EP4288293A1 - Matériau d'enregistrement pour impression par sublimation thermique ayant des propriétés de transport améliorées - Google Patents
Matériau d'enregistrement pour impression par sublimation thermique ayant des propriétés de transport amélioréesInfo
- Publication number
- EP4288293A1 EP4288293A1 EP22703928.6A EP22703928A EP4288293A1 EP 4288293 A1 EP4288293 A1 EP 4288293A1 EP 22703928 A EP22703928 A EP 22703928A EP 4288293 A1 EP4288293 A1 EP 4288293A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- recording material
- layer
- dye
- material according
- synthetic resin
- 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.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 84
- 238000007639 printing Methods 0.000 title claims abstract description 31
- 238000000859 sublimation Methods 0.000 title claims abstract description 16
- 230000008022 sublimation Effects 0.000 title claims abstract description 15
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 58
- 239000000057 synthetic resin Substances 0.000 claims abstract description 58
- 239000002985 plastic film Substances 0.000 claims abstract description 34
- 229920006255 plastic film Polymers 0.000 claims abstract description 34
- 230000004888 barrier function Effects 0.000 claims abstract description 24
- 239000010410 layer Substances 0.000 claims description 138
- 239000000203 mixture Substances 0.000 claims description 20
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 15
- 239000000049 pigment Substances 0.000 claims description 15
- -1 aluminum silicates Chemical class 0.000 claims description 12
- 239000012790 adhesive layer Substances 0.000 claims description 11
- 239000011230 binding agent Substances 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 7
- 230000003287 optical effect Effects 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 229920006378 biaxially oriented polypropylene Polymers 0.000 claims description 4
- 239000011127 biaxially oriented polypropylene Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 108010010803 Gelatin Proteins 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 229920000159 gelatin Polymers 0.000 claims description 2
- 239000008273 gelatin Substances 0.000 claims description 2
- 235000019322 gelatine Nutrition 0.000 claims description 2
- 235000011852 gelatine desserts Nutrition 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000000123 paper Substances 0.000 description 47
- 238000000034 method Methods 0.000 description 21
- 239000000975 dye Substances 0.000 description 14
- 230000008569 process Effects 0.000 description 14
- 229920001684 low density polyethylene Polymers 0.000 description 11
- 239000004702 low-density polyethylene Substances 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229920001903 high density polyethylene Polymers 0.000 description 8
- 239000004700 high-density polyethylene Substances 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 6
- 239000012876 carrier material Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000004513 sizing Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000001023 inorganic pigment Substances 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 230000000740 bleeding effect Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000032798 delamination Effects 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011121 hardwood Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000002346 layers by function Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
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- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 239000012792 core layer Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000004584 polyacrylic acid Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NJVOHKFLBKQLIZ-UHFFFAOYSA-N (2-ethenylphenyl) prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1C=C NJVOHKFLBKQLIZ-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 244000166124 Eucalyptus globulus Species 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- WMWXXXSCZVGQAR-UHFFFAOYSA-N dialuminum;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3] WMWXXXSCZVGQAR-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000005026 oriented polypropylene Substances 0.000 description 1
- 239000001254 oxidized starch Substances 0.000 description 1
- 235000013808 oxidized starch Nutrition 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical class OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 125000005624 silicic acid group Chemical class 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000007651 thermal printing Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
- B41M5/40—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
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/398—Processes based on the production of stickiness patterns using powders
-
- 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
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/02—Dye diffusion thermal transfer printing (D2T2)
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/32—Thermal receivers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/36—Backcoats; Back layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
- B41M2205/38—Intermediate layers; Layers between substrate and imaging layer
Definitions
- the invention relates to a recording material for thermal sublimation printing.
- Thermal sublimation printing is used to reproduce a digitally generated image in the form of a printed image, the image quality of which corresponds to that of a silver salt photograph.
- the digital image is selectively processed with regard to the basic colors cyan, magenta, yellow and black and converted into corresponding electrical signals, which are then locally converted into heat using a thermal head in the printer. Due to the local effect of heat, the dye sublimates from the donor layer of an ink ribbon or ink sheet that is in contact with the recording material to be printed and diffuses into the dye-receiving layer of the recording material.
- a recording material for thermal sublimation printing must have a good surface, low thermal conductivity, good heat resistance, good compressibility and good dimensional stability, among other things.
- the recording material for dye-sublimation prints have good shelf life after printing to prevent migration of dyes through the substrate over time and consequent deterioration in image quality.
- the compressibility of the recording material is important to ensure good contact between the printer's thermal head and the recording material.
- the exact positioning of the recording material in relation to the print heads is important, since only one of the four primary colors (cyan, magenta, yellow and black) can be applied at the same time in each printing process. For this reason, the print image must be created by applying dye in four consecutive passes (so-called multi-pass process). Since the same color pixel has to be precisely controlled up to four times at the same print position in order to generate the desired color tone, changing the positioning of the recording material in relation to the print heads during the colorant application leads to a deterioration in image quality. Such a change in positioning (so-called offset) can be caused, for example, by difficulties in transporting the recording material in the printer.
- the transport rollers used in printers specially developed for thermal sublimation printing have a surface roughness with needle-shaped elevations that are intended to ensure a good connection to the recording material.
- the recording materials currently in use due to the properties of the contact surfaces of the recording material and the transport rollers of the printer, friction occurs during transport of the recording material in the printer, so that optimal positioning of the recording material to the print head cannot be guaranteed.
- recording materials for thermal sublimation printing have already been sufficiently described in the prior art. They essentially consist of a carrier material, a dye-receiving layer and optionally other functional layers.
- uncoated or coated papers are used as the carrier material, with synthetic resin-coated, in particular polyolefin-coated papers or papers provided with a multi-layer plastic film being particularly suitable.
- carrier materials are described, for example, in EP 3 028 866 A1.
- the dye-receptive layer mainly contains a resin which has an affinity with the dye from the donor layer of the ink ribbon.
- Plastics with ester compounds such as polyester resins, polyacrylic acid ester resins, polycarbonate resins, polyvinyl acetate resins, styrene acrylate resins, or plastics with amide compounds, such as polyamide resins, or polyvinyl chloride and mixtures of the plastics mentioned are used for this purpose.
- copolymers which contain at least one of the abovementioned plastics as the main component, such as vinyl chloride/vinyl acetate copolymer is also known in the prior art.
- So-called anti-curl layers are used as further functional layers in order to counteract a buckling of the recording material after it has passed through the thermal printer.
- Well suited for this are, for example, plastic foils that are laminated on the back of the recording material.
- laminating the plastic films onto the back of the recording material has the disadvantage that it requires an additional process step, this increases the complexity of the recording material and the resultant surface quality of the recording material allows slip-free and thus offset-free transport in the printer not allowed.
- JP 2015 193251 describes a recording material in which a polyolefin layer has been applied to both sides of the carrier material, with the densities and coating weights of the polyolefin layers applied to both sides of the carrier material differing.
- the application of polyolefins still leads to the transport difficulties in the printer known from the prior art. A displacement-free transport of the recording material in the printer is therefore not guaranteed.
- Thermal sublimation printing comprising a. a base paper with a front and a back b. at least one layer of synthetic resin on at least the reverse side of the base paper c. a dye-receptive layer arranged on the front side of the base paper, d. at least one plastic film which is arranged between the base paper and the dye-receiving layer, and e. optionally a barrier layer which is arranged between the plastic film and the dye-receiving layer, the synthetic resin layer having a modulus of elasticity of at least 0.8 GPa.
- base paper means uncoated or surface-sized paper.
- a base paper can contain sizing agents such as alkylkentene dimers, fatty acids and/or fatty acid salts, epoxidized fatty acid amides, alkenyl or alkyl succinic anhydride, wet strength agents such as polyamine-polyamide-epichlorohydrin, dry strength agents such as anionic, cationic or amphoteric polyamides or cationic starches, optical brighteners, fillers, pigments , dyes, defoamers and other auxiliaries known in the paper industry.
- the base paper can be made on a Fourdrinier or a Yankee paper machine (cylinder paper machine).
- the basis weight of the raw paper can be 50 to 250 g/m 2 , in particular 80 to 180 g/m 2 .
- the base paper can uncompacted or compressed (smoothed) form.
- Raw papers with a density of 0.8 to 1.2 g/cm 3 , in particular with a density of 0.9 to 1.1 g/cm 3 are particularly suitable.
- bleached hardwood kraft pulp LLKP
- bleached softwood kraft pulp NKP
- bleached hardwood sulfite pulp LBSP
- bleached softwood sulfite pulp NBSP
- Pulp fibers obtained from waste paper can also be used.
- the cellulose fibers mentioned can also be used in a mixed form and proportions of other fibers, for example synthetic resin fibers, can be mixed in.
- pulp fibers made from 100% hardwood pulp are preferably used.
- the average fiber length of the unbeaten pulp is preferably 0.5 to 0.85 mm (Kajaani measurement).
- Kaolins calcium carbonate in its natural forms such as limestone, marble or dolomite, precipitated calcium carbonate, calcium sulfate, barium sulfate, titanium dioxide, talc, silica, aluminum oxide and mixtures thereof in the raw paper can be used as fillers.
- the base paper can be surface sized.
- Sizing agents suitable for this purpose are, for example, polyvinyl alcohol or oxidized starch.
- the sizing agent can additionally contain at least one pigment.
- the pigment is preferably selected from the group consisting of metal oxides, silicates, carbonates, sulfides or sulfates and mixtures thereof. Pigments such as kaolins, talc, calcium carbonate and/or barium sulfate have proven particularly useful in practice.
- the recording material according to the invention has at least one synthetic resin layer on at least the reverse side of the raw paper, the synthetic resin layer having a modulus of elasticity of at least 0.8 GPa.
- the determination of the modulus of elasticity can be carried out using the methods known to those skilled in the art.
- the modulus of elasticity is preferably determined using the Lorentzen & Wettre Tensile Tester in accordance with the tensile strength test described in the test section.
- the back of the base paper is understood to mean the side of the base paper facing the transport rollers in the printer.
- the synthetic resin layer has a modulus of elasticity of at least 0.90 GPa, particularly preferably at least 0.95 GPa, very particularly preferably at least 1.0 GPa.
- the synthetic resin layer may preferably contain a thermoplastic polymer.
- biotechnologically produced polymers are used as thermoplastic polymers.
- the thermoplastic polymers used are polymers that have been produced from renewable raw materials.
- polylactic acid (PLA) and native or modified starches and mixtures thereof are used as thermoplastic polymers.
- Preferred thermoplastic polymers are polyolefins, for example low-density polyethylene (LD-PE), high-density polyethylene (HD-PE), polypropylene (PP), 4-methylpentene-1 homo- and copolymers (TPX) and mixtures thereof, and also polyesters, for example polycarbonates .
- the synthetic resin layer contains HD-PE, LD-PE, 4-methylpentene-1 homo- and copolymers (TPX) and mixtures thereof. It has proven to be particularly practical if the synthetic resin layer contains at least 40% by weight HD-PE, in particular 60 to 80% by weight HD-PE.
- the HD-PE used in the synthetic resin layer preferably has a density of more than 0.95 g/cm 3 . It has also proven to be particularly practical if the synthetic resin layer contains up to 25% by weight of LDPE. Preferred the LD-PE used in the synthetic resin layer has a density of less than 0.935 g/cm 3 .
- the synthetic resin layer contains at least 5% by weight, in particular at least 10% by weight TPX, preferably between 5 and 20% by weight TPX, particularly preferably between 5 and 15% by weight TPX on the dry weight of the synthetic resin layer.
- TPX preferably between 5 and 20% by weight TPX, particularly preferably between 5 and 15% by weight TPX on the dry weight of the synthetic resin layer.
- the back synthetic resin layer consists of 0 to 25% by weight TPX, 55 to 85% by weight HD-PE and 5 to 25% by weight LD-PE, based on the dry weight of the synthetic resin layer.
- a recording material according to the invention with a synthetic resin layer designed in this way on the back has particularly good transport properties in the printer, so that offsetting of the printed image during printing can be largely prevented.
- the synthetic resin layer can contain white pigments such as titanium dioxide and other pigments as well as other auxiliaries such as optical brighteners, dyes and dispersants.
- the synthetic resin layer has a pigment content of at least 5% by weight, in particular at least 10% by weight, preferably at least 20% by weight, based on the dry weight of the synthetic resin layer.
- the pigments are preferably selected from calcium carbonate, aluminum oxides, aluminum silicates or mixtures thereof.
- the surface properties of the synthetic resin layer can be further optimized by adding the pigments.
- the synthetic resin layer on the back consists of 5 to 25% by weight of pigment, in particular calcium carbonate, 75 to 85% by weight of HD-PE and 0 to 15% by weight of LD-PE, based on the Dry weight of the synthetic resin layer.
- a synthetic resin layer designed in this way on the back of the recording material according to the invention leads to significantly less friction with the surfaces of the transport rollers of the printer, so that offset of the printed image during printing can be significantly reduced or largely prevented.
- the application weight of the synthetic resin layer can be 5 to 50 g/m 2 , in particular 5 to 30 g/m 2 , preferably 10 to 20 g/m 2 .
- the synthetic resin layer is extruded or applied as a film.
- the synthetic resin layer can be extruded onto the base paper in a single layer or co-extruded in multiple layers. Extrusion coating can take place at machine speeds of up to 600 m/min.
- the recording material according to the invention also comprises a dye-receiving layer which is arranged on the front side of the base paper.
- the front side of the base paper is understood to mean the side of the base paper facing the print head of the printer.
- any dye-receiving layer known from the prior art for thermal sublimation printing is suitable as the dye-receiving layer.
- the dye-receiving layer preferably contains a polymer selected from polyester, polyacrylic acid esters, polycarbonates, styrene acrylates, vinyl homo- and/or vinyl copolymers or mixtures thereof.
- vinyl polymers such as polyvinyl chloride, vinyl chloride/acrylate copolymer, vinyl chloride/vinyl acetate copolymer and/or Vinyl chloride/vinyl acetate/vinylidene chloride and mixtures thereof in the dye-receiving layer.
- Starch, polyethylene glycol (PEG) and polyvinyl alcohol are particularly preferably used as polar binders.
- Polyvinyl alcohols modified with carbonyl or carboxyl groups and mixtures thereof are particularly preferred. The use of these modified polyvinyl alcohols has the advantage that they are very compatible with the optical brighteners customarily used in dye-receiving layers and their use therefore does not impair the print quality.
- the amount of the polar binders in the dye-receiving layer can be 1 to 25% by weight, in particular 5 to 20% by weight, based on the dry weight of the dye-receiving layer.
- optical brighteners particularly preference is given to using stilbenes, ethylene, phenylethylene or thiophene derivatives as optical brighteners.
- the amount of the optical brighteners can be 0.01 to 10% by weight, in particular 0.05 to 5% by weight, based on the dry weight of the dye-receiving layer.
- the dye-receptive layer may further contain an inorganic and/or organic pigment.
- Finely divided inorganic pigments such as silicon dioxide, aluminum oxide, aluminum oxide hydrate, aluminum silicate, calcium carbonate, zinc oxide, tin oxide, antimony oxide, titanium dioxide, indium oxide or a mixed oxide of these oxides and mixtures thereof are particularly suitable.
- the amount of the pigment in the dye-receptive layer may be 10 to 90% by weight, particularly 30 to 70% by weight, based on the dry weight of the dye-receptive layer.
- the dye-receiving layer as a finely divided inorganic pigment silicon dioxide, in particular finely divided silicic acids.
- the dye-receptive layer can optionally also contain other auxiliaries, for example anionic or nonionic surface-active agents, matting agents, dyes, crosslinking agents, lubricants, anti-blocking agents and other customary additives.
- auxiliaries for example anionic or nonionic surface-active agents, matting agents, dyes, crosslinking agents, lubricants, anti-blocking agents and other customary additives.
- the amount of the auxiliaries can be 0.01 to 10% by weight, in particular 0.05 to 5% by weight, based on the dry weight of the dye-receiving layer.
- the coating composition for forming the dye-receiving layer can be applied inline or offline using any of the application units customary in papermaking. After drying, the application weight of the dye-receiving layer can be at most 5 g/m 2 , in particular 0.1 to 3 g/m 2 . According to a particularly preferred embodiment, the application weight after drying of the dye-receiving layer is 0.3 to 1.0 g/m 2 . It has been found that these application weights improve the color densities in the print.
- the synthetic resin layer and/or the dye-receiving layer contain antistatic substances.
- the synthetic resin layer and/or the dye-receiving layer contains/contain antistatic substances, in particular electrically conductive inorganic pigments.
- antistatic substances may be added in addition to the above pigments optionally contained in the synthetic resin layer and/or dye-receptive layer.
- the antistatic substances are preferably selected from semiconductors, betaines or ampholytes. The addition of such antistatic substances to the synthetic resin layer and/or dye-receiving layer has proven to be advantageous in preventing charging of the recording material during storage, transport and in the printer and thus prevent the print quality from being impaired by recording material that has already been loaded.
- the recording material according to the invention comprises at least one plastic film which is arranged between the base paper and the dye-receiving layer.
- the plastic film is preferably a biaxially oriented plastic film.
- the plastic film can be single-layer, but preferably has a multi-layer structure with a porous core layer and at least one non-porous surface layer.
- the porous core layer is used for thermal insulation, while the non-porous surface layer ensures the smoothest possible surface.
- the plastic film is a biaxially oriented polypropylene film. It has proven particularly advantageous if a plastic film with a thickness of 30 to 60 ⁇ m, in particular 35 to 50 ⁇ m, is used.
- the plastic film comprises organic and/or inorganic fillers.
- the recording material according to the invention optionally comprises a barrier layer which is arranged between the plastic film and the dye-receiving layer.
- a barrier layer which is arranged between the plastic film and the dye-receiving layer.
- a barrier layer usually also has an adhesive function in order to ensure good adhesion of the colorant-receiving layer to the plastic film.
- a mixture of gelatin and a water-dispersible polymeric binder is used as the barrier layer.
- the water-dispersible polymeric binder in the barrier layer is preferably a water-dispersible polyester-polyurethane copolymer.
- crosslinkers are used in the barrier layer which improve the intrinsic and intermediate adhesion. These are preferably polyaziridines.
- the coating masses for forming the barrier layer and the dye-receiving layer can be applied to the plastic film separately from one another and using gravure rollers, blades, curtains or all common application methods, i.e. the coating mass produced to form the barrier layer is first applied to the plastic film. In the next step, the coating composition for forming the dye-receiving layer is applied to the dried barrier layer and dried.
- coating compositions described above can also be applied “wet-on-wet”, for example by means of a multi-layer curtain coating unit.
- a disadvantage of the separate application of the barrier layer and the plastic film is that delamination can occur between the individual layers.
- a plastic film is used that already includes a barrier layer. through the Using such a plastic film, delamination between the individual layers can be prevented from occurring. Furthermore, raw material and one process step can advantageously be saved in the production of the recording material.
- the adhesive layer there is an adhesive layer between the base paper and the dye-receiving layer.
- the adhesive layer consists of low-density polyethylene (LD-PE).
- the adhesive layer can be constructed like the synthetic resin layer. This means that the structure of the adhesive layer is identical to that of the synthetic resin layer or it can be composed of the materials described above for the synthetic resin layer in the specified amounts.
- the adhesive layer can be applied to the base paper, for example by extrusion, and can serve as an adhesive layer for the plastic film applied over it.
- the thickness of the adhesive layer is preferably 10 to 30 ⁇ m, in particular 15 to 25 ⁇ m.
- Fig. 2 SEM photograph of the synthetic resin layer on the back of a recording material of the prior art with transport roller needle punctures with offset
- FIG. 1 shows a schematic structure of a preferred embodiment of a recording material according to the invention.
- the recording material comprises a base paper 1, on the front of which a dye-receiving layer 2 is arranged.
- a plastic film 3 is arranged between the base paper 1 and the dye-receiving layer 2 .
- the recording material has a synthetic resin layer 4 on the back of the base paper 1 .
- a barrier layer 5 is arranged on the front of the base paper 1 between the plastic film 3 and the dye-receiving layer 2 .
- an adhesive layer 6 is arranged on the front of the base paper 1 between the plastic film 3 and the base paper 1 .
- Figure 2 shows an SEM photograph of the surface of the synthetic resin layer on a back surface of a prior art recording medium after successive printing operations.
- the back shows punctures from the transport roller needles that show an offset. Due to friction between the recording material and the transport rollers, an optimal positioning of the recording material to the print head could not be guaranteed, so that in successive printing processes there is an offset between the print image that has already been applied and the print image that is applied in the subsequent printing process, and thus the print image quality is impaired.
- This offset can be seen on the surface of the synthetic resin layer on the reverse side of the recording material using the SEM image from the offset feed needle punctures.
- FIG. 3 shows an SEM photograph of the surface of the synthetic resin layer 4 on the reverse side of a recording material according to the invention after successive printing processes.
- Figure 3 shows that the surface of the synthetic resin layer 4 on the back of the recording material according to the invention has no offset of the punctures Has transport roller needles.
- the recording material according to the invention therefore ensures optimal positioning of the recording material in relation to the print head during transport in the printer, so that excellent print image quality is achieved in successive printing processes.
- FIG. 4 shows two printed images of a crosshair for determining the offset.
- the offset is determined using the microscope based on the color shift of cyan, yellow, magenta (see crosshairs on the right) in the crosshairs. The sum of all color shifts gives the offset.
- the offset is a measure of transport properties in the printer. A small offset or no offset (left crosshair) is very desirable.
- a base paper A was made from eucalyptus pulp.
- the cellulose was ground as an approximately 5% aqueous suspension (high-density stock) using a refiner to a degree of beating of 36° SR.
- the concentration of pulp fibers in the thin stock was 1% by weight, based on the mass of the pulp suspension.
- Additives were added to the thin stock such as cationic starch at 0.4% by weight, as a neutral sizing agent alkyl ketene dimer (AKD) at 0.48% by weight, wet strength agent polyamine-polyamide-epichlorohydrin resin (Kymene®) in an amount of 0.36% by weight and a natural CaCOs in an amount of 10% by weight.
- the amounts given relate to the dry pulp mass.
- the thin stock the pH of which was adjusted to about 7.5, was transferred from the headbox to the wire of the paper machine, whereupon sheet formation took place with dewatering of the web in the wire section of the paper machine.
- the paper web was further dewatered to a water content of 60% by weight, based on the web weight. Further drying took place in the drying section of the paper machine with heated drying cylinders.
- a raw paper with a basis weight of 132 g/m 2 and a moisture content of about 7% was produced.
- the side of the base paper opposite the side to be printed was coated in the extruder with a layer of synthetic resin composed of the polymer mixtures listed in Table 1.
- the cooling cylinder was selected in such a way that the resulting rear surface has a roughness of 0.9 ⁇ m, measured as the Rz value according to DIN 4768.
- the surface intended for printing (front side) of the raw paper was, after irradiation with a corona discharge, treated with a three-layer biaxial oriented polypropylene film (Plastic film, H1PHANE BOPP, Hwaseung Industries Co. Ltd) was laminated in the extruder, with a low-density polyethylene (LD-PE) film being extruded between the face of the base paper and the biaxially oriented polypropylene film.
- the thickness of the adhesion-promoting polyethylene film (adhesive layer) was 20 ⁇ m.
- the carrier material obtained was then coated with a barrier layer on the side coated with the plastic film (25 wire doctor blade) and dried at 78°C for three minutes.
- the composition of the respective barrier layer is given in Table 2.
- the applied amounts of the barrier layer were chosen such that a dry application of 1.6 g/m 2 resulted in each case.
- a dye-receiving layer was applied to the barrier layer (15 gauge wire squeegee) and dried (2 minutes, 78° C.).
- the application amount of the coating slip of the dye-receiving layer was chosen so that a dry application of 0.5 g/m 2 resulted.
- the composition of the coating slip for the dye-receptive layer is given in Table 3.
- Table 4 shows the structure of the recording materials obtained according to the examples and comparative examples. To the one thus obtained The offset in the printer was determined for the recording materials, and the dye migration and cloudiness (mottling) were evaluated using the methods described below.
- the nature of the synthetic resin layer on the back of the recording material plays an important role with regard to the offset, which is critical in the printing process.
- Acceptable behavior in the multipass printing process i.e. little or no offset, is only achieved with the recording materials according to the invention, the synthetic resin layer of which has a modulus of elasticity of at least 0.8 GPa.
- the samples are printed with the maximum color densities of yellow, cyan, magenta and black on the Mitsubishi CP-D70DW printer with standard donor ribbon.
- the print format is 10 x 15 cm and the colored areas are 1 x 1 cm.
- Samples and printer CP-D70DW from Mitsubishi are preconditioned for 12 hours at 40°C and 80% relative humidity.
- a 10 x 15 cm full-surface black print is then carried out with the existing climate.
- the mottle evaluation of the patterns takes place in grades from 1 to 5.
- the grade 1 means no mottle (no cloudiness) and grade 5 means strong mottle (strong cloudiness).
- the grade gradation between 1 and 5 is relative to grades 1 and 5.
- the modulus of elasticity is determined according to the tensile strength test using the Lorentzen & Wettre Tensile Tester. For this purpose, samples of the synthetic resin layer are cut to a width of 50 mm and a length of 120 mm. The gauge length is fixed at 100 mm. The measuring speed is 100 mm/min. The thickness and basis weight of the samples are determined and included in the Lorentzen & Wettre Tensile Tester's "E-modulus" test program. The tensile strength test is then carried out on the samples. The modulus of elasticity is determined from the relationship between mechanical stress and strain in the linear area of the stress-strain diagram.
- the offset is determined using a crosshair. First, a print image with different crosshairs is printed. The printed crosshairs are then located on the printed image. The offset is determined on the basis of the color shift from cyan, yellow, magenta (see FIG. 4, right crosshairs) in the crosshairs using a microscope. The sum of all color shifts gives the offset. The offset is a measure of transport properties in the printer. A small offset or no offset (see FIG. 4, left cross hairs) is very desirable.
- Table 2 Composition of the coating slip of the barrier layer in wt.% Commercial product and solids content and pH of the
- Table 3 Composition of the coating slip for the dye-receiving layer in % by weight of commercial product and solids content and pH of the coating slip for the dye-receiving layer
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
- Laminated Bodies (AREA)
Abstract
L'invention concerne un matériau d'enregistrement pour impression par sublimation thermique, comprenant du papier brut (1) ayant un côté avant et un côté arrière, au moins une couche de résine synthétique (4) sur au moins le côté arrière du papier brut (1), une couche de réception de colorant (2) qui est agencée sur le côté avant du papier brut (1), au moins un film en matière plastique (3) qui est agencé entre le papier brut (1) et la couche de réception de colorant (2) et facultativement une couche barrière qui est agencée entre le film plastique (3) et la couche de réception de colorant (2), la couche de résine synthétique (4) ayant un module d'élasticité d'au moins 0,8 GPa.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP21155249.2A EP4039486A1 (fr) | 2021-02-04 | 2021-02-04 | Support d'enregistrement pour l'impression à sublimation thermique ayant des propriétés de transport améliorées |
PCT/EP2022/052693 WO2022167572A1 (fr) | 2021-02-04 | 2022-02-04 | Matériau d'enregistrement pour impression par sublimation thermique ayant des propriétés de transport améliorées |
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EP4288293A1 true EP4288293A1 (fr) | 2023-12-13 |
Family
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Application Number | Title | Priority Date | Filing Date |
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EP21155249.2A Withdrawn EP4039486A1 (fr) | 2021-02-04 | 2021-02-04 | Support d'enregistrement pour l'impression à sublimation thermique ayant des propriétés de transport améliorées |
EP22703928.6A Pending EP4288293A1 (fr) | 2021-02-04 | 2022-02-04 | Matériau d'enregistrement pour impression par sublimation thermique ayant des propriétés de transport améliorées |
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EP21155249.2A Withdrawn EP4039486A1 (fr) | 2021-02-04 | 2021-02-04 | Support d'enregistrement pour l'impression à sublimation thermique ayant des propriétés de transport améliorées |
Country Status (5)
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US (1) | US20240083187A1 (fr) |
EP (2) | EP4039486A1 (fr) |
JP (1) | JP2024505504A (fr) |
CN (1) | CN116847993A (fr) |
WO (1) | WO2022167572A1 (fr) |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US5143904A (en) * | 1989-07-18 | 1992-09-01 | Oji Paper Co., Ltd | Thermal transfer dye image-receiving sheet |
US9889694B2 (en) | 2014-03-27 | 2018-02-13 | Dai Nippon Printing Co., Ltd. | Support for thermal transfer image-receiving sheet, thermal transfer image-receiving sheet, and producing method therefor |
PL3028866T3 (pl) | 2014-12-05 | 2020-07-27 | Schoeller Technocell Gmbh & Co. Kg | Materiał zapisujący dla procesu drukowania termicznego |
US20200307296A1 (en) * | 2018-03-22 | 2020-10-01 | Dai Nippon Printing Co., Ltd. | Thermal transfer image-receiving sheet |
-
2021
- 2021-02-04 EP EP21155249.2A patent/EP4039486A1/fr not_active Withdrawn
-
2022
- 2022-02-04 US US18/275,770 patent/US20240083187A1/en active Pending
- 2022-02-04 WO PCT/EP2022/052693 patent/WO2022167572A1/fr active Application Filing
- 2022-02-04 CN CN202280013309.7A patent/CN116847993A/zh active Pending
- 2022-02-04 JP JP2023545304A patent/JP2024505504A/ja active Pending
- 2022-02-04 EP EP22703928.6A patent/EP4288293A1/fr active Pending
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JP2024505504A (ja) | 2024-02-06 |
US20240083187A1 (en) | 2024-03-14 |
CN116847993A (zh) | 2023-10-03 |
WO2022167572A1 (fr) | 2022-08-11 |
EP4039486A1 (fr) | 2022-08-10 |
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