EP0761462B1 - Wärmeübertragungsaufzeichnungsmaterial - Google Patents
Wärmeübertragungsaufzeichnungsmaterial Download PDFInfo
- Publication number
- EP0761462B1 EP0761462B1 EP19960112490 EP96112490A EP0761462B1 EP 0761462 B1 EP0761462 B1 EP 0761462B1 EP 19960112490 EP19960112490 EP 19960112490 EP 96112490 A EP96112490 A EP 96112490A EP 0761462 B1 EP0761462 B1 EP 0761462B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- thermal transfer
- heat
- transfer recording
- color
- meltable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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- 229920000178 Acrylic resin Polymers 0.000 claims description 22
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- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 9
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- HDPBBNNDDQOWPJ-UHFFFAOYSA-N 4-[1,2,2-tris(4-hydroxyphenyl)ethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 HDPBBNNDDQOWPJ-UHFFFAOYSA-N 0.000 claims description 8
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- 238000004381 surface treatment Methods 0.000 description 5
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
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- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
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- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
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- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
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- YXALYBMHAYZKAP-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]heptan-4-ylmethyl 7-oxabicyclo[4.1.0]heptane-4-carboxylate Chemical compound C1CC2OC2CC1C(=O)OCC1CC2OC2CC1 YXALYBMHAYZKAP-UHFFFAOYSA-N 0.000 description 1
- VVAVKBBTPWYADW-UHFFFAOYSA-L Biebrich scarlet Chemical compound [Na+].[Na+].OC1=CC=C2C=CC=CC2=C1N=NC(C(=C1)S([O-])(=O)=O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 VVAVKBBTPWYADW-UHFFFAOYSA-L 0.000 description 1
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- LMULDSDQRQVZMW-UHFFFAOYSA-N N-(5-chloro-2,4-dimethoxyphenyl)-4-[[5-(diethylsulfamoyl)-2-methoxyphenyl]diazenyl]-3-hydroxynaphthalene-2-carboxamide Chemical compound CCN(CC)S(=O)(=O)C1=CC=C(OC)C(N=NC=2C3=CC=CC=C3C=C(C=2O)C(=O)NC=2C(=CC(OC)=C(Cl)C=2)OC)=C1 LMULDSDQRQVZMW-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
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- 125000002723 alicyclic group Chemical group 0.000 description 1
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- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 description 1
- KTPIWUHKYIJBCR-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohex-4-ene-1,2-dicarboxylate Chemical compound C1C=CCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 KTPIWUHKYIJBCR-UHFFFAOYSA-N 0.000 description 1
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- PZTQVMXMKVTIRC-UHFFFAOYSA-L chembl2028348 Chemical compound [Ca+2].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 PZTQVMXMKVTIRC-UHFFFAOYSA-L 0.000 description 1
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- 150000001896 cresols Chemical class 0.000 description 1
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- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
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- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 235000010187 litholrubine BK Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- VAUOPRZOGIRSMI-UHFFFAOYSA-N n-(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CNC1=CC=CC=C1 VAUOPRZOGIRSMI-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- CTIQLGJVGNGFEW-UHFFFAOYSA-L naphthol yellow S Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C([O-])=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 CTIQLGJVGNGFEW-UHFFFAOYSA-L 0.000 description 1
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- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
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- 239000005011 phenolic resin Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
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- 229920006324 polyoxymethylene Polymers 0.000 description 1
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- 238000004886 process control Methods 0.000 description 1
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
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- VVNRQZDDMYBBJY-UHFFFAOYSA-M sodium 1-[(1-sulfonaphthalen-2-yl)diazenyl]naphthalen-2-olate Chemical compound [Na+].C1=CC=CC2=C(S([O-])(=O)=O)C(N=NC3=C4C=CC=CC4=CC=C3O)=CC=C21 VVNRQZDDMYBBJY-UHFFFAOYSA-M 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
- B41M5/395—Macromolecular additives, e.g. binders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/392—Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
Definitions
- the present invention relates to thermal transfer recording materials for providing printed images having excellent fastness on diverse receptors.
- Conventional thermal transfer recording materials include those comprising a foundation and, applied onto the foundation, a heat-meltable ink containing a vehicle composed mainly of a wax or another type of heat-meltable ink containing a vehicle composed mainly of a resin for ensuring printed images of good quality even on paper sheets having relatively poor surface smoothness or printed images of high scratch resistance.
- bar code printers and label printers using thermal transfer recording materials have been used to print bar codes or like codes for management of parts or products in production processes of manufacturing factories, merchandise management in distribution field, management of articles at using sites, and the like.
- bar codes are frequently scratched or rubbed. Therefore, such bar codes are required to have particularly high scratch resistance.
- thermal transfer printers have been used in the production of diversified products in small quantities, including outdoor advertising materials, election posters, common posters, standing signboards, stickers, catalogs, pamphlets, calenders and the like in the commercial printing field; bags for light packaging, labels of containers for foods, drinks, medicines, paints and the like, and binding tapes in the packaging field; and labels for indicating quality characteristics, labels for process control, labels for product management and the like in the apparel field. These articles are also required to exhibit scratch resistance.
- thermal transfer recording materials using the heat-meltable ink containing a vehicle composed mainly of a wax exhibit poor scratch resistance though the ink enjoys satisfactory transferability (separability of the ink layer).
- the conventional thermal transfer recording materials using the heat-meltable ink containing a vehicle composed mainly of a resin such as ethylene-vinyl acetate copolymer the transferability of the ink is inferior to the former ink due to its relatively high melt viscosity though resulting printed images enjoy relatively high scratch resistance.
- both of the thermal transfer recording materials provide printed images having poor adhesion to common plastic films, resulting in poor scratch resistance.
- the thermal transfer recording material described in EP-A-0 696 517 (prior art according to Art. 54(3) EPC) uses a heat-meltable ink comprising a vehicle comprising not less than 85% by weight of an epoxy resin.
- thermo transfer recording material which is capable of exhibiting satisfactory transferability (separability of the ink layer) while at the same time forming printed images having excellent adhesion to diverse plastic films and excellent scratch resistance.
- a thermal transfer recording material comprising a foundation and, provided thereon, a heat-meltable ink layer comprising at least a heat-meltable material and a coloring agent, the heat-meltable material comprising 30 to 90 % by weight of an epoxy resin and 10 to 70 % by weight of an acrylic resin having a number average molecular weight of 30,000 to 300,000.
- the epoxy resin comprises at least one member selected from the group consisting of tetraphenolethane tetraglycidyl ether, cresol novolac polyglycidyl ether, bisphenol A diglycidyl ether and bisphenol F diglycidyl ether.
- the epoxy resin comprises at least one member selected from the group consisting of tetraphenolethane tetraglycidyl ether, cresol novolac polyglycidyl ether and bisphenol F diglycidyl ether.
- the acrylic resin has a glass transition point of 30° to 120°C.
- Fig. 1 is a partial plan view showing an example of an arrangement of color ink layers of respective colors in an embodiment of the thermal transfer recording material of the present invention.
- the heat-meltable ink layer comprises at least a heat-meltable material and a coloring agent, the heat-meltable material comprising 30 to 90 % by weight, preferably 40 to 60 % by weight of an epoxy resin and 10 to 70 % by weight, preferably 40 to 60 % by weight of an acrylic resin having a number average molecular weight of 30,000 to 300,000.
- the combination use of the epoxy resin and the high molecular weight acrylic resin in the specific ratio in the heat-meltable ink layer improves the adhesion of the ink to a variety of plastic films as well as the transferability (separability) of the ink layer as compared with the conventional resin-type ink layer, resulting in printed images having excellent scratch resistance and like property.
- the term "separability of a heat-meltable ink lalyer" means the property that when being transferred, the heated portion of a heat-meltable ink layer is easily separated from the unheated portion of the heat-meltable ink layer and only the heated portion is transferred on a receptor to give a sharp print image.
- the epoxy resin mainly contributes to the improvement of separability of the ink layer, leading to excellent transferability.
- the high molecular weight acrylic resin contributes to the improvement of scratch resistance of printed images formed on plastic films due to its excellent adhesion to a variety of plastic films and its excellent durability and toughness.
- the ink layer is excellent in transparency, resulting in good adaptability to the formation of color images.
- the use of such a high molecular weight acrylic resin as prescribed in the present invention is liable to degrade the separability of the resulting ink layer though the acrylic resin contributes to the improvement of scratch resistance of printed images.
- the proportion of the epoxy resin is smaller than the above range or the proportion of the acrylic resin is larger than the above range, the transferability of the ink layer is not satisfactorily improved because the amount of the epoxy resin contributing to an improvement in separability of the ink layer is small and the adhesion of the ink to the foundation is excessively strong.
- the proportion of the epoxy resin is larger than the above range or the proportion of the acrylic resin is smaller than the above range, the fastness of the ink constituting printed images formed on various plastic films is not satisfactorily improved, resulting in poor scratch resistance.
- the epoxy resin used in the present invention is not limited to particular one, and any usual epoxy resins can be used. From the viewpoints of dispersibility of a coloring agent and transferability of the resulting ink, however, the epoxy resin component preferably comprises not less than 50 % (% by weight, hereinafter the same), more preferably not less than 70 % of at least one epoxy resin selected from the group consisting of tetraphenolethane tetraglycidyl ether, cresol novolac polyglycidyl ether, bisphenol A diglycidyl ether and bisphenol F diglycidyl ether.
- the epoxy resin used in the present invention is intended to mean an epoxy resin in an uncured or non-crosslinked state.
- the epoxy resin component be entirely composed of at least one of the above-specified epoxy resins. It is, however, not necessarily required to do so, and the epoxy resin component comprising not less than 50 %, preferably not less than 70 % of at least one of the four specified epoxy resins can serve the purpose. If the proportion of such specified epoxy resin component in the overall epoxy resin is less than the foregoing range, poor dispersibility of a pigment in the heat-meltable material will result, thus deteriorating the transferability of the ink layer.
- Tetraphenolethane tetraglycidyl ether (hereinafter referred to as "TPETGE" as the need arises) as aforementioned, having a softening point of 92°C, is a species of polyfunctional epoxy resins and represented by the formula (I):
- Cresol novolac polyglycidyl ether (hereinafter referred to as "CNPGE" as the need arises) as aforementioned is a species of polyfunctional epoxy resins.
- examples of preferred cresol novolac polygylcidyl ethers include those represented by the formula (II): wherein m is usually an integer of from 3 to 7.
- CNPGEs useful in the present invention include mixtures of those of the formula (II) wherein values for m are different from each other.
- CNPGE preferably has a softening point of 60° to 120°C.
- Bisphenol A diglycidyl ether (hereinafter referred to as "BPADGE" as the need arises) is a species of difunctional epoxy resins. Preferred are those represented by the formula (III): wherein n is usually an integer of from 0 to 13. BPADGEs useful in the present invention include mixtures of those of the formula (III) wherein values for n are different from each other. BPADGE preferably has a softening point of 60° to 140°C .
- Bisphenol F diglycidyl ether (hereinafter referred to as "BPFDGE" as the need arises) is a species of difunctional epoxy resins. Preferred are those represented by the formula (IV): wherein p is usually an integer of from 0 to 33. BPFDGEs useful in the present invention include mixtures of those of the formula (IV) wherein values for p are different from each other. BPFDGE preferably has a softening point of 60° to 140°C .
- epoxy resins usable in combination with the aforementioned specified epoxy resins are:
- epoxy resins may be used either alone or as mixtures of two or more species thereof.
- epoxy resins usable in combination with the above-specified epoxy resins are those having softening points of not lower than 60°C.
- an epoxy resin in a liquid state can also be used so long as the overall heat-meltable material resulting from mixing it with the specified epoxy resin or the epoxy resin usable in combination therewith or the acrylic resin has a softening point of not lower than 60°C .
- the acrylic resin usable in the present invention has a number average molecular weight of 30,000 to 300,000. More preferable are acrylic resins having a number average molecular weight of 30,000 to 150,000, particularly 40,000 to 150,000. When the number average molecular weight of the acrylic resin is smaller than the above range, the resulting ink is prone to provide printed images having unsatisfactory scratch resistance. When the number average molecular weight is larger than the above range, the resulting ink is prone to offer poor transferability.
- the acrylic resin preferably has a glass transition point of 30° to 120°C .
- acrylic resin examples include homopolymers or copolymers of one or more acrylic monomers such as (meth)acrylic acid, (meth)acrylic acid alkyl esters (wherein examples of the alkyl group are those having 1 to 25 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, amyl, octyl and stearyl), and (meth)acrylonitrile; and copolymers of one or more of the foregoing acrylic monomers and one or more other monomers copolymerizable therewith, such as styrene, butadiene, vinyl monomer containing siloxane bond and fluorine-containing vinyl monomer.
- acrylic monomers such as (meth)acrylic acid, (meth)acrylic acid alkyl esters (wherein examples of the alkyl group are those having 1 to 25 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, amy
- acrylic resins are, for instance, acrylic acid resin, methacrylic acid resin, alkyl acrylate resins, alkyl methacrylate resins, acrylonitrile resin, acrylonitrile-styrene copolymer resin and acrylonitrile-styrene-butadiene copolymer resin.
- the heat-meltable material according to the present invention may be incorporated with one or more heat-meltable resins other than the above-mentioned so long as the purpose of the present invention is attained.
- heat-meltable resins include ethylene-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate copolymer resin, phenolic resin, polyester resin and polyamide resin.
- Such heat-meltable resins are used in an amount of preferably not greater than 30 %, more preferably not greater than 15 %, most preferably not greater than 5 %, based on the amount of the overall heat-meltable material.
- the softening point of the overall heat-meltable material is preferably within the range of from 60° to 120°C in terms of the storage stability and transferability of the thermal transfer recording material.
- the proportion of the overall heat-meltable material in the heat-meltable ink is preferably from about 40 to about 95 % in terms of the transferability and like properties of the ink layer.
- the coloring agent in the present invention are various organic and inorganic pigments, inclusive of carbon black.
- organic and inorganic pigments include azo pigments (such as insoluble azo pigments, azo lake pigments and condensed azo pigments), phthalocyanine pigments, nitro pigments, nitroso pigments, anthraquinonoid pigments, nigrosine pigments, quinacridone pigments, perylene pigments, isoindolinone pigments, dioxazine pigments, titanium white, calcium carbonate and barium sulfate.
- azo pigments such as insoluble azo pigments, azo lake pigments and condensed azo pigments
- phthalocyanine pigments such as insoluble azo pigments, azo lake pigments and condensed azo pigments
- phthalocyanine pigments such as insoluble azo pigments, azo lake pigments and condensed azo pigments
- phthalocyanine pigments such as insoluble azo pigments, azo lake
- Yellow pigments, magenta pigments, and cyan pigments, and optionally black pigments are used for forming multi-color or full-color printed images utilizing subtractive color mixture.
- the pigments for yellow, magenta and cyan for use in the ink layer are preferably transparent, while the pigments for black are usually opaque.
- transparent yellow pigments examples include organic pigments such as Naphthol Yellow S, Hansa Yellow 5G, Hansa Yellow 3G, Hansa Yellow G, Hansa Yellow GR, Hansa Yellow A, Hansa Yellow RN, Hansa Yellow R, Benzidine Yellow, Benzidine Yellow G, Benzidine Yellow GR, Permanent Yellow NCG and Quinoline Yellow Lake. These pigments may be used either alone or in combination of two or more species thereof.
- transparent magenta pigments examples include organic pigments such as Permanent Red 4R, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Carmine FB, Lithol Red, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Rhodamine Lake B, Rhodamine Lake Y, Arizalin Lake and Quinacridone Red. These pigments may be used either alone or in combination of two or more species thereof.
- transparent cyan pigments examples include organic pigments such as Victoria Blue Lake, metal-free Phthalocyanine Blue, Phthalocyanine Blue and Fast Sky Blue. These pigments may be used either alone or in combination of two or more species thereof.
- transparent pigment means a pigment which gives a transparent ink when dispersed in a transparent vehicle.
- black pigments examples include inorganic pigments having insulating or conductive properties such as carbon black, and organic pigments such as Aniline Black. These pigments may be used either alone or in combination of two or more species thereof.
- the proportion of the coloring agent in respective color ink layers is usually from about 5 to about 60 %.
- a pigment such as carbon black
- a pigment having an oil absorption of not less than 80 is good in dispersibility against bisphenol A diglycidyl ether and, hence, provides a heat-meltable ink wherein the pigment is uniformly dispersed and which exhibits good transferability.
- oil absorption of a pigment means the amount (ml) of dibutyl phthalate which is absorbed by 100 g of the pigment.
- the heat-meltable ink layer may be incorporated with appropriate additives such as dispersing agent as well as the aforementioned ingredients.
- the heat-meltable ink layer can be formed by applying onto a foundation a coating liquid prepared by dissolving the epoxy resin and the acrylic resin in a solvent which is capable of dissolving the resins or dispersing the epoxy resin and the acrylic resin in a solvent (inclusive of water) which is incapable of dissolving the resins and then dissolving or dispersing the coloring agent together with other additives, followed by drying.
- the coating amount (on a solid basis, hereinafter the same) of the heat-meltable ink layer in the present invention is usually 0.02 to 5 g/m 2 , preferably 0.5 to 3 g/m 2 .
- polyester films such as polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film, polybutylene naphthalate film and polyarylate film, polycarbonate film, polyamide film, aramid film, polyether sulfone film, polysulfone film, polyphenylene sulfide film, polyether ether ketone film, polyether imide film, modified polyphenylene ether film and polyacetal film, and other various plastic films commonly used for the foundation of ink ribbons of this type.
- thin paper sheets of high density such as condenser paper can also be used.
- the thickness of the foundation is usually from about 1 to about 10 ⁇ m. From the standpoint of reducing heat spreading to increase the resolution of printed images, the thickness of the foundation is preferably from 1 to 6 ⁇ m.
- a conventionally known stick-preventive layer is preferably provided on the back side (the side to be brought into slide contact with the thermal head) of the foundation.
- materials for the stick-preventive layer include various heat-resistant resins such as silicone resins, fluorine-containing resins and nitrocellulose resins, and other resins modified with these heat-resistant resins such as silicone-modified urethane resins and silicone-modified acrylic resins, and mixtures of the foregoing heat-resistant resins and lubricating agents.
- thermal transfer recording material means to include a thermal transfer recording material for forming monochromatic images, and a thermal transfer recording material for forming multi-color or full-color images utilizing subtractive color mixture.
- the thermal transfer recording material for forming monochromatic images is of a structure in which a monochromatic heat-meltable ink layer is provided on a foundation.
- Colors for the monochromatic heat-meltable ink layer include black, red, blue, green, yellow, magenta and cyan.
- An embodiment of the thermal transfer recording material for forming multi-color or full-color images is of a structure in which on a single foundation are disposed a yellow heat-meltable ink layer, a magenta heat-meltable ink layer and a cyan heat-meltable ink layer and, optionally, a black heat-meltable ink layer in a side-by-side relation.
- Such color ink layers can be disposed in various manners on a foundation depending on the kind of printer.
- Fig. 1 is a partial plan view showing an example of the thermal transfer recording material according to the foregoing embodiment.
- a yellow heat-meltable ink layer 2Y on a single foundation 1 are disposed a yellow heat-meltable ink layer 2Y, a magenta heat-meltable ink layer 2M and a cyan heat-meltable ink layer 2C in a side-by-side relation.
- These ink layers 2Y, 2M and 2C are periodically disposed longitudinally of the foundation 1 in recurring units U each comprising ink layers 2Y, 2M and 2C arranged in a predetermined order.
- the order of arrangement of these color ink layers in each recurring unit U can be suitably determined according to the order of transfer of the color ink layers.
- Each recurring unit U may comprise a black ink layer in addition to the layers 2Y, 2M and 2C.
- thermal transfer recording material for forming multi-color or full-color images is a set of thermal transfer recording materials comprising a first thermal transfer recording material having a yellow heat-meltable ink layer on a foundation, a second thermal transfer recording material having a magenta heat-meltable ink layer on another foundation, and a third thermal transfer recording material having a cyan heat-meltable ink layer on yet another foundation, and, optionally a fourth thermal transfer recording material having a black heat-meltable ink layer on still another foundation.
- thermal transfer recording materials will give multi-color or full-color images having excellent scratch resistance. Further, individual color heat-meltable ink layers in the present invention are excellent in superimposing properties, thus ensuring multi-color or full-color images of superior color reproducibility.
- the ink layer is superimposed on an image-receiving body and heat energy is applied imagewise to the ink layer.
- a thermal head is typically used as a heat source of the heat energy.
- any conventional heat sources can be used such as laser light, infrared flash and heat pen.
- thermal transfer method using laser light is advantageous since application of heat energy is easy.
- the formation of multi-color or full-color images with use of the thermal transfer recording material of the present invention is performed, for example, as follows.
- the yellow ink layer, the magenta ink layer and the cyan ink layer are selectively melt-transferred onto a receptor in a predetermined order in response to separation color signals of an original multi-color or full-color image, i.e., yellow signals, magenta signals and cyan signals to form yellow ink dots, magenta ink dots and cyan ink dots on the receptor in a predetermined order, thus yielding a yellow separation image, a magenta separation image and a cyan separation image superimposed on one another on the receptor.
- the order of transfer of the yellow ink layer, magenta ink layer and cyan ink layer can be determined as desired.
- all the three color ink layers are selectively transferred in response to the corresponding three color signals to form three color separation images on the receptor.
- the corresponding two of the three color ink layers are selectively transferred to form two color separation images.
- a multi-color or full-color image comprising: (A) at least one region wherein a color is developed by subtractive color mixture of at least two superimposed inks of yellow, magenta and cyan, or (B) a combination of the region (A) and at least one region of a single color selected from yellow, magenta and cyan where different color inks are not superimposed.
- a region where yellow ink dots and magenta ink dots are present in a superimposed state develops a red color
- a region where yellow ink dots and cyan ink dots are present in a superimposed state develops a green color
- a region where magenta ink dots and cyan ink dots are present in a superimposed state develops a blue color
- a region where yellow ink dots, magenta ink dots and cyan ink dots are present in a superimposed state develops a black color.
- a region where only yellow, magenta or cyan ink dots are present develops a yellow, magenta or cyan color.
- a black color is developed by the superimposing of yellow ink dots, magenta ink dots and cyan ink dots.
- a black color may otherwise be obtained by using only black ink dots instead of three color ink dots.
- a black color may be obtained by superimposing black ink dots on at least one of yellow, magenta and cyan ink dots, or on superimposed ink dots of at least two of yellow, magenta and cyan ink dots.
- the printed images may be directly formed on a final object, or alternatively by previously forming the printed images on a sheet-like image-receiving body (receptor) and then bonding the image-receiving body thus bearing the printed images to a final object with suitable means such as an adhesive.
- receptors Usable as the receptor are a variety of plastic films (this term is intended to include sheets, hereinafter the same) including usual polyethylene terephthalate film and vinyl chloride resin films such as polyvinyl chloride film. Of course, receptors subjected to a surface treatment for thermal transfer can be used.
- a 5 ⁇ m-thick polyethylene terephthalate film was formed on one side thereof with a stick-preventive layer composed of a silicone resin with a coating amount of 0.25 g/m 2 .
- a stick-preventive layer composed of a silicone resin with a coating amount of 0.25 g/m 2 .
- an ink coating liquid of the formula shown in Table 1 was applied onto the opposite side of the polyethylene terephthalate film with respect to the stick-preventive layer, followed by drying to form a heat-meltable ink layer with a coating amount of 2 g/m 2 , yielding a thermal transfer recording material.
- thermal transfer type bar code printer (B-30 made by TEC Corp.) under the following conditions:
- the resulting printed images were evaluated for their transferability and scratch resistance (crocking resistance and smear resistance).
- the printed images were rubbed under the following conditions and then subjected to the reading test as above.
- the printed images were rubbed under the following conditions and then subjected to the reading test as above.
- the thermal transfer recording material of the present invention offers excellent transferability of the ink layer thereof (separability of the ink layer) and provides printed images exhibiting good adhesion to diverse plastic films and high scratch resistance and hence is highly useful in printing images such as bar codes.
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Claims (4)
- Wärmeübertragungsaufzeichnungsmaterial, das eine Grundlage und eine darauf aufgebrachte wärme-schmelzbare Tintenschicht umfaßt, die mindestens ein wärme-schmelzbares Material und ein Färbemittel umfaßt,
wobei das wärme-schmelzbare Material 30 bis 90 Gewichts-% eines Epoxidharzes und 10 bis 70 Gewichts-% eines Acrylharzes mit einem Zahlenmittel des Molekulargewichts von 30.000 bis 300.000 umfaßt. - Wärmeübertragungsaufzeichnungsmaterial nach Anspruch 1, wobei das Epoxidharz mindestens ein Element umfaßt, das aus der Gruppe ausgewählt ist, die aus Tetraphenolethantetraglycidylether, Kresolnovolak-polyglycidylether, Bisphenol A-diglycidylether und Bisphenol F-diglycidylether besteht.
- Wärmeübertragungsaufzeichnungsmaterial nach Anspruch 1, wobei das Epoxidharz mindestens ein Element umfaßt, das aus der Gruppe ausgewählt ist, die aus Tetraphenolethantetraglycidylether, Kresolnovolak-polyglycidylether und Bisphenol F-diglycidylether besteht.
- Wärmeübertragungsaufzeichnungsmaterial nach Anspruch 1, wobei das Acrylharz einen Glasübergangspunkt von 30 °C bis 120 °C aufweist.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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JP19859695 | 1995-08-03 | ||
JP19859695 | 1995-08-03 | ||
JP198596/95 | 1995-08-03 |
Publications (2)
Publication Number | Publication Date |
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EP0761462A1 EP0761462A1 (de) | 1997-03-12 |
EP0761462B1 true EP0761462B1 (de) | 1999-11-03 |
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EP19960112490 Expired - Lifetime EP0761462B1 (de) | 1995-08-03 | 1996-08-02 | Wärmeübertragungsaufzeichnungsmaterial |
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EP (1) | EP0761462B1 (de) |
DE (1) | DE69604989T2 (de) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH09142031A (ja) * | 1995-11-22 | 1997-06-03 | Fujicopian Co Ltd | 熱転写記録材料 |
US5674805A (en) * | 1996-11-27 | 1997-10-07 | Eastman Kodak Company | Binder for thermal transfer pigment donor element |
CN101570091B (zh) * | 2009-06-05 | 2011-07-20 | 焦作市卓立烫印材料有限公司 | 输血袋用烫印箔及其制备方法 |
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FR2637095B1 (fr) * | 1988-09-28 | 1994-03-25 | Ricoh Cy Ltd | Milieu d'enregistrement par transfert d'image thermique |
JP2938578B2 (ja) * | 1990-12-14 | 1999-08-23 | フジコピアン株式会社 | 熱転写記録媒体 |
EP0696517B1 (de) * | 1994-07-22 | 1998-11-18 | Fujicopian Co., Ltd. | Thermotransferaufzeichnungsmaterial |
-
1996
- 1996-08-02 EP EP19960112490 patent/EP0761462B1/de not_active Expired - Lifetime
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