EP0441396A1 - Thermal transfer recording sheet and ink composition for producing the same - Google Patents
Thermal transfer recording sheet and ink composition for producing the same Download PDFInfo
- Publication number
- EP0441396A1 EP0441396A1 EP91101766A EP91101766A EP0441396A1 EP 0441396 A1 EP0441396 A1 EP 0441396A1 EP 91101766 A EP91101766 A EP 91101766A EP 91101766 A EP91101766 A EP 91101766A EP 0441396 A1 EP0441396 A1 EP 0441396A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- group
- substituted
- resins
- dyestuff
- sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
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- 239000000203 mixture Substances 0.000 title claims abstract description 38
- 239000000975 dye Substances 0.000 claims abstract description 46
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 29
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 28
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 17
- 239000003086 colorant Substances 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 10
- -1 polyethylene terephthalate Polymers 0.000 claims description 60
- 239000011347 resin Substances 0.000 claims description 25
- 229920005989 resin Polymers 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000000123 paper Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 239000002216 antistatic agent Substances 0.000 claims description 3
- 239000002981 blocking agent Substances 0.000 claims description 3
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002301 cellulose acetate Polymers 0.000 claims description 3
- 239000012461 cellulose resin Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 229920001249 ethyl cellulose Polymers 0.000 claims description 3
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 3
- 239000010419 fine particle Substances 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 3
- 229920006287 phenoxy resin Polymers 0.000 claims description 3
- 239000013034 phenoxy resin Substances 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920002223 polystyrene Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 2
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 229920003235 aromatic polyamide Polymers 0.000 claims description 2
- 239000003990 capacitor Substances 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000011086 glassine Substances 0.000 claims description 2
- 229920006015 heat resistant resin Polymers 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 229940035429 isobutyl alcohol Drugs 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- CMMXCVYESRODNH-UHFFFAOYSA-N trichloroepoxyethane Chemical class ClC1OC1(Cl)Cl CMMXCVYESRODNH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 2
- 125000001424 substituent group Chemical group 0.000 claims 2
- 125000002252 acyl group Chemical group 0.000 claims 1
- 125000005336 allyloxy group Chemical group 0.000 claims 1
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims 1
- 125000004104 aryloxy group Chemical group 0.000 claims 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 239000000976 ink Substances 0.000 description 38
- 238000001454 recorded image Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000010410 layer Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- NJKRTPRVMKIKER-UHFFFAOYSA-N 2,5-dimethoxy-n-(2-methylpropyl)aniline Chemical compound COC1=CC=C(OC)C(NCC(C)C)=C1 NJKRTPRVMKIKER-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- 125000006228 2-isobutoxyethyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000004200 2-methoxyethyl group Chemical group [H]C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000006227 2-n-butoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- HDBSFPIZKKRTAI-UHFFFAOYSA-N 3-methoxy-n,n-bis(2-methylpropyl)aniline Chemical compound COC1=CC=CC(N(CC(C)C)CC(C)C)=C1 HDBSFPIZKKRTAI-UHFFFAOYSA-N 0.000 description 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 1
- OWNRRUFOJXFKCU-UHFFFAOYSA-N Bromadiolone Chemical compound C=1C=C(C=2C=CC(Br)=CC=2)C=CC=1C(O)CC(C=1C(OC2=CC=CC=C2C=1O)=O)C1=CC=CC=C1 OWNRRUFOJXFKCU-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 125000005160 aryl oxy alkyl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002425 furfuryl group Chemical group C(C1=CC=CO1)* 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000002245 particle Substances 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
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000010023 transfer printing Methods 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
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
- B41M5/3854—Dyes containing one or more acyclic carbon-to-carbon double bonds, e.g., di- or tri-cyanovinyl, methine
Definitions
- thermosensitive transfer recording sheet (which has the same meaning as "thermal transfer recording sheet") for use in thermosensitive transfer recording, particularly in sublimation-type thermosensitive transfer recording, and to an ink composition for use in producing the thermosensitive transfer recording sheet.
- thermosensitive transfer recording technique is more advantageous than the others because the maintenance and operation of the apparatus are easy and the apparatus and its expendable supplies are inexpensive.
- thermosensitive transfer recording There are two systems in the thermosensitive transfer recording: fusion-type transfer in which a transfer recording sheet composed of a base film and formed thereon a thermally fusible ink layer is heated with a thermal head to fuse the ink and transfer the fused ink to an image-receiving surface, thereby recording an image on the receiving surface; and sublimation-type transfer in which a transfer recording sheet composed of a base film and formed thereon a colorant layer containing a sublimable dyestuff is heated with a thermal head to sublimate and/or heat-diffuse the dyestuff and transfer the dyestuff from the transfer recording sheet to an image-receiving surface, thereby recording an image on the receiving surface.
- the sublimation-type transfer is particularly advantageous to full-color recording over the fusion-type in that gradation recording is easy since the transferred amount of the dyestuff can be controlled by changing the energy fed to the thermal head.
- thermosensitive transfer recording of the sublimation type sublimable dyestuffs used in transfer recording sheets and in ink compositions for producing transfer recording sheets greatly affect the speed of transfer recording and the quality and storage stability of prints. Therefore, the sublimable dyestuffs are highly important and need to satisfy the following requirements:
- magenta dyestuffs having suitability to thermosensitive transfer recording of the sublimation type are disclosed, for example, in JP-A-60- 31563, JP-A-59-78896, and JP-A-63-203393.
- JP-A as used herein means an "unexamined published Japanese patent application”.
- These magenta dyestuffs are tricyanovinyl dyestuffs having the same basic structure as that of the dyestuff employed in the present invention.
- the dyestuffs whose structural formulae are specified in those references have had still insufficient performances, particularly in light resistance.
- An object of the present invention is to provide a thermosensitive transfer recording sheet employing a magenta dyestuff which satisfies all of the above-listed requirements.
- Another object of the present invention is to provide an ink composition for use in manufacturing the thermosensitive transfer recording sheet.
- thermosensitive transfer recording sheet which comprises a substrate having thereon a colorant layer, the colorant layer comprising a binder and a dyestuff represented by the following general formula (I): wherein X and Y independently represent a hydrogen atom, a lower alkyl group, or a lower alkoxyl group, provided that either of X and Y represents a lower alkoxyl group; and R1 and R2 independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an allyl group, or a substituted or unsubstituted phenyl group, provided that in the case where both of X and Y represent a lower alkoxyl group, R1 represents a hydrogen atom.
- X and Y independently represent a hydrogen atom, a lower alkyl group, or a lower alkoxyl group, provided that either of X and Y represents a lower alkoxyl group
- R1 and R2 independently represent
- thermosensitive transfer recording sheet which ink composition comprises the tricyanovinyl dyestuff represented by general formula (I), a binder resin, and a medium.
- ink composition comprises the tricyanovinyl dyestuff represented by general formula (I), a binder resin, and a medium.
- the dyestuff employed in the present invention is represented by general formula (I) given above, and includes dyestuffs represented by general formula (II) given below and dyestuffs represented by general formula (III) given next.
- R3 and R4 independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, allyl group, or a substituted or unsubstituted phenyl group
- X1 and Y1 independently represent a hydrogen atom, a lower alkyl group, or a lower alkoxyl group, provided that either of X1 and Y1 represents a lower alkoxyl group and the remaining one represents another group.
- R5 represents a substituted or unsubstituted alkyl group, a cycloalkyl group, allyl group, or a substituted or unsubstituted phenyl group
- X2 and Y2 independently represent a substituted or unsubstitute
- substituted or unsubstituted alkyl group, cycloalkyl group, allyl group, or substituted or unsubstituted phenyl group represented by R1, R2, R3, R4, and R5 in general formulae (I), (II), and (III) given above are as follows.
- Examples of the unsubstituted alkyl group include straight-chain or branched alkyl groups having 1 to 8 carbon atoms.
- Examples of the substituted alkyl group include hydroxy-substituted alkyl groups such as 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, and 2-hydroxypropyl group; carboxy-substituted alkyl groups such as carboxymethyl group, 2-carboxyethyl group, and 3-carboxypropyl group; cyano-substituted alkyl groups such as 2-cyanoethyl group and cyanomethyl group; amino-substituted alkyl groups such as 2-aminoethyl group; halogen-substituted alkyl groups such as 2-chloroethyl group, 3-chloropropyl group, 2-chloropropyl group, and 2,2,2-trifluoroethyl group; alkyl groups substituted with phenyl group which may further
- Examples of the cycloalkyl group include the cyclopentyl and cyclohexyl group.
- substituted phenyl group examples include phenyl group substituted with a straight-chain or branched alkyl group having 1 to 8 carbon atoms; phenyl group substituted with a straight-chain or branched alkoxyl group having 1 to 4 carbon atoms; phenyl group substituted with a halogen atom such as fluorine atom, chlorine atom, or bromine atom; and phenyl group substituted with nitro group, cyano group, trifluoromethyl group.
- R1, R2, R3, R4, and R5 include hydrogen atom, straight-chain or branched alkyl groups having 1 to 8 carbon atoms, and alkoxyalkyl groups having 3 to 8 carbon atoms, provided that R5 preferably represents groups other than a hydrogen atom.
- dyestuffs represented by the above-described general formula (I) those represented by the general formula (I) in which either of R1 and R2 is hydrogen atom are particularly preferred from the standpoints of the tints of dyestuffs and the light resistance of prints obtained therefrom, etc.
- Examples of the lower alkyl group represented by X, Y, X1, and Y1 include straight-chain or branched alkyl groups having 1 to 4 carbon atoms.
- Examples of the lower alkoxyl group represented by X, Y, X1, Y1, X2, and Y2 include straight-chain and branched alkoxyl groups, having 1 to 4 carbon atoms.
- either of X and Y and either of X1 and Y1 represent a lower alkoxyl group, and the remaining ones preferably represent a lower alkyl group or a lower alkoxyl group. More preferably, both X and Y and both X1 and Y1 are a lower alkoxyl group.
- the most preferred of the dyestuffs of general formula (I) which can be used in the present invention are dyestuffs represented by general formula (III) given hereinabove, from the standpoints of the tints of dyestuffs, and the light resistance of prints obtained therefrom.
- the tricyanovinyl dyestuff of general formula (I) to be employed in the present invention can be produced according to conventionally known methods. For example, it may be obtained by reacting tetracyanoethylene with a compound represented by the following general formula (IV): (wherein R1, R2, X and Y have the same meanings as in general formula (I) given hereinabove) in an organic solvent.
- thermosensitive transfer recording sheet of the present invention methods for forming the colorant layer containing the dyestuff of general formula (I) are not particularly limited.
- the dyestuff is dissolved or finely dispersed, along with a binder, in a medium to prepare an ink, which is then applied on a substrate and dried, thereby forming a colorant layer on the substrate.
- the binder for use in the ink preparation should have good heat resistance for the purpose of preventing the heat fusion-adhesion of the binder onto an image-receiving surface at the time of transfer recording.
- Especially preferred binders are those having softening points and/or heat deformation temperatures of 100°C or more.
- binder examples include water soluble resins such as cellulose resins, acrylic acid-based resins, starches, polyvinyl alcohols, and polyethylene oxides, organic solvent-soluble resins such as acrylic resins, methacrylic resins, polystyrenes, polycarbonates, polysulfones, AS resins, polyethersulfones, epoxy resins, polyvinyl acetals, phenoxy resins, polyvinyl butyrals, polyesters, ethyl cellulose, and acetyl celluloses.
- water soluble resins such as cellulose resins, acrylic acid-based resins, starches, polyvinyl alcohols, and polyethylene oxides
- organic solvent-soluble resins such as acrylic resins, methacrylic resins, polystyrenes, polycarbonates, polysulfones, AS resins, polyethersulfones, epoxy resins, polyvinyl acetals, phenoxy resins, polyvinyl butyrals, polyesters
- a binder soluble or uniformly dispersible into the medium may be suitably selected from the above resins.
- the amount of such a binder resin used is generally in the range of from 1 to 40% by weight, preferably from 5 to 30% by weight, based on the total amount of the ink composition.
- examples of the medium for use in ink preparation are organic solvents which include alcohols such as methyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and isobutyl alcohol, Cellosolves such as methyl Cellosolve, ethyl Cellosolve and butyl Cellosolve, aromatics such as toluene, xylene, and chlorobenzene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, chlorine-containing solvents such as methylene chloride, chloroform, and trichloroethylene, ethers such as tetrahydrofuran and dioxane, N,N-dimethylformamide, and N-methylpyrrolidone. These may be used alone or as a mixture of two or more thereof.
- alcohols such
- organic or inorganic non-sublimable fine particles may be incorporated into the ink if required and necessary.
- a dispersant an anti-static agent, an anti-blocking agent, an anti-foaming agent, an antioxidant, a viscosity modifier and a release agent may be incorporated into the ink if required and necessary.
- thermosensitive transfer recording sheet examples include a sheet of paper such as capacitor paper and glassine paper, and a film of heat-resistant plastics such as polyesters, polycarbonates, polyamides, polyimides and polyaramides.
- the thickness of such a substrate is generally in the range of from 1 to 50 ⁇ m.
- polyethylene terephthalate film is particularly advantageous because of its high mechanical strength, good solvent resistance and low cost. In some cases, however, even the polyethylene terephthalate film is not always satisfactory in heat resistance, resulting in insufficient running of the thermal head. Therefore, a heat-resistant resin layer containing a surface-active agent or lubricating heat-resistant particles may be provided on the side opposite to the colorant layer, thus providing improved thermal head-running properties.
- Coating of the ink on the substrate can be accomplished by use of a reverse-roll coater, a gravure coater, a rod coater, or an air-doctor coater .
- the coating may be performed so as to give an ink coating layer thickness in the range of from 0.1 to 5 ⁇ m on a dry basis. (Reference may be made to Yuji Harasaki, Coating Techniques, published in 1979 by Maki Shoten, Japan.)
- the ink composition for use in producing the thermosensitive transfer recording sheet which ink composition is provided according to another aspect of the present invention, comprises a tricyanovinyl dyestuff represented by the above-described general formula (I), a binder resin, and a medium that may be an organic solvent and/or water.
- the tricyanovinyl dyestuff is as described in detail hereinabove.
- the binder to be used is suitably selected from the above-mentioned resins which are soluble in water or organic solvents, according to the medium to be used.
- any of the above-mentioned solvents may be used.
- non-sublimable fine particles and additives such as a dispersant, anti-static agent, anti-blocking agent, anti-foaming agent, antioxidant, viscosity modifier, and release agent may be used as mentioned hereinabove.
- the amount of the dyestuff of general formula (I) contained in the ink composition of the present invention is generally from 1 to 30% by weight, preferably from 3 to 20% by weight, based on the total amount of the ink composition.
- the ink composition of the present invention may be prepared as follows. In one method, a liquid mixture composed of the dyestuff, a medium, and a resin is placed in a proper vessel equipped with a stirrer and the dyestuff is dissolved in the medium, with heating if required and with addition of additives if necessary, thereby to prepare an ink composition.
- the liquid mixture may be treated with a paint conditioner, a ball mill or a sand grinding mill to uniformly disperse the dyestuff into the medium, with addition of additives if necessary, thereby to prepare an ink composition.
- the tricyanovinyl dyestuff of general formula (I) which is employed in the thermosensitive transfer recording sheet of the present invention possesses a vivid magenta color, it is suited for use in combining it with suitable cyan color dyestuffs and suitable yellow color dyestuffs to attain full-color recording with good color reproduction. Further, because the dyestuff of general formula (I) readily sublimates and/or heat-diffuses and has a high molecular absorption coefficient, recorded images having high color densities can be obtained at a high speed without a heavy load on the thermal head.
- the dyestuff also has good stability to heat, light, moisture and chemicals, and, hence, it never undergoes thermal decomposition during transfer recording and the permanence properties of the resulting recorded images are also good, particularly in light resistance.
- the dyestuff of general formula (I) has good solubility in organic solvents and good dispersibility into water, it is easy to prepare an ink composition in which the dyestuff has been uniformly dissolved or dispersed at a high concentration, and by use of such an ink composition, a thermosensitive transfer recording sheet having a colorant coating layer in which the dyestuff is distributed uniformly at a high concentration can be obtained. Therefore, by use of such a thermosensitive transfer recording sheet, printed images having good homogeneity and color density can be obtained.
- thermosensitive transfer recording sheet of the present invention infrared rays or laser light as well as a thermal head may be utilized as a heating means.
- thermosensitive sheet It is also possible to coat the ink composition of the present invention on a film that is heated by application of electric current and to use the resulting sheet as an electrically-heated thermosensitive sheet.
- a mixture having the above composition was treated with a paint conditioner for 10 minutes, thereby preparing an ink.
- the above-obtained ink was coated with a wire bar on a polyethylene terephthalate film (6 ⁇ m thick) whose back side had undergone treatment for imparting heat resistance and lubricating properties.
- the coating was then dried (coating layer dry thickness, about 1 ⁇ m) to obtain a transfer recording sheet.
- the above treatment for imparting heat resistance and lubricating properties to the polyethylene terephthalate film was conducted by coating the film with a composition consisting of 8 parts of a polycarbonate resin having the repeating unit of the formula 1 part of a phosphoric ester-type surfactant (trade name, "Plysurf A-208B"; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Japan), and 91 parts of toluene, and drying the coating (coating layer dry thickness, about 0.5 ⁇ m).
- a composition consisting of 10 parts of a saturated polyester resin (trade name, "TP-220”; manufactured by Nihon Gosei Co., Ltd., Japan), 0.5 part of an amino-modified silicone (trade name, "KF 393”; manufactured by Shin-Etsu Chemical Co., Ltd., Japan), 15 parts of methyl ethyl ketone, and 15 parts of xylene was coated on a synthetic paper (trade name, "Yupo FPG 150”; manufactured by Oji-Yuka Co., Ltd., Japan) with a wire bar, and then dried (coating layer dry thickness, about 5 ⁇ m).
- the coated synthetic paper was further heat-treated in an oven at 100°C for 30 minutes to prepare an image-receiving sheet.
- the transfer recording sheet prepared in (b) above was superimposed on the image-receiving sheet in such a manner that the ink coating side of the transfer recording sheet was in contact with the receiving sheet, and recording was conducted by use of a thermal head under the conditions shown below. As a result, a recorded image which was of a vivid magenta color and had a uniform color density as shown in Table 3 could be obtained.
- the light resistance of the recorded image obtained was examined by means of a carbon arc fade meter (manufactured by Suga Testing Machine Co., Ltd., Japan) at a black panel temperature of 63 ⁇ 2°C.
- the degree of discoloration through a 40-hour irradiation in the light resistance test was shown in Table 3 in terms of ⁇ E * value. Further, the transfer recording sheet and the print obtained were found to be stable to heat and moisture and show good storage stability in the dark.
- the dyestuff used in this example had been synthesized by reacting 3-methoxy-N,N-di-isobutylaniline with tetracyanoethylene in N,N-dimethylformamide. Its maximum absorption wavelength in acetone was as shown in Table 3 and its melting point was 116-117°C.
- Inks and transfer recording sheets were prepared and transfer recording was conducted in the same manner as in Example 1 except that in place of the dyestuff used in Example 1, the dyestuffs shown in Table 3 were used. As a result, recorded images which were of a vivid magenta color and respectively had color densities shown in Table 3 could be obtained, and the light resistance of each recorded image was good as shown in Table 3.
- the dyestuff used in this example had been synthesized by reacting 2,5-dimethoxy-N-isobutylaniline with tetracyanoethylene in N,N-dimethylformamide. Its maximum absorption wavelength in acetone was as shown in Table 3 and its melting point was 181-182°C.
- Inks and transfer recording sheets were prepared and transfer recording was conducted in the same manner as in Example 1 except that in place of the dyestuff used in Example 1, the dyestuffs shown in Table 3 were used. As a result, recorded images which were of a vivid magenta color and respectively had color densities shown in Table 3 could be obtained, and the light resistance of each recorded image was good as shown in Table 3.
- a transfer recording sheet was prepared and transfer recording was conducted in the same manner as in Example 1 except that an ink prepared according to the following formulation was used in place of the ink used in Example 1. As a result, a recorded image which was of a vivid magenta color and had a uniform color density of 2.15 could be obtained. Further, the recorded image was subjected to a light resistance test and the transfer recording sheet and recorded image were subjected to a storage stability test in the dark. As a result, good results were obtained in each test.
- a transfer recording sheet was prepared and transfer recording was conducted in the same manner as in Example 21 except that in place of the dyestuff used in Example 21, the same dyestuff as that used in Example 11, i.e., dyestuff No. 4 in Table 2, was used. As a result, a recorded image which was of a vivid magenta color and had a uniform color density of 2.15 could be obtained. Further, the recorded image was subjected to a light resistance test and the transfer recording sheet and recorded image were subjected to a storage stability test in the dark. As a result, good results were obtained in each test.
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
A thermosensitive transfer recording sheet comprising a substrate having thereon a colorant layer, the colorant layer comprising a binder and a dyestuff represented by the following general formula (I):
wherein X and Y independently represent a hydrogen atom, a lower alkyl group, or a lower alkoxyl group, provided that either of X and Y represents a lower alkoxyl group; and R¹ and R² independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an allyl group, or a substituted or unsubstituted phenyl group, provided that in the case where both of X and Y represent a lower alkoxyl group, R¹ represents a hydrogen atom. A thermosensitive transfer recording ink composition for use in forming the colorant layer on a substrate is also disclosed.
wherein X and Y independently represent a hydrogen atom, a lower alkyl group, or a lower alkoxyl group, provided that either of X and Y represents a lower alkoxyl group; and R¹ and R² independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an allyl group, or a substituted or unsubstituted phenyl group, provided that in the case where both of X and Y represent a lower alkoxyl group, R¹ represents a hydrogen atom. A thermosensitive transfer recording ink composition for use in forming the colorant layer on a substrate is also disclosed.
Description
- The present invention relates to a thermosensitive transfer recording sheet (which has the same meaning as "thermal transfer recording sheet") for use in thermosensitive transfer recording, particularly in sublimation-type thermosensitive transfer recording, and to an ink composition for use in producing the thermosensitive transfer recording sheet.
- In the field of facsimile, copying machines, or printers, studies are conventionally being made of color recording techniques based on electrophotographic printing, ink-jet printing and thermosensitive transfer printing.
- Among these, the thermosensitive transfer recording technique is more advantageous than the others because the maintenance and operation of the apparatus are easy and the apparatus and its expendable supplies are inexpensive.
- There are two systems in the thermosensitive transfer recording: fusion-type transfer in which a transfer recording sheet composed of a base film and formed thereon a thermally fusible ink layer is heated with a thermal head to fuse the ink and transfer the fused ink to an image-receiving surface, thereby recording an image on the receiving surface; and sublimation-type transfer in which a transfer recording sheet composed of a base film and formed thereon a colorant layer containing a sublimable dyestuff is heated with a thermal head to sublimate and/or heat-diffuse the dyestuff and transfer the dyestuff from the transfer recording sheet to an image-receiving surface, thereby recording an image on the receiving surface. The sublimation-type transfer is particularly advantageous to full-color recording over the fusion-type in that gradation recording is easy since the transferred amount of the dyestuff can be controlled by changing the energy fed to the thermal head.
- In the thermosensitive transfer recording of the sublimation type, sublimable dyestuffs used in transfer recording sheets and in ink compositions for producing transfer recording sheets greatly affect the speed of transfer recording and the quality and storage stability of prints. Therefore, the sublimable dyestuffs are highly important and need to satisfy the following requirements:
- (1) the dyestuffs should readily sublimate and/or heat-diffuse under operation conditions for the thermorecording head;
- (2) they should not undergo thermal decomposition under operation conditions for the thermorecording head;
- (3) they should possess tints favorable for color reproduction;
- (4) they should have high molecular absorption coefficients;
- (5) they should be stable to heat, light, moisture and chemicals;
- (6) they should be able to be easily synthesized;
- (7) they should have good suitability for use in preparing inks; and
- (8) they should have no health and safety problems.
- However, a dyestuff which meets all the above requirements has not been found so far. Magenta dyestuffs, in particular, have various defects and satisfactory one has not yet been developed.
- Conventionally known magenta dyestuffs having suitability to thermosensitive transfer recording of the sublimation type are disclosed, for example, in JP-A-60- 31563, JP-A-59-78896, and JP-A-63-203393. (The term "JP-A" as used herein means an "unexamined published Japanese patent application".) These magenta dyestuffs are tricyanovinyl dyestuffs having the same basic structure as that of the dyestuff employed in the present invention. However, even the dyestuffs whose structural formulae are specified in those references have had still insufficient performances, particularly in light resistance.
- An object of the present invention is to provide a thermosensitive transfer recording sheet employing a magenta dyestuff which satisfies all of the above-listed requirements.
- Another object of the present invention is to provide an ink composition for use in manufacturing the thermosensitive transfer recording sheet.
- In one aspect of the present invention, a thermosensitive transfer recording sheet is provided which comprises a substrate having thereon a colorant layer, the colorant layer comprising a binder and a dyestuff represented by the following general formula (I):
wherein X and Y independently represent a hydrogen atom, a lower alkyl group, or a lower alkoxyl group, provided that either of X and Y represents a lower alkoxyl group; and R¹ and R² independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an allyl group, or a substituted or unsubstituted phenyl group, provided that in the case where both of X and Y represent a lower alkoxyl group, R¹ represents a hydrogen atom. - In another aspect of the present invention, an ink composition for use in manufacturing the above thermosensitive transfer recording sheet is provided which ink composition comprises the tricyanovinyl dyestuff represented by general formula (I), a binder resin, and a medium.
- The dyestuff employed in the present invention is represented by general formula (I) given above, and includes dyestuffs represented by general formula (II) given below and dyestuffs represented by general formula (III) given next.
(In general formula (II), R³ and R⁴ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, allyl group, or a substituted or unsubstituted phenyl group; and X¹ and Y¹ independently represent a hydrogen atom, a lower alkyl group, or a lower alkoxyl group, provided that either of X¹ and Y¹ represents a lower alkoxyl group and the remaining one represents another group.) (In general formula (III), R⁵ represents a substituted or unsubstituted alkyl group, a cycloalkyl group, allyl group, or a substituted or unsubstituted phenyl group, and X² and Y² independently represent a lower alkoxyl group.) - Specific examples of the substituted or unsubstituted alkyl group, cycloalkyl group, allyl group, or substituted or unsubstituted phenyl group represented by R¹, R², R³, R⁴, and R⁵ in general formulae (I), (II), and (III) given above are as follows.
- Examples of the unsubstituted alkyl group include straight-chain or branched alkyl groups having 1 to 8 carbon atoms. Examples of the substituted alkyl group include hydroxy-substituted alkyl groups such as 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, and 2-hydroxypropyl group; carboxy-substituted alkyl groups such as carboxymethyl group, 2-carboxyethyl group, and 3-carboxypropyl group; cyano-substituted alkyl groups such as 2-cyanoethyl group and cyanomethyl group; amino-substituted alkyl groups such as 2-aminoethyl group; halogen-substituted alkyl groups such as 2-chloroethyl group, 3-chloropropyl group, 2-chloropropyl group, and 2,2,2-trifluoroethyl group; alkyl groups substituted with phenyl group which may further be substituted, such as benzyl group, p-chlorobenzyl group, and 2-phenylethyl group; alkoxy-substituted alkyl groups such as 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxyethyl group, 2-isobutoxyethyl group, 2-(2-ethylhexyloxy)ethyl group, 3-methoxypropyl group, 4-methoxybutyl group, and 2-methoxypropyl group; alkoxyalkoxy-substituted alkyl groups such as 2-(2-methoxyethoxy)ethyl group, 2-(2-ethoxyethoxy)ethyl group, 2-(2-n-propoxyethoxy)ethyl group, 2-(2-isopropoxyethoxy)ethyl group, 2-(2-n-butoxyethoxy)ethyl group, 2-(2-isobutoxyethoxy)ethyl group, and 2-(2-(2-ethylhexyloxy)ethoxy)ethyl group; allyloxyethyl group; aryloxyalkyl groups such as 2-phenoxyethyl group; aralkyloxyalkyl groups such as 2-benzyloxyethyl group; acyloxy-substituted alkyl groups such as 2-acetyloxyethyl group, 2-propionyloxyethyl group, 2-n-butyryloxyethyl group, 2-isobutyryloxyethyl group, and 2-trifluoroacetyloxyethyl group; alkyl groups substituted with a substituted or unsubstituted alkoxycarbonyl group, such as methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, isopropoxycarbonylmethyl group, n-butoxycarbonylmethyl group, isobutoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyl group, benzyloxycarbonylmethyl group, furfuryloxycarbonylmethyl group, tetrahydrofurfuryloxycarbonylmethyl group, 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2-n-propoxycarbonylethyl group, 2-isopropoxycarbonylethyl group, 2-n-butoxycarbonylethyl group, 2-isobutoxycarbonylethyl group, 2-(2-ethylhexyloxycarbonyl)ethyl group, 2-benzyloxycarbonylethyl group, and 2-furfurylcarbonylethyl group; alkyl groups substituted with a substituted or unsubstituted alkoxycarbonyloxy group, such as 2-methoxycarbonyloxyethyl group, 2-ethoxycarbonyloxyethyl group, 2-n-propoxycarbonyloxyethyl group, 2-isopropoxycarbonyloxyethyl group, 2-n-butoxycarbonyloxyethyl group, 2-isobutoxycarbonyloxyethyl group, 2-(2-ethylhexyloxycarbonyloxy)ethyl group, 2-benzyloxycarbonyloxyethyl group, and 2-furfuryloxycarbonyloxyethyl group; and heterocyclic ring-substituted alkyl groups such as furfuryl group and tetrahydrofurfuryl group.
- Examples of the cycloalkyl group include the cyclopentyl and cyclohexyl group.
- Examples of the substituted phenyl group include phenyl group substituted with a straight-chain or branched alkyl group having 1 to 8 carbon atoms; phenyl group substituted with a straight-chain or branched alkoxyl group having 1 to 4 carbon atoms; phenyl group substituted with a halogen atom such as fluorine atom, chlorine atom, or bromine atom; and phenyl group substituted with nitro group, cyano group, trifluoromethyl group.
- Particularly preferred examples of the groups of R¹, R², R³, R⁴, and R⁵ include hydrogen atom, straight-chain or branched alkyl groups having 1 to 8 carbon atoms, and alkoxyalkyl groups having 3 to 8 carbon atoms, provided that R⁵ preferably represents groups other than a hydrogen atom.
- Among the dyestuffs represented by the above-described general formula (I), those represented by the general formula (I) in which either of R¹ and R² is hydrogen atom are particularly preferred from the standpoints of the tints of dyestuffs and the light resistance of prints obtained therefrom, etc.
- Examples of the lower alkyl group represented by X, Y, X¹, and Y¹ include straight-chain or branched alkyl groups having 1 to 4 carbon atoms. Examples of the lower alkoxyl group represented by X, Y, X¹, Y¹, X², and Y² include straight-chain and branched alkoxyl groups, having 1 to 4 carbon atoms.
- In the above general formulae (I) and (II), either of X and Y and either of X¹ and Y¹ represent a lower alkoxyl group, and the remaining ones preferably represent a lower alkyl group or a lower alkoxyl group. More preferably, both X and Y and both X¹ and Y¹ are a lower alkoxyl group.
- Therefore, the most preferred of the dyestuffs of general formula (I) which can be used in the present invention are dyestuffs represented by general formula (III) given hereinabove, from the standpoints of the tints of dyestuffs, and the light resistance of prints obtained therefrom.
-
- The tricyanovinyl dyestuff of general formula (I) to be employed in the present invention can be produced according to conventionally known methods. For example, it may be obtained by reacting tetracyanoethylene with a compound represented by the following general formula (IV):
(wherein R¹, R², X and Y have the same meanings as in general formula (I) given hereinabove) in an organic solvent. - In manufacturing the thermosensitive transfer recording sheet of the present invention, methods for forming the colorant layer containing the dyestuff of general formula (I) are not particularly limited. Generally, the dyestuff is dissolved or finely dispersed, along with a binder, in a medium to prepare an ink, which is then applied on a substrate and dried, thereby forming a colorant layer on the substrate.
- The binder for use in the ink preparation should have good heat resistance for the purpose of preventing the heat fusion-adhesion of the binder onto an image-receiving surface at the time of transfer recording. Especially preferred binders are those having softening points and/or heat deformation temperatures of 100°C or more.
- Examples of the binder include water soluble resins such as cellulose resins, acrylic acid-based resins, starches, polyvinyl alcohols, and polyethylene oxides, organic solvent-soluble resins such as acrylic resins, methacrylic resins, polystyrenes, polycarbonates, polysulfones, AS resins, polyethersulfones, epoxy resins, polyvinyl acetals, phenoxy resins, polyvinyl butyrals, polyesters, ethyl cellulose, and acetyl celluloses.
- According to the medium to be used for the ink preparation, a binder soluble or uniformly dispersible into the medium may be suitably selected from the above resins.
- The amount of such a binder resin used is generally in the range of from 1 to 40% by weight, preferably from 5 to 30% by weight, based on the total amount of the ink composition.
- Besides water, examples of the medium for use in ink preparation are organic solvents which include alcohols such as methyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and isobutyl alcohol, Cellosolves such as methyl Cellosolve, ethyl Cellosolve and butyl Cellosolve, aromatics such as toluene, xylene, and chlorobenzene, esters such as ethyl acetate and butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, chlorine-containing solvents such as methylene chloride, chloroform, and trichloroethylene, ethers such as tetrahydrofuran and dioxane, N,N-dimethylformamide, and N-methylpyrrolidone. These may be used alone or as a mixture of two or more thereof.
- In addition to the ingredients described above, organic or inorganic non-sublimable fine particles, a dispersant, an anti-static agent, an anti-blocking agent, an anti-foaming agent, an antioxidant, a viscosity modifier and a release agent may be incorporated into the ink if required and necessary.
- Preferred examples of the substrate on which the ink is to be applied for preparing the thermosensitive transfer recording sheet include a sheet of paper such as capacitor paper and glassine paper, and a film of heat-resistant plastics such as polyesters, polycarbonates, polyamides, polyimides and polyaramides. The thickness of such a substrate is generally in the range of from 1 to 50 µm.
- Among the above substrates, polyethylene terephthalate film is particularly advantageous because of its high mechanical strength, good solvent resistance and low cost. In some cases, however, even the polyethylene terephthalate film is not always satisfactory in heat resistance, resulting in insufficient running of the thermal head. Therefore, a heat-resistant resin layer containing a surface-active agent or lubricating heat-resistant particles may be provided on the side opposite to the colorant layer, thus providing improved thermal head-running properties.
- Coating of the ink on the substrate can be accomplished by use of a reverse-roll coater, a gravure coater, a rod coater, or an air-doctor coater . The coating may be performed so as to give an ink coating layer thickness in the range of from 0.1 to 5 µm on a dry basis. (Reference may be made to Yuji Harasaki, Coating Techniques, published in 1979 by Maki Shoten, Japan.)
- On the other hand, the ink composition for use in producing the thermosensitive transfer recording sheet, which ink composition is provided according to another aspect of the present invention, comprises a tricyanovinyl dyestuff represented by the above-described general formula (I), a binder resin, and a medium that may be an organic solvent and/or water.
- The tricyanovinyl dyestuff is as described in detail hereinabove.
- The binder to be used is suitably selected from the above-mentioned resins which are soluble in water or organic solvents, according to the medium to be used.
- Of the above-mentioned resins, those having heat deformation temperatures and/or softening points of 100°C or more are particularly preferred. As the organic solvent, any of the above-mentioned solvents may be used. In addition to these, non-sublimable fine particles and additives such as a dispersant, anti-static agent, anti-blocking agent, anti-foaming agent, antioxidant, viscosity modifier, and release agent may be used as mentioned hereinabove.
- The amount of the dyestuff of general formula (I) contained in the ink composition of the present invention is generally from 1 to 30% by weight, preferably from 3 to 20% by weight, based on the total amount of the ink composition.
- The ink composition of the present invention may be prepared as follows. In one method, a liquid mixture composed of the dyestuff, a medium, and a resin is placed in a proper vessel equipped with a stirrer and the dyestuff is dissolved in the medium, with heating if required and with addition of additives if necessary, thereby to prepare an ink composition. Alternatively, the liquid mixture may be treated with a paint conditioner, a ball mill or a sand grinding mill to uniformly disperse the dyestuff into the medium, with addition of additives if necessary, thereby to prepare an ink composition.
- Because the tricyanovinyl dyestuff of general formula (I) which is employed in the thermosensitive transfer recording sheet of the present invention possesses a vivid magenta color, it is suited for use in combining it with suitable cyan color dyestuffs and suitable yellow color dyestuffs to attain full-color recording with good color reproduction. Further, because the dyestuff of general formula (I) readily sublimates and/or heat-diffuses and has a high molecular absorption coefficient, recorded images having high color densities can be obtained at a high speed without a heavy load on the thermal head. The dyestuff also has good stability to heat, light, moisture and chemicals, and, hence, it never undergoes thermal decomposition during transfer recording and the permanence properties of the resulting recorded images are also good, particularly in light resistance. In addition, because the dyestuff of general formula (I) has good solubility in organic solvents and good dispersibility into water, it is easy to prepare an ink composition in which the dyestuff has been uniformly dissolved or dispersed at a high concentration, and by use of such an ink composition, a thermosensitive transfer recording sheet having a colorant coating layer in which the dyestuff is distributed uniformly at a high concentration can be obtained. Therefore, by use of such a thermosensitive transfer recording sheet, printed images having good homogeneity and color density can be obtained.
- In practicing transfer recording using the thermosensitive transfer recording sheet of the present invention, infrared rays or laser light as well as a thermal head may be utilized as a heating means.
- It is also possible to coat the ink composition of the present invention on a film that is heated by application of electric current and to use the resulting sheet as an electrically-heated thermosensitive sheet.
- The present invention will be explained below in more detail by reference to the following examples, which should not be construed to be limiting the scope of the invention. In these examples, all parts are by weight.
-
- A mixture having the above composition was treated with a paint conditioner for 10 minutes, thereby preparing an ink.
- The above-obtained ink was coated with a wire bar on a polyethylene terephthalate film (6 µm thick) whose back side had undergone treatment for imparting heat resistance and lubricating properties. The coating was then dried (coating layer dry thickness, about 1 µm) to obtain a transfer recording sheet.
- The above treatment for imparting heat resistance and lubricating properties to the polyethylene terephthalate film was conducted by coating the film with a composition consisting of 8 parts of a polycarbonate resin having the repeating unit of the formula
1 part of a phosphoric ester-type surfactant (trade name, "Plysurf A-208B"; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., Japan), and 91 parts of toluene, and drying the coating (coating layer dry thickness, about 0.5 µm). - A composition consisting of 10 parts of a saturated polyester resin (trade name, "TP-220"; manufactured by Nihon Gosei Co., Ltd., Japan), 0.5 part of an amino-modified silicone (trade name, "KF 393"; manufactured by Shin-Etsu Chemical Co., Ltd., Japan), 15 parts of methyl ethyl ketone, and 15 parts of xylene was coated on a synthetic paper (trade name, "Yupo FPG 150"; manufactured by Oji-Yuka Co., Ltd., Japan) with a wire bar, and then dried (coating layer dry thickness, about 5 µm). The coated synthetic paper was further heat-treated in an oven at 100°C for 30 minutes to prepare an image-receiving sheet.
- The transfer recording sheet prepared in (b) above was superimposed on the image-receiving sheet in such a manner that the ink coating side of the transfer recording sheet was in contact with the receiving sheet, and recording was conducted by use of a thermal head under the conditions shown below. As a result, a recorded image which was of a vivid magenta color and had a uniform color density as shown in Table 3 could be obtained.
- Color density was measured with densitometer TR-927 manufactured by Macbeth Corporation, U.S.A.
- The light resistance of the recorded image obtained was examined by means of a carbon arc fade meter (manufactured by Suga Testing Machine Co., Ltd., Japan) at a black panel temperature of 63±2°C. The degree of discoloration through a 40-hour irradiation in the light resistance test was shown in Table 3 in terms of ΔE* value. Further, the transfer recording sheet and the print obtained were found to be stable to heat and moisture and show good storage stability in the dark.
- The dyestuff used in this example had been synthesized by reacting 3-methoxy-N,N-di-isobutylaniline with tetracyanoethylene in N,N-dimethylformamide. Its maximum absorption wavelength in acetone was as shown in Table 3 and its melting point was 116-117°C.
- Inks and transfer recording sheets were prepared and transfer recording was conducted in the same manner as in Example 1 except that in place of the dyestuff used in Example 1, the dyestuffs shown in Table 3 were used. As a result, recorded images which were of a vivid magenta color and respectively had color densities shown in Table 3 could be obtained, and the light resistance of each recorded image was good as shown in Table 3.
- An ink and a transfer recording sheet were prepared and transfer recording was conducted in the same manner as in Example 1 except that dyestuff No. 4 in Table 2 given hereinabove was used in place of the dyestuff used in Example 1. The results obtained are shown in Table 3.
- The dyestuff used in this example had been synthesized by reacting 2,5-dimethoxy-N-isobutylaniline with tetracyanoethylene in N,N-dimethylformamide. Its maximum absorption wavelength in acetone was as shown in Table 3 and its melting point was 181-182°C.
- Inks and transfer recording sheets were prepared and transfer recording was conducted in the same manner as in Example 1 except that in place of the dyestuff used in Example 1, the dyestuffs shown in Table 3 were used. As a result, recorded images which were of a vivid magenta color and respectively had color densities shown in Table 3 could be obtained, and the light resistance of each recorded image was good as shown in Table 3.
- Inks and transfer recording sheets were prepared and transfer recording was conducted in the same manner as in Example 1 except that the dyestuffs shown below were used in place of the dyestuff used in Example 1. The results obtained are summarized in Table 3.
-
-
-
-
-
-
-
-
- A transfer recording sheet was prepared and transfer recording was conducted in the same manner as in Example 1 except that an ink prepared according to the following formulation was used in place of the ink used in Example 1. As a result, a recorded image which was of a vivid magenta color and had a uniform color density of 2.15 could be obtained. Further, the recorded image was subjected to a light resistance test and the transfer recording sheet and recorded image were subjected to a storage stability test in the dark. As a result, good results were obtained in each test.
- A transfer recording sheet was prepared and transfer recording was conducted in the same manner as in Example 21 except that in place of the dyestuff used in Example 21, the same dyestuff as that used in Example 11, i.e., dyestuff No. 4 in Table 2, was used. As a result, a recorded image which was of a vivid magenta color and had a uniform color density of 2.15 could be obtained. Further, the recorded image was subjected to a light resistance test and the transfer recording sheet and recorded image were subjected to a storage stability test in the dark. As a result, good results were obtained in each test.
Claims (18)
- A thermal transfer recording sheet comprising a substrate having thereon a colorant layer, said colorant layer comprising a binder and a dyestuff represented by the following general formula (I):
wherein X and Y independently represent a hydrogen atom, a lower alkyl group, or a lower alkoxyl group, provided that either of X and Y represents a lower alkoxyl group; and R¹ and R² independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an allyl group, or a substituted or unsubstituted phenyl group, provided that in the case where both of X and Y represent a lower alkoxyl group, R¹ represents a hydrogen atom. - A sheet as claimed in claim 1, wherein said dyestuff is represented by the following general formula (II)
wherein R³ and R⁴ independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, allyl group, or a substituted or unsubstituted phenyl group; and X¹ and Y¹ independently represent a hydrogen atom, a lower alkyl group, or a lower alkoxyl group, provided that either of X¹ and Y¹ represents a lower alkoxyl group and the remaining one represents another group. - A sheet as claimed in claim 1, wherein said dyestuff is represented by general formula (I) in which R¹ represents a hydrogen atom.
- A sheet as claimed in claim 1, wherein said dyestuff is represented by general formula (I) in which one of X and Y is a lower alkoxyl group and the other is a lower alkoxyl group or a lower alkyl group.
- A sheet as claimed in claim 1, wherein said dyestuff is represented by the following general formula (III)
wherein R⁵ represents a substituted or unsubstituted alkyl group, a cycloalkyl group, allyl group, or a substituted or unsubstituted phenyl group, and X² and Y² independently represent a lower alkoxyl group. - A sheet as claimed in claim 1, wherein said dyestuff is represented by general formula (I) in which R¹ and R² independently represent a hydrogen atom; a straight-chain or branched alkyl group which has 1 to 8 carbon atoms and which may be substituted with a substituent selected from the group consisting of phenyl group which may be substituted with hydroxyl group, carboxyl group, cyano group, amino group, or a halogen atom, an alkoxyl group, an alkoxyalkoxyl group, allyloxy group, an aryloxy group, an aralkyloxy group, an acyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted alkoxycarbonyloxy group, and a heterocyclic group; cyclohexyl or cyclopentyl group; allyl group; or phenyl group which may be substituted with a substituent selected from the group consisting of a straight-chain or branched alkyl group having 1 to 8 carbon atoms, a straight-chain or branched alkoxyl group having 1 to 4 carbon atoms, a halogen atom, nitro group, cyano group, and trifluoromethyl group.
- A sheet as claimed in claim 1, wherein said dyestuff is represented by general formula (I) in which R¹ and R² independently represent a hydrogen atom, a straight-chain or branched alkyl group having 1 to 8 carbon atoms, or an alkoxyalkyl group having 3 to 8 carbon atoms.
- A sheet as claimed in claim 1, wherein said binder is a resin selected from the group consisting of water-soluble resins which are cellulose resins, acrylic acid-based resins, polyvinyl alcohols, polyethylene oxides, and starches and organic solvent-soluble resins which are acrylic resins, methacrylic resins, polystyrenes, polycarbonates, polysulfones, AS resins, polyethersulfones, epoxy resins, polyvinyl acetals, phenoxy resins, polyvinyl butyrals, polyesters, ethyl celluloses, and acetyl celluloses.
- A sheet as claimed in claim 1, wherein said substrate is a sheet of paper selected from capacitor paper and glassine paper or a film of a heat-resistant plastic selected from the group consisting of polyesters, polycarbonates, polyamides, polyimides, and polyaramids, and has a thickness in the range of from 1 to 50 µm.
- A sheet as claimed in claim 1, wherein said substrate is a polyethylene terephthalate film.
- A sheet as claimed in claim 1, wherein said substrate has a heat-resistant resin layer on the side thereof opposite to the colorant layer.
- An ink composition for use in producing a thermal transfer recording sheet, said ink composition comprising a dyestuff represented by the following general formula (I), a binder resin, and a medium:
wherein X and Y independently represent a hydrogen atom, a lower alkyl group, or a lower alkoxyl group, provided that either of X and Y represents a lower alkoxyl group; and R¹ and R² independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a cycloalkyl group, an allyl group, or a substituted or unsubstituted phenyl group, provided that in the case where both of X and Y represent a lower alkoxyl group, R¹ represents a hydrogen atom. - An ink composition as claimed in claim 12, wherein said medium is water, an organic solvent, or a mixture thereof.
- An ink composition as claimed in claim 13, wherein said organic solvent is a single compound or a mixture of two or more compounds, said compound and compounds being selected from the group consisting of alcohols which are methyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, and isobutyl alcohol, Cellosolves which are methyl Cellosolve, ethyl Cellosolve and butyl Cellosolve, aromatics which are toluene, xylene, and chlorobenzene, esters which are ethyl acetate and butyl acetate, ketones which are acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, chlorine-containing solvents which are methylene chloride, chloroform, and trichloroethylene, ethers which are tetrahydrofuran and dioxane, N,N-dimethylformamide, and N-methylpyrrolidone.
- An ink composition as claimed in claim 12, wherein said binder is a resin selected from the group consisting of water-soluble resins which are cellulose resins, acrylic acid-based resins, polyvinyl alcohols, polyethylene oxides, and starches and organic solvent-soluble resins which are acrylic resins, methacrylic resins, polystyrenes, polycarbonates, polysulfones, AS resins, polyethersulfones, epoxy resins, polyvinyl acetals, phenoxy resins, polyvinyl butyrals, polyesters, ethyl celluloses, and acetyl celluloses.
- An ink composition as claimed in claim 12, wherein the content of said binder is in the range of from 1 to 40% by weight based on the total amount of the ink composition.
- An ink composition as claimed in claim 12, wherein the content of said dyestuff of general formula (I) is in the range of from 1 to 30% by weight based on the total amount of the ink composition.
- An ink composition as claimed in claim 12, which further contains organic or inorganic non-sublimable fine particles, a dispersant, an anti-static agent, an anti-blocking agent, an anti-foaming agent, an antioxidant, a viscosity modifier, and a release agent.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2031226A JPH03234589A (en) | 1990-02-09 | 1990-02-09 | Thermosensitive transfer sheet and ink composition therefor |
| JP31226/90 | 1990-02-09 | ||
| JP2033063A JPH03236993A (en) | 1990-02-14 | 1990-02-14 | Heat-sensitive transfer sheet and ink composition for heat-sensitive transfer sheet |
| JP33063/90 | 1990-02-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP0441396A1 true EP0441396A1 (en) | 1991-08-14 |
Family
ID=26369675
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91101766A Withdrawn EP0441396A1 (en) | 1990-02-09 | 1991-02-08 | Thermal transfer recording sheet and ink composition for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| EP (1) | EP0441396A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0593817A1 (en) * | 1992-10-20 | 1994-04-27 | Agfa-Gevaert N.V. | Dye-donor element comprising tricyanovinylaniline dyes |
| EP0594239A1 (en) * | 1992-10-20 | 1994-04-27 | Agfa-Gevaert N.V. | Dye-donor element comprising magenta tricyanovinylaniline dyes |
| EP0594238A1 (en) * | 1992-10-20 | 1994-04-27 | Agfa-Gevaert N.V. | Dye-donor element comprising magenta-coloured tricyanovinylaniline dyes |
| WO1995028286A1 (en) * | 1994-04-19 | 1995-10-26 | Zeneca Limited | Dye diffusion thermal transfer printing |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2159971A (en) * | 1984-06-06 | 1985-12-11 | Mitsubishi Chem Ind | Transfer recording method |
| EP0258856A2 (en) * | 1986-09-05 | 1988-03-09 | BASF Aktiengesellschaft | Dye transfer method |
| EP0279467A2 (en) * | 1987-02-20 | 1988-08-24 | Dai Nippon Insatsu Kabushiki Kaisha | Heat transfer sheet |
-
1991
- 1991-02-08 EP EP91101766A patent/EP0441396A1/en not_active Withdrawn
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2159971A (en) * | 1984-06-06 | 1985-12-11 | Mitsubishi Chem Ind | Transfer recording method |
| EP0258856A2 (en) * | 1986-09-05 | 1988-03-09 | BASF Aktiengesellschaft | Dye transfer method |
| EP0279467A2 (en) * | 1987-02-20 | 1988-08-24 | Dai Nippon Insatsu Kabushiki Kaisha | Heat transfer sheet |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0593817A1 (en) * | 1992-10-20 | 1994-04-27 | Agfa-Gevaert N.V. | Dye-donor element comprising tricyanovinylaniline dyes |
| EP0594239A1 (en) * | 1992-10-20 | 1994-04-27 | Agfa-Gevaert N.V. | Dye-donor element comprising magenta tricyanovinylaniline dyes |
| EP0594238A1 (en) * | 1992-10-20 | 1994-04-27 | Agfa-Gevaert N.V. | Dye-donor element comprising magenta-coloured tricyanovinylaniline dyes |
| WO1995028286A1 (en) * | 1994-04-19 | 1995-10-26 | Zeneca Limited | Dye diffusion thermal transfer printing |
| US5783518A (en) * | 1994-04-19 | 1998-07-21 | Zeneca Limited | Dye diffusion thermal transfer printing |
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