EP0319331B1 - Thermische Farbstoffübertragungsdruckschicht - Google Patents
Thermische Farbstoffübertragungsdruckschicht Download PDFInfo
- Publication number
- EP0319331B1 EP0319331B1 EP88311469A EP88311469A EP0319331B1 EP 0319331 B1 EP0319331 B1 EP 0319331B1 EP 88311469 A EP88311469 A EP 88311469A EP 88311469 A EP88311469 A EP 88311469A EP 0319331 B1 EP0319331 B1 EP 0319331B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dye
- colored layer
- transfer
- printing sheet
- type thermal
- 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.)
- Expired - Lifetime
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
Definitions
- This invention relates to a dye-transfer-type thermal printing sheet that is used for recording by means of thermal transfer. More particularly, it relates to a transfer-type thermal printing sheet that is effective when the dye used is likely to sublimate.
- This printing sheet can be used for high-speed printing by electronic devices with heads through which current flows, laser elements, or the like.
- Dye-transfer-type printing sheets comprise a substrate and a colored layer.
- some of the sublimated dye that is contained in the colored layer is transferred to an image-receiving sheet such as a recording paper, resulting in an image on the image-receiving sheet.
- the colored layer is usually composed of a dye that is likely to sublimate and a bonding material that binds this colored layer on the top of the substrate.
- the dye-transfer-type printing sheet composed of a substrate and a colored layer contains non-volatile granules, surfactants with aliphatic groups, silicones, or fluorides so as to prevent the sticking together of the colored layer and the image-receiving sheet and also the transfer by pressure of the dye from the colored layer to the image-receiving sheet, both of which phenomena are causes of deterioration of the image quality.
- This kind of transfer printing sheet has the following problems:
- a dye-transfer-type thermal printing sheet which comprises a substrate and a colored layer disposed on the substrate, the colored layer comprising a dye, a binding material and a combination of wax and one or more fatty acid amides, wherein the heat deformation temperature of the entire colored layer is in the range of 60 to 120°C.
- the fatty acid amide is at least one selected from oleamide, stearamide, cis -13-docosenoamide (erucamide), lauramide, oxystearamide, and n-oleylpalmitamide.
- the wax is at least one selected from the group consisting of paraffin wax, microcrystalline wax, and oxidized wax.
- the wax and the fatty acid amides, respectively, are contained in said colored layer in the proportion of 1 to 10% by weight.
- the colored layer contains a resin with a glass transition temperature of 65°C or more as a binding material.
- the binding material that constitutes said colored layer is a product derived from the reaction of cross-linking agents with resins with a glass transition temperature of 65°C or more.
- an adhesive layer is disposed between said substrate and said colored layer, said adhesive layer containing an adhesive resin and dye.
- the dye that is contained in said adhesive layer can be the same as the dye in the colored layer.
- Preferably the percentage of the dye that is contained in said adhesive layer is at least one half of that of dye included in said colored layer.
- An adhesive resin that constitutes said adhesive layer is at least one selected from saturated polyester resin, polyurethane resin, and acrylic resin.
- the invention described herein makes possible the objectives of (1) providing a dye-transfer-type thermal printing sheet with high recording density at the time of the recording of an image on an image-receiving sheet; (2) providing a dye-transfer-type thermal printing sheet, the properties of which will deteriorate only slightly in conveyance and storage; and (3) providing a dye-transfer-type thermal printing sheet that can be peeled off readily from the image-receiving sheet once recording has been accomplished.
- Figure 1 shows a dye-transfer-type thermal printing sheet 11 of this invention, which comprises a substrate 1 and a colored layer 2.
- the substrate 1 there are no particular restrictions concerning the substrate 1, provided that it supports the colored layer 2 that contains the dye to be transferred from the colored layer 2 to an image-receiving sheet (not shown).
- a film made of PET, cellophane, polyamide, polyarylate, or the like can be used as the substrate 1. Heat-resistance and/or smoothness can be added to these materials. Materials that have conductivity can be also used as the substrate 1 so as to perform current-heating recording and induction heating recording.
- the colored layer 2 is composed of, at least, dye, a binding material, fatty acid amides, and wax and has a heat deformation temperature of 60 to 120°C.
- the image quality becomes rough and/or the recording sensitivity is lowered if the dye has condensed, has crystallized, or the like, so the dye must be soluble in the binding material.
- the dye should be a dye that confers color and/or a color former.
- the colored layer is readily deformed or melted with the application of heat, it can readily adhere to the image-receiving sheet.
- surfactants and separating agents that have aliphatic groups or silicones are added to the colored layer. These surfactants and separating agents have a low molecular weight, so they move to the surface of the colored layer with the passage of time to thereby prevent adhesion by the incompatibility or non-adhesion of the long-chain aliphatic segment or the dimethylsiloxane segment.
- the properties of the printing sheet can change during commercial use such as transport and storage; the dye may spread from the front surface of the printing sheet to the back surface thereof when the printing sheet is wrapped; or pressure transfer may occur.
- polymers that contain fluorine are present in the surface area of the colored layer, the above problems do not arise, because the fluoroalkyl group of the polymers that contain fluorine does not dissolve the dye.
- the intermolecular energy of the fluoroalkyl group is small, which makes the surface energy small, there is incompatibility and non-adhesion between the fluoroalkyl group and the resin that forms the image-receiving sheet, so that the removability of the image-receiving sheet from the printing sheet after recording is finished is improved.
- the removability of an image-receiving sheet with good durability of the recorded image from the printing sheet is still inferior; the reason is that an image-receiving sheet with good durability has a coloration layer that does not contain substances that have parting properties such as those of silicone oil or silicone surfactants.
- the colored layer of the dye-transfer-type thermal printing sheet of this invention contains, in addition to a dye and a binding material, wax and fatty acid amides that make the wax compatible with thermoplastic resins.
- a dye and a binding material wax and fatty acid amides that make the wax compatible with thermoplastic resins.
- wax and fatty acid amides that make the wax compatible with thermoplastic resins.
- the wax incorporated into the colored layer 2 is not limited to any particular wax, but can be paraffin wax, microcrystalline wax, oxidized wax, polyethylene wax, polypropylene wax, polystyrene wax, and other kinds of vinyl compounds with a low degree of polymerization. From the point of view of removability, paraffin wax, microcrystalline wax, and oxidized wax are preferable. If the proportion of wax to the entire colored layer is very large, the compatibility of the wax with the binding resin is lowered, and so the amount of wax that should be incorporated into the colored layer is from 1 to 10% by weight.
- fatty acid amides monoamides such as stearamide, oleamide, cis -13-docosenoamide, lauramide, palmitamide, behenamide, ricinolamide, oxystearamide, methylolstearamide, methylolbehenamide and/or bisamides such as methylenebisstearamide, ethylenebisstearamide, ethylenebisoleamide, and ethylenebislauramide can be used. If the solubility of the ink in solvents is considered when the ink is being prepared for use in the colored layer, oleamide, stearamide, cis -13-docosenoamide, lauramide, oxystearamide, and n-oleylpalmitamide are preferable.
- the amount of fatty acid amide in the entire colored layer is very large, the stability during storage of the printing sheet is lowered. From the point of view of the compatible effect of the wax and the binding-resin material, the amount of fatty acid amide should be about one-half to two times that of wax, and it is preferable that the amount of fatty acid amide in the colored layer be 1-10% by weight.
- the heat deformation temperature of the entire colored layer should be 60-120°C.
- the heat deformation temperature of the entire colored layer changes with changes in the amount of dye in the colored layer as shown in Figure 2.
- the heat deformation temperature of the entire colored layer changes depending on the heat deformation temperature or on the glass transition temperature of the resin that is used as the binding material as shown in Figure 3. Even when wax and fatty acid amide are present, the heat deformation temperature of the entire colored layer decreases if the proportion in the colored layer are large.
- the relationship between the heat deformation temperature of the entire colored layer and the recording density have the relationship shown in Figure 4. If the heat deformation temperature of the entire colored layer is 120°C or less, the heat at the time of recording readily softens the entire colored layer, and the movement of the dye to the front surface of the colored layer is thereby facilitated, so that the dye is more readily transferred from the colored layer to the image-receiving sheet by sublimation, heat diffusion, and/or the like.
- the heat deformation temperature of the entire colored layer is 60°C or higher, migration of dye that causes transfer to the image-receiving sheet surface or condensation of dye such as was mentioned above does not occur, because the ambient temperature during transport and storage in industrial and other uses is generally les than 60°C.
- the following method can be used to keep the heat deformation temperature of the entire colored layer at 60°C or more.
- the following method can be used to make the heat deformation temperature of the entire colored layer 120°C or less.
- the heat deformation temperature of the entire colored layer is measured with a steady rate of temperature increase in a tensile test under a constant load or a penetration test under a constant load by the use of a thermo-mechanical tester, and defined as follows:
- the adhesion of the substrate to the colored layer of the printing sheet is not sufficient, as shown in Figure 7, it is possible to form an adhesive layer 3 between the substrate 1 and the colored layer 2.
- an adhesive layer there is some dispersion of the dye from the colored layer to the adhesive layer, so the recording sensitivity declines.
- the percentage of dye to be contained in the adhesive layer be 30% or more of the percentage of dye to be contained in the colored layer, and more preferably 50% or more.
- the resin that is used as the adhesion layer there are no particular limitations, provided that the substance confers adhesion between the substrate and the colored layer.
- an oil-soluble resin that is used as the adhesion layer when the substrate is made of PET there are saturated polyester resin, polyurethane resin, modified acrylic resin, and the like.
- a water-soluble resin that is used as the adhesion layer there are ionomer resin, acrylate resin, and the like. These resins can be further hardened by cross-linking agents.
- Figure 8 shows an image-receiving sheet 12 of this invention, which is composed of a substrate 4 and a coloration layer 5 disposed on the said substrate 4.
- the substrate 4 it is possible to use ordinary paper, coated paper, art paper, synthetic paper, PET film, and so on.
- the coloration layer 5, resin, etc., that can be colored well by the dye can be used.
- a heat-resistant and lubricating layer was disposed on the back surface of PET film with a thickness of 4 ⁇ m, resulting in a substrate.
- On the front surface of the PET film of the substrate there was painted with a wire bar an ink obtained by dissolving, in a mixture of 42 g of toluene and 18 g of MEK as the solvents, 2 g of Dye A of the structural formula described below, 4 g of polyvinylbutylal (S-LEC BX-1; Sekisui Kagaku) as a binding material with a glass transition temperature of 86°C, 0.2 g of paraffin wax with a melting point of 50°C, and 0.2 g of oleamide. This was dried in a warm draft, resulting in a dye-transfer-type thermal printing sheet.
- Dye A 2.5 g of Dye A, 4 g of AS resin (Denki Kagaku Kogyo Co.; Denka Styrol AS-SU) as a binding material, 0,4 g of microcrystalline wax (Nihon Seiro Co.; Hi-Mic-2045), and 0.4 g of cis -13-docosenoamide were dissolved in 60 g of monochlorobenzene to make ink, which was then painted with a wire bar on the same substrate as was used in Example 1 and dried, resulting in a dye-transfer-type printing sheet.
- AS resin Denka Styrol AS-SU
- microcrystalline wax Nihon Seiro Co.
- Hi-Mic-2045 0.4 g of cis -13-docosenoamide
- Dye A 3.0 g of Dye A, 4.0 g of polycarbonate resin (Teijin Kasei Co.; Panlite L-1225) as a binding material, 0.2 g of paraffin wax, and 0.2 g of oleamide were dissolved in 60 g of dichloromethane to make ink, which was then painted with a wire bar on the same substrate as was used in Example 1 and dried in a warm draft, resulting in a dye-transfer-type printing sheet.
- polycarbonate resin Teijin Kasei Co.; Panlite L-1225
- Dye A 3.2 g of acrylonitrilestyrene copolymer (Denki Kagaku Kogyo Co., Denka AS S-312) as a binding material
- 0.3 g of paraffin wax with a melting point of about 70°C 0.5 g of lauramide
- a mixture of 30 g of toluene and 30 g of MEK to make ink, which was then painted with a wire bar on the same substrate as was used in Example 1 and dried in a warm draft, resulting in a dye-transfer-type thermal printing sheet.
- Dye A 3 g of Dye A, 4 g of a saturated polyester resin (Nihon Gosei Kagaku Kogyo Co.; polyester TP-236) with a glass transition temperature of 60°C, 0.4 g of isocyanate (Nihon Polyurethane Co.; Coronate L), 0.2 g of paraffin wax with a melting point of 70°C, and 0.2 g of oleamide were dissolved in 60 g of dichloromethane to make ink, which was then painted with a wire bar on the same substrate as was used in Example 1 and dried, after which it was left in a drier at a fixed temperature of 50°C for 4 hours, which hardened the colored layer, resulting in a dye-transfer-type thermal printing sheet.
- Dye A 1 g of Dye A, 4 g of a saturated polyester resin (Toyo Boseki Co.; Vylon 200), and 0.3 g of isocyanate (Nihon Polyurethane Co.; Coronate L) were dissolved in 60 g of dichloromethane to form a coating, which was then painted with a wire bar on the top surface of the same substrate as was used in Example 1 and dried, giving an adhesive layer with a thickness of about 0.2 ⁇ m. On the top surface of this layer, the same ink as was used in Example 3 was painted with use of a wire bar and dried, resulting in a dye-transfer-type thermal printing sheet.
- a saturated polyester resin Toyo Boseki Co.; Vylon 200
- isocyanate Nihon Polyurethane Co.; Coronate L
- Example 2 On the same substrate as was used in Example 1, an ink that was obtained by dissolving, into a mixture of 42 g of toluene and 18 g of MEK, 2 g of Dye A, and 4 g of polyvinylbutylal (Denki Kagaku Kogyo Co.; Denkabutyral #6000-C) with a glass transition temperature of 90°C as a binding material was applied with a wire bar and dried, giving a dye-transfer-type thermal printing sheet.
- polyvinylbutylal Denkabutyral #6000-C
- Example 2 On the same substrate as was used in Example 1, an ink that was obtained by dissolving 2 g of Dye A, 4 g of polyvinylbutylal (same as above) as a binding material, and 0.2 g of paraffin wax with a melting point of 50°C into 60 g of the same solvent as was used in Control 1 was applied with a wire bar and dried with a warm draft, giving a dye-transfer-type thermal printing sheet.
- Example 2 On the same substrate as was used in Example 1, an ink that was obtained by dissolving 2 g od Dye A and 4 g of polysulphone (Nissan Kagaku Kogyo Co.; P-1700) into 60 g of chlorobenzene was applied with a wire bar and dried with a warm draft, giving a dye-transfer-type thermal printing sheet.
- polysulphone Nisan Kagaku Kogyo Co.; P-1700
- Example 2 On the same substrate as was used in Example 1, an ink that was obtained by dissolving 5 g of Dye A dna 4 g of polysulphone (Nissan Kagaku Kogyo Co.; P-1700) into 60 g of chlorobenzene was applied with a wire bar and dried with a warm draft, giving a dye-transfer-type thermal printing sheet.
- Example 2 On the same base as was used in Example 1, a coating that was obtained by dissolving 4 g of saturated polyester resin (Toyo Boseki Co.; Vylon 200) and 0.3 g of isocyanate (Nihon Polyurethane Co.; Coronate L) into 60 g of dichloromethane was applied with a wire bar and dried, resulting in an adhesive layer with a thickness of about 0.2 ⁇ m. On the top surface of this layer, the same ink that was used in Example 3 was applied, giving a dye-transfer-type thermal printing sheet.
- saturated polyester resin Toyo Boseki Co.; Vylon 200
- isocyanate Nihon Polyurethane Co.; Coronate L
- the following items were measured under the below-mentioned recording conditions for thermal heads by the use of the dye-transfer-type thermal printing sheets and the image-receiving sheets obtained above: the recording density; the force needed to remove the image-receiving sheet from the printing sheet per recording width after recording; the presence or absence of transfer of dye from the front surface of the printing sheet to the back surface of the printing sheet after storage for 200 hours at 60°C at 60% relative humidity with the printing sheets in a rolled condition; and the heat deformation temperature of the entire colored layer.
- Table 1 The results of measurements of the above-mentioned items are shown in Table 1.
- the units used to express the force needed to remove the image-receiving sheet from the printing sheet per recording width after recording were x 0.98 N/m (gw/cm).
- the measurements of the transfer of dye from the front surface of the printing sheet to the back surface thereof were made after storage for 200 hours at 60°C at 60% relative humidity.
- TH is the value found for the heat deformation temperature of the entire colored layer.
- the dye-transfer-type thermal printing sheet of this invention that contains wax and fatty acid amides in its colored layer results in a high recording density and satisfactory properties for storage and removability of image-receiving sheets therefrom.
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Claims (10)
- Thermische Farbstoffübertragungsdruckschicht mit einem Substrat und einer auf dem Substrat angeordneten gefärbten Schicht, wobei die gefärbte Schicht einen Farbstoff, ein Bindematerial und eine Kombination von Wachs und einem oder mehreren Fettsäure-Amiden aufweist, wobei die Wärmeverformungstemperatur der gesamten gefärbten Schicht im Bereich von 60 bis 120°C ist.
- Thermische Farbstoffübertragungsdruckschicht nach Anspruch 1, wobei die Fettsäure-Amide mindestens eine der folgenden Substanzen aufweisen: Oleinsäureamid, Stearinsäureamid, Cis-13-Behensäureamid, Laurinsäureamid, Oxystearinsäureamid und n-Oleylpalmitinsäureamid.
- Thermische Farbstoffübertragungsdruckschicht nach Anspruch 1 oder 2, wobei das Wachs mindestens eine der folgenden Substanzen aufweist: Paraffin-Wachs, mikrokristallines Wachs und oxydiertes Wachs.
- Thermische Farbstoffübertragungsdruckschicht nach einem der vorhergehenden Ansprüche, wobei das Wachs und die Fettsäure-Amide in der gefärbten Schicht jeweils zu einem Anteil von 1 bis 10 Gew.-% enthalten sind.
- Thermische Farbstoffübertragungsdruckschicht nach einem der vorhergehenden Ansprüche, wobei die gefärbte Schicht als Bindematerial ein Harz mit einer Glasumwandlungstemperatur von mindestens 65°C oder ein Produkt umfaßt, das aus der Reaktion von Vernetzungsmitteln mit einem Harz mit einer Glasumwandlungstemperatur von mindestens 65°C hervorging.
- Thermische Farbstoffübertragungsdruckschicht nach einem der vorhergehenden Ansprüche, wobei eine adhäsive Schicht mit einem adhäsiven Harz und einem Farbstoff zwischen dem Substrat und der gefärbten Schicht angeordnet ist.
- Thermische Farbstoffübertragungsdruckschicht nach Anspruch 6, wobei in der adhäsiven Schicht und in der gefärbten Schicht derselbe Farbstoff verwendet wird.
- Thermische Farbstoffübertragungsdruckschicht nach Anspruch 6 oder 7, wobei der Prozentsatz des in der adhäsiven Schicht enthaltenen Farbstoffs mindestens die Hälfte des Prozentsatzes des Farbstoffs , der in der gefärbten Schicht enthalten ist, beträgt.
- Thermische Farbstoffübertragungsdruckschicht nach Anspruch 6, 7 oder 8, wobei das in der adhäsiven Schicht enthaltene adhäsive Harz mindestens eines der folgenden aufweist: gesättigtes Polyesterharz, Polyurethanharz und Acrylharz.
- Verwendung einer thermischen Farbstoffübertragungsdruckschicht nach einem der vorhergehenden Ansprüche bei der Aufzeichnung einer Abbildung auf einem Bildempfangs-Flächengebilde.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP304808/87 | 1987-12-02 | ||
JP62304808A JP2829956B2 (ja) | 1987-12-02 | 1987-12-02 | 感熱記録用転写体 |
JP304803/87 | 1987-12-02 | ||
JP62304803A JPH01146792A (ja) | 1987-12-02 | 1987-12-02 | 感熱記録用転写体 |
JP133270/88 | 1988-05-31 | ||
JP63133270A JPH01301372A (ja) | 1988-05-31 | 1988-05-31 | 染料転写体 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0319331A2 EP0319331A2 (de) | 1989-06-07 |
EP0319331A3 EP0319331A3 (en) | 1990-08-16 |
EP0319331B1 true EP0319331B1 (de) | 1994-05-11 |
Family
ID=27316659
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP88311469A Expired - Lifetime EP0319331B1 (de) | 1987-12-02 | 1988-12-02 | Thermische Farbstoffübertragungsdruckschicht |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0319331B1 (de) |
DE (1) | DE3889527T2 (de) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5629129A (en) * | 1994-08-11 | 1997-05-13 | Fuji Photo Film Co., Ltd. | Heat sensitive ink sheet and image forming method |
US5747217A (en) * | 1996-04-03 | 1998-05-05 | Minnesota Mining And Manufacturing Company | Laser-induced mass transfer imaging materials and methods utilizing colorless sublimable compounds |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0227092A2 (de) * | 1985-12-24 | 1987-07-01 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Trennmittel für die thermische Farbstoffübertragung |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6083889A (ja) * | 1983-10-17 | 1985-05-13 | Konishiroku Photo Ind Co Ltd | 感熱転写記録媒体 |
JPS60183196A (ja) * | 1984-02-29 | 1985-09-18 | Fujitsu Ltd | 熱転写記録用インクシ−ト |
WO1986005197A1 (en) * | 1985-03-07 | 1986-09-12 | Ncr Corporation | Thermal transfer ink formulation and medium and method of producing the same |
DE3520308A1 (de) * | 1985-06-07 | 1986-12-11 | Pelikan Ag, 3000 Hannover | Verfahren zur herstellung eines thermofarbbandes fuer den thermotransferdruck und das danach erhaeltliche thermofarbband |
JPS61295089A (ja) * | 1985-06-25 | 1986-12-25 | Canon Inc | 感熱転写材 |
KR920001485B1 (ko) * | 1985-12-18 | 1992-02-15 | 후지쓰 가부시끼가이샤 | 열전사 기록에 반복 사용하는 잉크 시트(ink sheet) |
-
1988
- 1988-12-02 EP EP88311469A patent/EP0319331B1/de not_active Expired - Lifetime
- 1988-12-02 DE DE19883889527 patent/DE3889527T2/de not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0227092A2 (de) * | 1985-12-24 | 1987-07-01 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Trennmittel für die thermische Farbstoffübertragung |
Also Published As
Publication number | Publication date |
---|---|
EP0319331A2 (de) | 1989-06-07 |
EP0319331A3 (en) | 1990-08-16 |
DE3889527D1 (de) | 1994-06-16 |
DE3889527T2 (de) | 1994-12-08 |
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