight parts of the binder resin in a total amount including the hardening agent, the filler and the like.
  • An excessively small added amount of the organic phosphoric ester derivative causes an insufficient releasing ability of the heat resistant slip layer with respect to the thermal head or another heating element, thus resulting in the dropping out or the misregistration of the print to be caused by the crumples of the thermal transfer sheet or the image-receiving material in a printing process, and the sticking of a thermal head to the thermal transfer sheet.
  • an excessively large added amount of the organic phosphoric ester derivatives causes the deposition of the head grime on the thermal head or another heating element during the heating operation and the cooling process thereafter, thus resulting in a bad influence on the surface to be printed.
  • a lubricant other than the organic phosphoric ester derivative represented by formulas (1) or (2) may be used in combination therewith in order to further improve and stabilize the property of the heat resistant slip layer.
  • the lubricant other than the organic phosphoric ester derivative there may be used: for example, a phosphoric ester series surface active agent; polyethylene phenyl polysiloxane; fatty acid amide; fatty acid ester; long chain aliphatic compound; low molecular polypropylene; a block copolymer of ethylene oxide and propylene oxide; a condensation product of fatty acid salt and polyether compound; an addition product of perfluoro ethylene oxide; a nonionic surfactant such as a sorbitan acid ester series surface active agent; and sodium salt of long chain alkyl sulfonic acid.
  • An amount for use of such an lubricant is usually 5 to 100 weight parts, and preferably 5 to 50 weight parts, with respect to 100 weight parts of the above organic phosphoric ester derivative.
  • an organic or inorganic filler for the heat resistant slip layer.
  • the filler should have a proper particle diameter and a proper particle shape for forming convexo-concave to the surface of the heat resistant slip layer, and not cause wear of the thermal head.
  • the inorganic filler such as talc, kaoline, clay, calcium carbonate, magnesium hydroxide, magnesium carbonate, magnesium oxide, precipitated barium sulfate, molybdenum disulfide, hydrotulcite silica
  • the organic filler such as acrylic resin, benzoguanamine resin, silicone resin, fluoro resin. It is preferable that the filler has a slipping ability, a low hardness and a capability to clean the thermal head.
  • the filler may directly be added and dispersed into the binder resin. Further, it is preferable that a mixture containing the filler is prepared by dispersing the filler in a dispersion medium such as resin and surface active agent any one of which has a good wetting to the filler and a relatively low viscosity, and the thus prepared mixture is added into the binder resin.
  • a dispersion medium such as resin and surface active agent any one of which has a good wetting to the filler and a relatively low viscosity
  • the dispersion medium includes polyether polyol such as UNIOL TG-1000, -2000 and -3000 (manufactured by Nihon Yushi Co. Ltd.), polyurethane resin such as OLESTER -C1000 and -C1066 (manufactured by Mitsuitoatsu Co. Ltd.), PEG and various kinds of surface active agent.
  • the heat resistant slip layer may be formed by: previously selecting proper solvent such as acetone, methyl ethyl ketone, toluene, xylene and another organic solvent or water in order to control the coating suitability; dissolving or dispersing the raw material as described above in the selected solvent to prepare a coating liquid; applying the coating liquid on the back surface side of the substrate film through the known coating method or means such as a gravure coater, a roll coater and a wire coater; and then drying it to solidify.
  • proper solvent such as acetone, methyl ethyl ketone, toluene, xylene and another organic solvent or water in order to control the coating suitability
  • dissolving or dispersing the raw material as described above in the selected solvent to prepare a coating liquid
  • applying the coating liquid on the back surface side of the substrate film through the known coating method or means such as a gravure coater, a roll coater and a wire coater; and then drying it to solidify.
  • An applied amount of the coating liquid i.e., a thickness of the heat resistant slip layer is usually up to 3.0 g/m 2 , and preferably in a range of 0.1 to 1.0 g/m 2 based on a content of a solid component, and the heat resistant slip layer having a sufficient property can be formed within such an amount.
  • a thickness of the heat resistant slip layer is usually up to 3.0 g/m 2 , and preferably in a range of 0.1 to 1.0 g/m 2 based on a content of a solid component, and the heat resistant slip layer having a sufficient property can be formed within such an amount.
  • the polyisocyanate is used together, because the unreacted polyisocyanate group is liable to be left in the coated layer even after the drying process, it is preferable to carry out a heating and aging treatment so as to run out of the unreacted polyisocyanate group.
  • the primer layer is desired to have a sufficient adhesiveness to the substrate film and the heat resistant slip layer, and a sufficient heat resistance and a sufficient dimensional stability so as to prevent a thermal deformation of the substrate film.
  • the primer layer may be formed of any one of thermoplastic resin, thermosetting resin, a mixture of a hardening agent and a resin having reaction group which is reactive with the hardening agent, and a coating composition capable of the cross linking reaction by the irradiation of the light or the ionizing radiation.
  • a coating amount of the primer layer is usually up to 1.0 g/m 2 , and preferably in a range of 0.1 to 0.5 g/m 2 , based on the content of the solid component.
  • a thermal transferable coloring material layer may be formed on the front surface of the substrate film.
  • a dye layer containing sublimation dye is formed on the substrate film, and in a case of the heat fusion type thermal transfer sheet, a heat fusible ink layer colored with pigment or the like is formed thereon.
  • the sublimation thermal transfer sheet will intensively be described hereunder. Though detail of another coloring material layer is omitted, the coloring material layer is not limited to only the sublimation type dye layer.
  • a dye for the sublimation type dye layer is not limited to a specific one, and a dye conventionally used for the known thermal transfer sheet may be used in the present invention.
  • a preferable red dye includes MS Red G, Macro Red Violet R, Ceres Red 7B, Samaron Red HBSL and Resolin Red F3BS; and a yellow dye includes Phorone Brilliant Yellow 6GL, PTY-52 and Macrolex Yellow 6G; and a preferable blue dyes includes Kayaset Blue 714, Waxoline Blue AP-FW, Phorone Brilliant Blue S-R and MS Blue 100.
  • a binder resin to carry and sustain the dye any kind of known binder resin can be used.
  • a preferable binder resin includes: for example, cellulose resin such as ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxycellulose, hydroxypropyl cellulose, methyl cellulose, cellulose acetate and cellulose acetate butyrate; vinyl resin such as polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetoacetal and polyvinyl pyrrolidone; acrylic resin such as poly(metha)acrylate and poly(metha)acrylamide; polyurethane resin; polyamide resin; and polyester resin.
  • these binder resins there may preferably be used the cellulose series, vinyl series, acrylic series, polyurethane series and polyester series resins in view of heat resistance, transability of the dye and the like.
  • the dye layer may be formed on one surface of the substrate film by the following manner. More specifically, a mixture of the dye, the resin binder and an optionally added additive such as release agent, organic or inorganic particle are dispersed in a proper organic solvent such as toluene, methyl ethyl ketone, ethanol, isopropyl alcohol, cyclohexanone and DMF, or dissolved in the above organic solvent or water to prepare a coating liquid, and the thus prepared coating liquid is applied on the substrate film and dried through any coating method such as the gravure printing, the screen printing and the reverse roll coating with the use of a gravure plate.
  • a proper organic solvent such as toluene, methyl ethyl ketone, ethanol, isopropyl alcohol, cyclohexanone and DMF
  • An applied amount of the dye layer is usually in a range of 0.2 to 5.0 g/m 2 , and preferably 0.4 to 2.0 g/m 2 , based on a content of a solid component.
  • an amount ratio of the sublimation dye in the dye layer is usually in a range of 5 to 90 weight %, and preferably 10 to 70 weight %, with respect to a weight of the dye layer.
  • one kind of the dye layer may be formed by selecting only one proper dye.
  • at least two kinds of the dye layers should be formed in a combination of, for example, Yellow, Magenta and Cyan, or further with Black by selecting respective proper dyes.
  • the image receiving material to be used together with the thermal transfer sheet of the present invention is not limited to a specific one.
  • any image receiving material as far as its record surface has receptiveness to the above dye, and furthermore, though the receiving material is formed of non-receptive material such as paper, metal, glass and synthetic resin, such a non-receptive receiving material can also be used by forming a dye receptor layer on its one surface.
  • the surface of the receiving material has no need of the receptiveness to the dye, and a normal paper, a plastic film or the like can be used with no receptor layer.
  • thermal transfer sheet of the present invention is subjected to the thermal transfer printing
  • any known thermal transfer printer is applicable.
  • the lubricant having a good compatibility to the binder resin for the heat resistant slip layer and a low transferring ability is added into the heat resistant slip layer, it is possible to provide a thermal transfer sheet which has the excellent heat responsiveness in the slipping ability and the releasing ability, prevents the formation of the head grim in the heating operation with use of the thermal head and the cooling process thereafter, prevents the formation of the crumple at the time of printing, and provides the printed image having high quality with no dropping out and misregistration.
  • NIKKOL manufactured by Nikko Chemical Co. Ltd.
  • TAA manufactured by Nihon Soda Co. Ltd.
  • the coating material A for the heat resistant slip layer having the following composition was applied onto one surface of the substrate film of the polyester film having a thickness of 4.5 ⁇ m in an applied amount of about 1.0 g/m 2 (in dried state), and then dried to form the heat resistant slip layer.
  • Example A-1 the thermal transfer sheet of Example A-1 according to the present invention was obtained.
  • SOLVENT BLUE 22 5.5 parts Polyvinyl acetoacetal resin (ETHLEC KS-5, manufactured by Sekisui Kagaku Kogyo Co., Ltd.) 3.0 parts Methyl ethyl ketone 22.0 parts Toluene 68.0 parts
  • Example A-2 The thermal transfer sheet of Example A-2 according to the present invention was obtained in the same manner as that in Example A-1, except that the coating material B for the heat resistant slip layer having the following composition was used instead of the coating material A, and the heating and aging step for the hardening treatment was carried out after the coating and drying step.
  • Example A-3 The thermal transfer sheet of Example A-3 according to the present invention was obtained in the same manner as that in Example A-1, except that the coating material C for the heat resistant slip layer having the following composition was used instead of the coating material A, and the electron ray irradiation step at 175 KeV of an accelerating voltage and 3 Mrad for the cross linking and hardening treatment was carried out after the coating and drying step.
  • Example A-4 The thermal transfer sheet of Example A-4 according to the present invention was obtained in the same manner as that in Example A-1, except that the coating material D for the heat resistant slip layer having the following composition was used instead of the coating material A.
  • Example A-5 The thermal transfer sheet of Example A-5 according to the present invention was obtained in the same manner as that in Example A-1, except that the coating material E for the heat resistant slip layer having the following composition was used instead of the coating material A.
  • Example A-6 The thermal transfer sheet of Example A-6 according to the present invention was obtained in the same manner as that in Example A-1, except that the coating material F for the heat resistant slip layer having the following composition was used instead of the coating material A.
  • the thermal transfer sheet of Comparative Example A-1 was obtained in the same manner as that in Example A-1, except that the coating material G for the heat resistant slip layer having the following composition was used instead of the coating material A, and the heating and aging step for the hardening treatment was carried out after the coating and drying step.
  • Phosphoric ester lubricant PLYSURF A208B, manufactured by Daiichi Kogyo Seiyaku Co. Ltd.
  • Oily polyol OLESTER C1066, manufactured by Mitsuitoatsu Kagaku Co. Ltd.
  • Kaolin Kaolin (KAOLINITE ASP-072, manufactured by Tsuchiya Kaolin Co., Ltd.) 0.2 parts Methyl ethyl ketone 28.0 parts Toluene 28.0 parts
  • the thermal transfer sheet of Comparative Example A-2 was obtained in the same manner as that in Example A-1, except that the coating material H for the heat resistant slip layer having the following composition was used instead of the coating material A, and the heating and aging step for the hardening treatment was carried out after the coating and drying step.
  • Nonionic surfactant NONION-OP85R, manufactured by Nihon Yushi Co. Ltd.
  • Clay ASP-200, manufactured by Tsuchiya Kaolin Co., Ltd.
  • the thermal transfer sheet of Comparative Example A-3 was obtained in the same manner as that in Example A-1, except that the coating material I for the heat resistant slip layer having the following composition was used instead of the coating material A, and the heating and aging step for the hardening treatment was carried out after the coating and drying step.
  • the thermal transfer sheet of Comparative Example A-4 was obtained in the same manner as that in Example A-1, except that the coating material J for the heat resistant slip layer having the following composition was used instead of the coating material A, and the electron ray irradiation step at 175 KeV of an accelerating voltage and 3 Mrad for the cross linking and hardening treatment was carried out after the coating and drying step.
  • thermal transfer sheets obtained in the above mentioned Examples and Comparative Examples were subjected to the thermal transfer printing to evaluate an uneveness of output color caused by an irregular conveyance, a dropping out or a misregistration of print caused by crumples of the thermal transfer sheet or an image-receiving material in a printing process, a formation of the head grime, and a contamination of the heat resistant slip layer caused by the dye.
  • the method and criterion for each evaluation are as follows. Further, the results are shown in TABLE 1.
  • the thermal transfer sheet made into a merchantable form by rolling up in a short diameter was stored at 40 °C for 48 hours, and then it was subjected to the thermal transfer printing with the use of a commercially available video printer having a low precision in a control of drive and a pattern generator (CG-931, manufactured by Kenwood Co., Ltd.) to print out a hypochromatic solid printed pattern which was overprinted with three colors.
  • the above thermal transfer printing was carried out at an ordinary temperature and an ordinary humidity. Thereafter the uneveness of the out put color caused by the irregular conveyance and movement of the thermal transfer sheet was evaluated by visual observation on the basis of the following criterion.
  • the thermal transfer sheet made into a merchantable form by rolling up in a short diameter was stored at 40 °C for 48 hours, and then it was subjected to the thermal transfer printing with the use of a printer, in which a pressure of the thermal head was made imbalanced so as to easily cause the dropping out or the misregistration, and the pattern generator (CG-931, manufactured by Kenwood Co., Ltd.), to print out a hypochromatic solid printed pattern at 30 °C and 80 % RH. Thereafter, the dropping out or the misregistration of the print caused by the crumples of the thermal transfer sheet or the image-receiving material was evaluated by visual observation on the basis of the following criterion.
  • the thermal transfer sheet was subjected to the thermal transfer printing with the use of the commercially available printer and the pattern generator (CG-931, manufactured by Kenwood Co., Ltd.), to repeatedly print out fifty sheets of step pattern having an eight steps gradation. Thereafter, the surface of the heating portion of the thermal head was visually observed to evaluate the deposition of the head grim.
  • CG-931 manufactured by Kenwood Co., Ltd.
  • the thermal transfer sheet made into a merchantable form by rolling up in a short diameter was stored at 60 °C for 48 hours, and thereafter the dye transferring contamination was evaluated by visually observing the extent of the dye transferred to the heat resistant slip layer.
  • BARNOCK D750 manufactured by Dainippon Ink Kagaku Kogyo Co. Ltd.
  • 33 weight parts of ethyl acetate were added into a mixture of 50 weight parts of PLYSURF A208S (manufactured by Daiichi Kogyo Seiyaku Co. Ltd.) and 50 weight parts of JP-518-O (manufactured by Johoku Kagaku Co. Ltd.), and reaction was carried out to obtain a solution of compound having 75 % of solid component.
  • the coating material K for the heat resistant slip layer having the following composition was applied onto one surface of the substrate film of the polyester film having a thickness of 4.5 ⁇ m in an applied amount of about 1.0 g/m 2 (in dried state), and then dried to form the heat resistant slip layer.
  • Example B-1 the thermal transfer sheet of Example B-1 according to the present invention was obtained.
  • SOLVENT BLUE 22 5.5 parts Polyvinyl acetoacetal resin (ETHLEC KS-5, manufactured by Sekisui Kagaku Kogyo Co., Ltd.) 3.0 parts Methyl ethyl ketone 22.0 parts Toluene 68.0 parts
  • Example B-2 The thermal transfer sheet of Example B-2 according to the present invention was obtained in the same manner as that in Example B-1, except that the coating material L for the heat resistant slip layer having the following composition was used instead of the coating material K, and the heating and aging step for the hardening treatment was carried out after the coating and drying step.
  • Example B-3 The thermal transfer sheet of Example B-3 according to the present invention was obtained in the same manner as that in Example B-1, except that the coating material M for the heat resistant slip layer having the following composition was used instead of the coating material K, and the electron ray irradiation step at 175 KeV of an accelerating voltage and 3 Mrad for the cross linking and hardening treatment was carried out after the coating and drying step.
  • Example B-4 The thermal transfer sheet of Example B-4 according to the present invention was obtained in the same manner as that in Example B-1, except that the coating material N for the heat resistant slip layer having the following composition was used instead of the coating material K.
  • Example B-5 The thermal transfer sheet of Example B-5 according to the present invention was obtained in the same manner as that in Example B-1, except that the coating material O for the heat resistant slip layer having the following composition was used instead of the coating material K.
  • Example B-6 The thermal transfer sheet of Example B-6 according to the present invention was obtained in the same manner as that in Example B-1, except that the coating material P for the heat resistant slip layer having the following composition was used instead of the coating material K.
  • the thermal transfer sheet of Comparative Example B-1 was obtained in the same manner as that in Example B-1, except that the coating material Q for the heat resistant slip layer having the following composition was used instead of the coating material K, and the heating and aging step for the hardening treatment was carried out after the coating and drying step.
  • Phosphoric ester lubricant PLYSURF A208B, manufactured by Daiichi Kogyo Seiyaku Co. Ltd.
  • Oily polyol OLESTER C1066, manufactured by Mitsuitoatsu Kagaku Co. Ltd.
  • Kaolin Kaolin (KAOLINITE ASP-072, manufactured by Tsuchiya Kaolin Co., Ltd.) 0.2 parts Methyl ethyl ketone 28.0 parts Toluene 28.0 parts
  • the thermal transfer sheet of Comparative Example B-2 was obtained in the same manner as that in Example B-1, except that the coating material R for the heat resistant slip layer having the following composition was used instead of the coating material K, and the heating and aging step for the hardening treatment was carried out after the coating and drying step.
  • Nonionic surfactant NONION-OP85R, manufactured by Nihon Yushi Co. Ltd.
  • Clay ASP-200, manufactured by Tsuchiya Kaolin Co., Ltd.
  • the thermal transfer sheet of Comparative Example B-3 was obtained in the same manner as that in Example B-1, except that the coating material S for the heat resistant slip layer having the following composition was used instead of the coating material K, and the heating and aging step for the hardening treatment was carried out after the coating and drying step.
  • the thermal transfer sheet of Comparative Example B-4 was obtained in the same manner as that in Example B-1, except that the coating material T for the heat resistant slip layer having the following composition was used instead of the coating material K, and the electron ray irradiation step at 175 KeV of an accelerating voltage and 3 Mrad for the cross linking and hardening treatment was carried out after the coating and drying step.
  • the thermal transfer sheets obtained in the series of Example B were tested in the same manner as that in the series of Example A to evaluate the uneveness of output color caused by the irregular conveyance, the dropping out or misregistration of print caused by crumples of the thermal transfer sheet or the image-receiving material in the printing process, the formation of the head grime, and the contamination of the heat resistant slip layer caused by the dye.
  • the results of the series of Example B are shown in TABLE 2.
  • Example B-1 ⁇ ⁇ ⁇ ⁇ Example B-2 ⁇ ⁇ ⁇ ⁇ Example B-3 ⁇ ⁇ ⁇ ⁇ Example B-4 ⁇ ⁇ ⁇ ⁇ Example B-5 ⁇ ⁇ ⁇ ⁇ Example B-6 ⁇ ⁇ ⁇ ⁇ Comparative Example B-1 ⁇ ⁇ ⁇ ⁇ Comparative Example B-2 ⁇ ⁇ ⁇ ⁇ Comparative Example B-3 ⁇ ⁇ ⁇ ⁇ Comparative Example B-4 ⁇ ⁇ ⁇ ⁇ ⁇ ⁇

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)
EP97305483A 1996-07-24 1997-07-22 Thermisches Übertragungsblatt, das eine spezielle Schmierstoffgleitschicht verwendet Withdrawn EP0820875A1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP212185/96 1996-07-24
JP8212186A JPH1035122A (ja) 1996-07-24 1996-07-24 熱転写シート
JP212186/96 1996-07-24
JP8212185A JPH1035121A (ja) 1996-07-24 1996-07-24 熱転写シート

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2030798A3 (de) * 2007-08-29 2009-03-25 Fujifilm Corporation Wärmeempfindliches Übertragungsblatt
EP2168781A1 (de) * 2008-09-30 2010-03-31 Fujifilm Corporation Wärmeempfindliches Übertragungsblatt
EP2168782A1 (de) * 2008-09-30 2010-03-31 Fujifilm Corporation Wärmeempfindliches Übertragungsblatt
CN102616045A (zh) * 2011-01-26 2012-08-01 索尼公司 热转印片材
CN108891146A (zh) * 2018-07-23 2018-11-27 库尔兹压烫科技（合肥）有限公司 一种应用于薄膜基材的热烫箔

Citations (4)

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Publication number Priority date Publication date Assignee Title
EP0458538A1 (de) * 1990-05-25 1991-11-27 Imperial Chemical Industries Plc Thermische Farbstoffübertragungsschicht
EP0513630A1 (de) * 1991-05-06 1992-11-19 Eastman Kodak Company Eine ein Phosphonsäurederivat enthaltende Gleitschicht für ein Farbstoff-Donorelement, das bei der thermischen Farbstoffübertragung verwendet wird
EP0523623A1 (de) * 1991-07-17 1993-01-20 Sony Corporation Farbstoffenthaltende Schicht für Thermoübertragungsdruck
EP0577051A1 (de) * 1992-06-29 1994-01-05 Dai Nippon Printing Co., Ltd. Thermische Übertragungsschicht

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0458538A1 (de) * 1990-05-25 1991-11-27 Imperial Chemical Industries Plc Thermische Farbstoffübertragungsschicht
EP0513630A1 (de) * 1991-05-06 1992-11-19 Eastman Kodak Company Eine ein Phosphonsäurederivat enthaltende Gleitschicht für ein Farbstoff-Donorelement, das bei der thermischen Farbstoffübertragung verwendet wird
EP0523623A1 (de) * 1991-07-17 1993-01-20 Sony Corporation Farbstoffenthaltende Schicht für Thermoübertragungsdruck
EP0577051A1 (de) * 1992-06-29 1994-01-05 Dai Nippon Printing Co., Ltd. Thermische Übertragungsschicht

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2030798A3 (de) * 2007-08-29 2009-03-25 Fujifilm Corporation Wärmeempfindliches Übertragungsblatt
US8236728B2 (en) 2007-08-29 2012-08-07 Fujifilm Corporation Heat-sensitive transfer sheet
EP2168781A1 (de) * 2008-09-30 2010-03-31 Fujifilm Corporation Wärmeempfindliches Übertragungsblatt
EP2168782A1 (de) * 2008-09-30 2010-03-31 Fujifilm Corporation Wärmeempfindliches Übertragungsblatt
US8258079B2 (en) 2008-09-30 2012-09-04 Fujifilm Corporation Heat-sensitive transfer sheet
US8288314B2 (en) 2008-09-30 2012-10-16 Fujifilm Corporation Heat-sensitive transfer sheet
CN102616045A (zh) * 2011-01-26 2012-08-01 索尼公司 热转印片材
US8541341B2 (en) 2011-01-26 2013-09-24 Sony Corporation Thermal transfer sheet
CN108891146A (zh) * 2018-07-23 2018-11-27 库尔兹压烫科技（合肥）有限公司 一种应用于薄膜基材的热烫箔

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