JPS63205285A - Thermal transfer recording medium - Google Patents
Thermal transfer recording mediumInfo
- Publication number
- JPS63205285A JPS63205285A JP62039522A JP3952287A JPS63205285A JP S63205285 A JPS63205285 A JP S63205285A JP 62039522 A JP62039522 A JP 62039522A JP 3952287 A JP3952287 A JP 3952287A JP S63205285 A JPS63205285 A JP S63205285A
- Authority
- JP
- Japan
- Prior art keywords
- heat
- fluorescent
- ink layer
- resin
- substance
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- 239000000289 melt material Substances 0.000 claims description 2
- 239000006104 solid solution Substances 0.000 abstract description 18
- 238000007639 printing Methods 0.000 abstract description 6
- 238000010023 transfer printing Methods 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 64
- 238000002844 melting Methods 0.000 description 30
- 239000000463 material Substances 0.000 description 29
- 239000007850 fluorescent dye Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- 239000000123 paper Substances 0.000 description 12
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- 230000000052 comparative effect Effects 0.000 description 8
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- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- VYXSBFYARXAAKO-UHFFFAOYSA-N ethyl 2-[3-(ethylamino)-6-ethylimino-2,7-dimethylxanthen-9-yl]benzoate;hydron;chloride Chemical compound [Cl-].C1=2C=C(C)C(NCC)=CC=2OC2=CC(=[NH+]CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-UHFFFAOYSA-N 0.000 description 5
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- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 description 4
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- HYLDLLCHFLSKAG-UHFFFAOYSA-M lissamine flavine FF Chemical compound [Na+].C1=CC(C)=CC=C1N(C1=O)C(=O)C2=C3C1=CC=CC3=C(N)C(S([O-])(=O)=O)=C2 HYLDLLCHFLSKAG-UHFFFAOYSA-M 0.000 description 4
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- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
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- 229910052751 metal Inorganic materials 0.000 description 3
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- 150000003077 polyols Chemical class 0.000 description 3
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 3
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- NOFPXGWBWIPSHI-UHFFFAOYSA-N 2,7,9-trimethylacridine-3,6-diamine;hydrochloride Chemical compound Cl.CC1=C(N)C=C2N=C(C=C(C(C)=C3)N)C3=C(C)C2=C1 NOFPXGWBWIPSHI-UHFFFAOYSA-N 0.000 description 2
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- 235000021357 Behenic acid Nutrition 0.000 description 2
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- 150000004665 fatty acids Chemical class 0.000 description 2
- GNBHRKFJIUUOQI-UHFFFAOYSA-N fluorescein Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(O)C=C1OC1=CC(O)=CC=C21 GNBHRKFJIUUOQI-UHFFFAOYSA-N 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 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 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
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- 239000000600 sorbitol Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- FOFQZWWNSUAROF-UHFFFAOYSA-N 1,2-diphenylethanesulfonamide Chemical compound C=1C=CC=CC=1C(S(=O)(=O)N)CC1=CC=CC=C1 FOFQZWWNSUAROF-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- JFMYRCRXYIIGBB-UHFFFAOYSA-N 2-[(2,4-dichlorophenyl)diazenyl]-n-[4-[4-[[2-[(2,4-dichlorophenyl)diazenyl]-3-oxobutanoyl]amino]-3-methylphenyl]-2-methylphenyl]-3-oxobutanamide Chemical compound C=1C=C(C=2C=C(C)C(NC(=O)C(N=NC=3C(=CC(Cl)=CC=3)Cl)C(C)=O)=CC=2)C=C(C)C=1NC(=O)C(C(=O)C)N=NC1=CC=C(Cl)C=C1Cl JFMYRCRXYIIGBB-UHFFFAOYSA-N 0.000 description 1
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical compound CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N Alizarin Natural products C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-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
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- 244000163122 Curcuma domestica Species 0.000 description 1
- 235000003392 Curcuma domestica Nutrition 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- QZXSMBBFBXPQHI-UHFFFAOYSA-N N-(dodecanoyl)ethanolamine Chemical compound CCCCCCCCCCCC(=O)NCCO QZXSMBBFBXPQHI-UHFFFAOYSA-N 0.000 description 1
- OTGQIQQTPXJQRG-UHFFFAOYSA-N N-(octadecanoyl)ethanolamine Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCO OTGQIQQTPXJQRG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
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- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 235000019484 Rapeseed oil Nutrition 0.000 description 1
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000001154 acute effect Effects 0.000 description 1
- HFVAFDPGUJEFBQ-UHFFFAOYSA-M alizarin red S Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=C(S([O-])(=O)=O)C(O)=C2O HFVAFDPGUJEFBQ-UHFFFAOYSA-M 0.000 description 1
- WLDHEUZGFKACJH-UHFFFAOYSA-K amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1N=NC1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-UHFFFAOYSA-K 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- QFFVPLLCYGOFPU-UHFFFAOYSA-N barium chromate Chemical compound [Ba+2].[O-][Cr]([O-])(=O)=O QFFVPLLCYGOFPU-UHFFFAOYSA-N 0.000 description 1
- 229940083898 barium chromate Drugs 0.000 description 1
- BNZLJNRQXPJPJY-UHFFFAOYSA-L barium(2+) 4-[(5-chloro-4-methyl-2-sulfophenyl)diazenyl]-3-oxidonaphthalene-2-carboxylate Chemical compound CC1=CC(=C(C=C1Cl)N=NC2=C(C(=CC3=CC=CC=C32)C(=O)[O-])[O-])S(=O)(=O)O.[Ba+2] BNZLJNRQXPJPJY-UHFFFAOYSA-L 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
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- 238000009937 brining Methods 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
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- 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
- ZLFVRXUOSPRRKQ-UHFFFAOYSA-N chembl2138372 Chemical compound [O-][N+](=O)C1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 ZLFVRXUOSPRRKQ-UHFFFAOYSA-N 0.000 description 1
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- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 239000000982 direct dye Substances 0.000 description 1
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- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- FPVGTPBMTFTMRT-NSKUCRDLSA-L fast yellow Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-NSKUCRDLSA-L 0.000 description 1
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- 239000003925 fat Substances 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 235000010187 litholrubine BK Nutrition 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
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- 238000013508 migration Methods 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
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- 229920000573 polyethylene Polymers 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
- 235000012752 quinoline yellow Nutrition 0.000 description 1
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- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/41—Base layers supports or substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/423—Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
- B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は熱転写記録媒体に関し、詳しくは、蛍光を有す
るインク層の熱溶融性を利用して記録紙上に蛍光印字記
録を行なうための熱転写記録媒体に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a thermal transfer recording medium, and more particularly to a thermal transfer recording medium for recording fluorescent prints on recording paper by utilizing the heat-melting properties of an ink layer having fluorescence.
熱転写記録媒体として、ポリエステルフィルムのような
耐熱性支持体上に染料及び／又は顔料からなる着色剤、
固着剤としてのワックス類、及び樹脂結着剤を含む熱溶
融性インク層を設けたものは知られている。このような
記録媒体を用いる印字記録法は記録媒体の熱溶融性イン
ク層面に記録用紙などの記録体を重ね、記録媒体の耐熱
性支持体側からサーマルヘッドを当てて、その部分のイ
ンク層を記録体上に溶融転写することにより行なわれる
。As a thermal transfer recording medium, a coloring agent consisting of a dye and/or a pigment is placed on a heat-resistant support such as a polyester film,
It is known to provide a heat-melting ink layer containing a wax as a fixing agent and a resin binder. The print recording method using such a recording medium is to stack a recording medium such as recording paper on the heat-melting ink layer surface of the recording medium, and then apply a thermal head from the heat-resistant support side of the recording medium to record the ink layer in that area. This is done by melt transfer onto the body.
しかし、こうして得られる記録物を特殊な目的、例えば
小切手、郵便料金切手等に用いた場合は偽造される恐れ
がある。そこで、例えばインク層中に蛍光物質を存在さ
せることが考えられる。この場合の印字方式としてポジ
転写方式とネガ転写方式がある。However, if the recorded matter thus obtained is used for a special purpose, such as a check or postage stamp, there is a risk that it will be forged. Therefore, it is conceivable to include a fluorescent substance in the ink layer, for example. Printing methods in this case include a positive transfer method and a negative transfer method.
即ち、蛍光物質をインク層に含ませて印字すると１通常
状態（特定励起波長の光がない状態）では転写像は普通
の着色像であるが、特定励起波長の光を照射した時に蛍
光を発するので偽造防止が可能である。ところが、一般
の蛍光染料、蛍光顔料等の蛍光物質は着色力が低いので
、多量に用いる必要がある。しかし、蛍光物質は熱に対
する感応性がないため、このように多量に蛍光物質を用
いると、インク層の熱転写特性が低下して転写像のかす
れ、むら等の原因となる。In other words, when a fluorescent substance is included in the ink layer and printed, the transferred image is a normal colored image under normal conditions (no light with a specific excitation wavelength), but it emits fluorescence when irradiated with light with a specific excitation wavelength. Therefore, counterfeiting can be prevented. However, since fluorescent substances such as general fluorescent dyes and fluorescent pigments have low coloring power, it is necessary to use them in large quantities. However, since fluorescent substances are not sensitive to heat, using such a large amount of fluorescent substances deteriorates the thermal transfer characteristics of the ink layer, causing blurring, unevenness, etc. of the transferred image.
特に、平滑性の悪いエンベロープへの転写では画像のか
すれ、むら等が極めて多くみられるといった欠陥がある
。更に、ネガ転写方式の場合には転写性の良いインク層
が要求される。In particular, when transferring to an envelope with poor smoothness, there are defects such as blurring, unevenness, etc. of the image are extremely common. Furthermore, in the case of a negative transfer method, an ink layer with good transferability is required.
本発明は上記のような偽造の恐れがなく、しかも転写印
字品質に優れ、転写画像における色濃度が高いと共に、
高強度の蛍光色が得られる熱転写記録媒体を提供するこ
とである。The present invention eliminates the risk of forgery as described above, has excellent transfer printing quality, and has high color density in the transferred image.
An object of the present invention is to provide a thermal transfer recording medium capable of producing high-intensity fluorescent colors.
本発明の熱転写記録媒体は、耐熱性支持体上にワックス
類及び／又は樹脂を主成分とする熱溶融性物質層と１着
色剤（染料及び／又は顔料）、蛍光物質更にワックス類
及び／又は樹脂を主成分とする熱溶融性インク層を順次
設けたことを特徴とするものである。The thermal transfer recording medium of the present invention comprises a heat-resistant support, a layer of a heat-melting material mainly composed of waxes and/or resins, a coloring agent (dye and/or pigment), a fluorescent material, and a layer of wax and/or resin. It is characterized in that heat-melt ink layers containing resin as a main component are sequentially provided.
ちなみに、本発明者らは偽造防止の目的で熱溶融性イン
ク層中に蛍光物質を含有させ、しかも多量に用いても熱
転写印字品質を悪化することなく、印字画像の色濃度、
蛍光強度を満足させるべく熱溶融性インク層を有する熱
転写記録媒体について鋭意研究を重ねた結果、本発明を
完成するに至ったものである。Incidentally, the present inventors incorporated a fluorescent substance into the heat-melting ink layer for the purpose of preventing counterfeiting, and even when used in large amounts, the thermal transfer print quality did not deteriorate, and the color density of the printed image,
The present invention was completed as a result of intensive research into thermal transfer recording media having a heat-melting ink layer in order to satisfy the fluorescence intensity.
ところで、蛍光物質としては一般に蛍光染料又は蛍光顔
料が使用されている。このような蛍光物質を従来からあ
るタイプの熱転写記録媒体の熱溶融性インク層に加えれ
ば１本発明の目的である記録物の偽造防止は、一応達成
できる。By the way, fluorescent dyes or fluorescent pigments are generally used as fluorescent substances. If such a fluorescent substance is added to the heat-melting ink layer of a conventional type of thermal transfer recording medium, the purpose of the present invention, which is to prevent forgery of recorded products, can be achieved to some extent.
即ち、このような蛍光物質を含む熱溶融性インク層（着
色剤も含む）から得られる転写像は、外観上は通常の着
色画像と同一であるが、特定波長の励起光（ある物質が
効率よく励起される光）を照射することによって蛍光を
発するので、通常の着色画像とは識別し得る。しかし蛍
光染料や蛍光顔料では熱感応性がないので、充分な蛍光
強度を得るためにインク層に多量の蛍光物質を含有させ
ると、インク層の熱転写性が低下して転写像のかすれ、
むら等の原因となる。これに対し、本発明では耐熱性支
持体と熱溶融性インク層との間にワックス類及び／又は
樹脂を含有する熱溶融性物質層を設けたことにより熱溶
融性インク層の転写性を向上することができる。In other words, a transferred image obtained from a hot-melt ink layer containing such a fluorescent substance (also containing a coloring agent) has the same appearance as a normal colored image, but the transfer image obtained from the heat-melting ink layer containing such a fluorescent substance (also containing a coloring agent) has the same appearance as a normal colored image. They can be distinguished from ordinary colored images because they emit fluorescence when irradiated with light (which is often excited). However, fluorescent dyes and fluorescent pigments are not heat sensitive, so if the ink layer contains a large amount of fluorescent material in order to obtain sufficient fluorescence intensity, the thermal transferability of the ink layer will decrease, resulting in blurred transferred images.
This may cause unevenness, etc. In contrast, in the present invention, the transferability of the heat-melt ink layer is improved by providing a heat-melt material layer containing wax and/or resin between the heat-resistant support and the heat-melt ink layer. can do.
以下に１本発明の熱転写記録媒体を添付の図面によって
さらに詳細に説明する。The thermal transfer recording medium of the present invention will be explained in more detail below with reference to the accompanying drawings.
第３図は従来の熱転写記録媒体であり、この記録媒体１
′は耐熱性支持体１０上に熱溶融性インク層１１を設け
てなり、このインク層１１は耐熱性支持体１０の近傍に
は蛍光物質２を、また層表面近傍（自由表面寄り）には
着色剤３を存在させたものである。蛍光物質２及び着色
剤３は固着剤としてワックス類及び樹脂結着剤４中に含
有されそによって固着されている。FIG. 3 shows a conventional thermal transfer recording medium, and this recording medium 1
' is formed by providing a heat-melting ink layer 11 on a heat-resistant support 10, and this ink layer 11 has a fluorescent material 2 near the heat-resistant support 10 and a fluorescent substance 2 near the layer surface (closer to the free surface). Colorant 3 is present. The fluorescent substance 2 and the coloring agent 3 are contained in a wax and resin binder 4 as a fixing agent, and are fixed therewith.
一方、第１図は本発明の熱転写記録媒体であり、この記
録媒体１は耐熱性支持体１０上にワックス類及び／又は
樹脂を含有する熱溶融性物質層（第一の熱溶融性層）１
３と蛍光物質２及び着色剤３を含有する熱溶融性インク
層（第二の熱溶融性層）１１を順次設けてなるものであ
る。４はワックス類及び／又は樹脂である。On the other hand, FIG. 1 shows a thermal transfer recording medium of the present invention, and this recording medium 1 is a heat-fusible material layer (first heat-fusible layer) containing wax and/or resin on a heat-resistant support 10. 1
3, a heat-fusible ink layer (second heat-fusible layer) 11 containing a fluorescent material 2 and a colorant 3 are sequentially provided. 4 is wax and/or resin.
いま、例えば第３図のような従来の熱転写記録体１′を
用いて転写紙（記録体）に印字記録を行なえば、第４図
に示すようにサーマルヘッドＳのような印字手段によっ
て熱溶融性インク層１１は転写紙６上に溶融転写され、
印字転写画像１２の表面には蛍光物質２が、またその下
には着色剤３が存在するが、一部耐熱性支持体１０上に
は熱溶融性インク１４が残り、転写性の悪い画像１２′
となる傾向がある。これに対し、第１図ような本発明の
熱転写記録媒体１を用いて転写紙６に印字記録を行なえ
ば、第２図に示すように、サーマルヘッド５のような印
字手段によって熱溶融性インク層１１は転写紙６上に溶
融転写され、印字転写画像１２の表面には蛍光物質２が
またその下には着色剤３が存在する第一熱溶融性物質Ｎ
！Ｊ１３と、熱溶融性インク層１１との界面で熱溶融性
インク層１１が切れ易く、従って、転写性の高いかつ蛍
光強度も色濃度も高い画像１２が形成される。For example, if printing is performed on a transfer paper (recording material) using a conventional thermal transfer recording material 1' as shown in FIG. The ink layer 11 is melt-transferred onto the transfer paper 6,
Although the fluorescent material 2 is present on the surface of the printed transfer image 12 and the coloring agent 3 is present below it, the heat-melting ink 14 remains partially on the heat-resistant support 10, resulting in an image 12 with poor transferability. ′
There is a tendency to On the other hand, if printing is performed on the transfer paper 6 using the thermal transfer recording medium 1 of the present invention as shown in FIG. 1, as shown in FIG. The layer 11 is melt-transferred onto the transfer paper 6, and a first heat-fusible material N is formed on the surface of the printed transfer image 12 with the fluorescent material 2 and the colorant 3 underneath.
! The thermofusible ink layer 11 is easily cut at the interface between J13 and the thermofusible ink layer 11, so that an image 12 with high transferability, high fluorescence intensity, and high color density is formed.
次に本発明で使用される各成分について説明する。Next, each component used in the present invention will be explained.
まず、蛍光物質が前述のように多量に用いられても熱転
写性が低下しないように、蛍光染料にワックス的又は樹
脂的性状従って熱感応性を付与得るようなワックス状物
質固溶体及び／又は樹脂固溶体が使用される。これらの
固溶体に用いられるワックス状物質又は樹脂は蛍光染料
ともに固溶体としたときに融点又は軟化点が５０〜２５
０℃の範囲になり、且つ蛍光染料によって染着可能なも
のであれば全て使用できる。後者の条件を満たすために
は蛍光染料と親和し得る極性基（例えばアミド基、エス
テル基、水酸基、ラクトン結合基、アクリル基等）を有
するものが選ばれる。First, a solid solution of a wax-like substance and/or a solid solution of a resin that can impart wax-like or resin-like properties and thus heat sensitivity to the fluorescent dye is used so that thermal transferability does not deteriorate even when a large amount of the fluorescent substance is used as described above. is used. The wax-like substance or resin used in these solid solutions has a melting point or softening point of 50 to 25 when the fluorescent dye is made into a solid solution.
Any material can be used as long as it has a temperature range of 0° C. and can be dyed with a fluorescent dye. In order to satisfy the latter condition, those having polar groups (eg, amide group, ester group, hydroxyl group, lactone bonding group, acrylic group, etc.) that are compatible with fluorescent dyes are selected.
具体的には次の通りである。なお、参考のため融点又は
軟化点をカッコ内に併記した。まずワックス状物質とし
てはステアリン酸モノエタノールアミド（ｍｐ９１〜９
５℃）、ラウリン酸モノエタノールアミド（ｍｐ８０〜
８４℃）、やし油脂肪酸モノエタノールアミド（ｍｐ６
７〜７１℃）、ソルビタンベヘニン酸エステル（ｍｐ６
８．５°Ｃ）、ソルビタンステアリン酸エステル（ｍｐ
５１℃）、グリセリンモノステアリン酸エステル（ｍｐ
６３〜６８℃）、アセチルソルビット（ｍｐ９９．５℃
）、ベンゾイルソルビット（ｍｐ１２７℃）、アセチル
マンニット（ｍｐＨ９〜１２０℃）等が、また、樹脂と
しては数平均分子量１万のポリカプロラクトン（ｍｐ６
０〜６５℃）、平均分子量６０００のポリエチレングリ
コール（ｍｐ６２℃）、低縮重合メラミン・トルエンス
ルホンアミド樹脂（軟化点１０５℃）、低縮重合ベンジ
ルトルエンスルホンアミド樹脂（軟化点６８℃）、アク
リル樹脂（軟化点８５℃）、直鎖状ポリアミド樹脂（軟
化点６０℃）等が挙げられる。Specifically, it is as follows. For reference, the melting point or softening point is also shown in parentheses. First, as a waxy substance, stearic acid monoethanolamide (mp91-9
5℃), lauric acid monoethanolamide (mp80~
84°C), coconut oil fatty acid monoethanolamide (mp6
7-71℃), sorbitan behenic acid ester (mp6
8.5°C), sorbitan stearate (mp
51°C), glycerin monostearate (mp
63-68℃), acetyl sorbitol (mp99.5℃)
), benzoyl sorbitol (mp 127°C), acetyl mannite (mp 9 to 120°C), etc. As resins, polycaprolactone with a number average molecular weight of 10,000 (mp 6
0 to 65℃), polyethylene glycol with an average molecular weight of 6000 (mp 62℃), low condensation polymerization melamine/toluenesulfonamide resin (softening point 105℃), low condensation polymerization benzyltoluenesulfonamide resin (softening point 68℃), acrylic resin (softening point: 85°C), linear polyamide resin (softening point: 60°C), and the like.
一方、以上のワックス状物質又は樹脂を染着する蛍光染
料としてはチオフラビン（ＣＩ４９００５） ；ベーシ
ックイエローＨＧ （ＣＩ４６０４０） ；フルオレセ
イン（ＣＩ４５３５０） ；ローダミンＢ（ＣＩ４５１
７０） ：ローダミン６Ｇ（ＣＩ４５１６０） ；エオ
シン（Ｃ１１５３８０） ；一般的な白色の蛍光増白剤
例えばＣＩフルオレッセントブライテニグエージェント
８５、同１６６、同Ｉ７４；その他、以上の蛍光染料を
有機酸で油溶化（及び同時に水不溶化）したもの例えば
ローダミンＢと油溶化したオイルピンク＃３１２、ロー
ダミン６Ｇを油溶化したバリファストレッド１３０８
（以上はオリエント化学社製）；及び以上の蛍光染料を
金属塩、その他の沈殿剤でレーキ化したもの、例えばロ
ーダミン６Ｇをレーキ化したファーストローズ及びファ
ーストローズコンク（以上は大日精化社製）等が挙げら
れる。On the other hand, examples of fluorescent dyes that dye the above waxy substances or resins include Thioflavin (CI49005); Basic Yellow HG (CI46040); Fluorescein (CI45350); Rhodamine B (CI451);
70): Rhodamine 6G (CI45160); Eosin (C115380); General white fluorescent brighteners such as CI Fluorescent Breitenig Agent 85, CI Fluorescent Breitenig Agent 85, CI Fluorescent Breitenig Agent 166, CI CI I74; Oil-solubilized (and water-insolubilized at the same time), such as Oil Pink #312, which is made with Rhodamine B and oil-solubilized, Varifast Red 1308, which is made with Rhodamine 6G and made into oil-solubilized.
(The above are manufactured by Orient Kagaku Co., Ltd.); and lakes of the above fluorescent dyes with metal salts and other precipitants, such as First Rose and First Rose Conc which are lakes of Rhodamine 6G (the above are manufactured by Dainichiseika Kagaku Co., Ltd.) etc.
以上のような材料を用いて本発明の固溶体を製造する方
法としては塊状樹脂粉砕法、乳化重合法、樹脂析出法等
があるが、中でも塊状樹脂粉砕法が好ましい。ここで、
塊状樹脂粉砕法とは例えば英国特許第８４５４６２号明
細書に記載されているような樹脂及び蛍光染料を溶融混
和後、冷却固化せしめ、得られた塊を粉砕するという方
法であり、乳化重合法とは例えば英国特許第８２２７０
９号明細書に記載されているような蛍光染料の熱水溶液
に乳化重合による樹脂粉末を加えて染料を樹脂粉末に吸
尽せしめ、ついでこれを濾過乾燥するという方法であり
、また、樹脂析出法とは樹脂の水溶性塩及び蛍光染料を
溶融した水溶液にＡ Ｑ ２ （ＳＯ４）３・８Ｈ２０
のような水溶性金属塩の水溶液を加えて反応させ必要あ
れば液を酸性にして、溶存する樹脂を蛍光染料を付着し
たまま金属塩として析出させ、ついでこれを濾過乾燥す
るという方法である６
なお、このようにして得られる固溶体は蛍光染料の濃度
の増大とともに蛍光強度も増大するが、ある濃度以上に
なると濃度消耗を起こして蛍光強度は減少する。このた
め固溶体中の蛍光染料の割合は０．１〜５．０重量％程
度が適当である。Methods for producing the solid solution of the present invention using the above-mentioned materials include a lump resin pulverization method, an emulsion polymerization method, a resin precipitation method, etc. Among them, a lump resin pulverization method is preferred. here,
The lump resin pulverization method is a method of melting and mixing a resin and a fluorescent dye as described in British Patent No. 845,462, cooling and solidifying the resulting lump, and pulverizing the resulting lump. For example, British Patent No. 82270
9, a resin powder produced by emulsion polymerization is added to a hot aqueous solution of a fluorescent dye to exhaust the dye into the resin powder, which is then filtered and dried. What is A Q 2 (SO4)3.8H20 in an aqueous solution containing a water-soluble salt of a resin and a fluorescent dye?
This is a method in which an aqueous solution of a water-soluble metal salt such as is added and reacted, the solution is made acidic if necessary, the dissolved resin is precipitated as a metal salt with the fluorescent dye still attached, and this is then filtered and dried6. Note that the fluorescence intensity of the thus obtained solid solution increases as the concentration of the fluorescent dye increases, but when the concentration exceeds a certain level, concentration depletion occurs and the fluorescence intensity decreases. Therefore, the appropriate proportion of the fluorescent dye in the solid solution is about 0.1 to 5.0% by weight.
次に前記塊状樹脂粉砕法による蛍光染料のワックス状物
質又は樹脂固溶体の製造例を示す。Next, an example of producing a wax-like substance or a resin solid solution of a fluorescent dye by the above-mentioned bulk resin crushing method will be shown.
なお部は全て重量部である。All parts are by weight.
製造例１
（ｂ）ローダミンＢエキストラ １．０部（ｃ）
ローダミン６ＧＤＮエキストラ １．０部（ｄ）ブ
リリアントスルホフラビン ０．５部を用意し、まず（
ａ）を１００℃に加熱溶融し、透明になったところで温
度を１７０〜１８０℃に上昇せしめる。次にこれに（ｂ
）、（Ｃ）及び（ｄ）を加えて溶解し、冷却固化させた
後粉砕することにより、赤橙色の蛍光を発する軟化点１
０５℃の樹脂固溶体を得た。このものの蛍光極大波長は
６０５ｎｍであり、また、この樹脂固溶体をポリエステ
ルフィルム上で約１０μｍ厚の薄膜としたときの相対蛍
光強度は１１２であった。なお、これらの性能は日立製
作所社製の６５０−６０蛍光スペクトロホトメーターを
用いてスキャン速度：１２０ｎｍ／分、スリット巾：励
起側及び発光側ともにｌｎｍの条件で測定した。Production Example 1 (b) Rhodamine B Extra 1.0 part (c)
Prepare 1.0 part of Rhodamine 6GDN Extra (d) 0.5 part of brilliant sulfoflavin, and first (
A) is heated and melted at 100°C, and when it becomes transparent, the temperature is raised to 170-180°C. Then add this (b
), (C) and (d) are added, dissolved, cooled and solidified, and then crushed to give a softening point 1 that emits red-orange fluorescence.
A resin solid solution at 05°C was obtained. The maximum fluorescence wavelength of this product was 605 nm, and the relative fluorescence intensity was 112 when this resin solid solution was formed into a thin film with a thickness of about 10 μm on a polyester film. These performances were measured using a 650-60 fluorescence spectrophotometer manufactured by Hitachi, Ltd. under the conditions of a scan speed of 120 nm/min and a slit width of 1 nm on both the excitation side and the emission side.
製造例２〜６
下記処方のワックス状物質又は樹脂及び蛍光染料を用い
て製造例１と同様にして蛍光染料のワックス状物質固溶
体又は樹脂固溶体を作った。Production Examples 2 to 6 Waxy substance solid solutions or resin solid solutions of fluorescent dyes were prepared in the same manner as in Production Example 1 using waxy substances or resins and fluorescent dyes having the following formulations.
製造例２の処方：
鎖状ポリアミド樹脂 ９７．５部ローダミ
ンＢエキストラ １．０部ローダミン６ＧＤ
Ｎエキストラ １．０部ブリリアントスルホフ
ラビン ０．５部製造例３の処方：
ソルビタンベヘニン酸エステル ９８．５部ローダミ
ンＢエキストラ ０．６部ローダミン６ＧＤ
Ｎエキストラ ０．６部ブリリアントスルホフ
ラビン ０．３部製造例４の処方：
やし油脂肪酸モノエタノールアミド ９９．５部ブリ
リアントスルホフラビン ０．５部製造例５の処方
：
ソルビタンベヘニン酸エステル ９６．５部Ｃ，１，
フルオレツセン：ブライニング ３．５部エージニント
１７６
製造例６の処方：
鎖状ポリアミド樹脂 ７３．１部ソルビタ
ンベヘニン酸エステル ２４．４部ローダミンＢエキ
ストラ １．０部ローダミン６ＧＤＮエキス
トラ １．０部ブリリアントスルホフラビン
０．５部以上のようにして得られた各固溶体の蛍光
極大波長、蛍光色及び相対蛍光強度は−１の通りである
。融点又は軟化点も併記した。Prescription of Production Example 2: Chain polyamide resin 97.5 parts Rhodamine B Extra 1.0 parts Rhodamine 6GD
N Extra 1.0 parts Brilliant Sulfoflavine 0.5 parts Preparation of Production Example 3: Sorbitan behenate 98.5 parts Rhodamine B Extra 0.6 parts Rhodamine 6GD
N Extra 0.6 parts Brilliant sulfoflavine 0.3 parts Formula for Production Example 4: Coconut oil fatty acid monoethanolamide 99.5 parts Brilliant Sulfoflavine 0.5 parts Formula for Production Example 5: Sorbitan behenate 96 .5 Part C, 1,
Fluoretscen: Brining 3.5 parts Agenint 176 Preparation of Production Example 6: Chain polyamide resin 73.1 parts Sorbitan behenic acid ester 24.4 parts Rhodamine B Extra 1.0 parts Rhodamine 6GDN Extra 1.0 parts Brilliant Sulfonate Flavin
The fluorescence maximum wavelength, fluorescence color, and relative fluorescence intensity of each solid solution obtained in the manner of 0.5 parts or more are as shown in -1. The melting point or softening point is also listed.
表−１
本発明で使用される固溶体蛍光物質はまた市販品として
例えばシンロイヒ社製のＦＺ−２０００（軟化点１１０
℃）、ＦＺ−３０００（軟化点１２０〜１３０°Ｃ）、
ＢＯ−１００（軟化点９０〜１００℃）、ＦＭ−１１（
軟化点１１０〜１．２５℃）（以上はメラミン・トルエ
ンスルホンアミド樹脂系） ； ５Ｍ−１３（軟化点７
１℃）、５Ｂ−１０（軟化点９０℃）（以上はアクリル
樹脂系）等が入手できる。Table 1 The solid solution fluorescent material used in the present invention is also commercially available, such as FZ-2000 manufactured by Shinloihi Co., Ltd. (softening point 110
°C), FZ-3000 (softening point 120-130 °C),
BO-100 (softening point 90-100℃), FM-11 (
5M-13 (softening point 7)
1°C), 5B-10 (softening point: 90°C) (acrylic resin type), and the like.
以上のような固溶体蛍光物質の使用量は転写像の蛍光強
度によって任意に選択できるが、一般には熱溶融性イン
ク層１１の総重量の２０〜７０％、好ましくは２０〜６
０％程度が適当である。The amount of the solid solution fluorescent substance used as described above can be arbitrarily selected depending on the fluorescence intensity of the transferred image, but generally it is 20 to 70% of the total weight of the heat-melting ink layer 11, preferably 20 to 6%.
Approximately 0% is appropriate.
次に熱溶融性インク層１１に使用されるその他の材料に
ついて説明する。Next, other materials used for the heat-melting ink layer 11 will be explained.
まず、着色剤として使用される染料又は顔料はこの分野
で通常使用されているものでよい。First, the dyes or pigments used as colorants may be those commonly used in this field.
即ち、染料としては油溶性染料例えばスミカロンバイオ
レットＲＳ、ダイアニクスファーストバイオレット３Ｒ
−ＦＳ、カヤロンポリオールブリリアントブルーＮ−Ｂ
ＧＭ（以上はアントラキノン系染料）、 カヤロンポリ
オールブリリアントブルーＢＭ、カヤロンポリオールダ
ークブルー２８Ｍ、スミカロンジアゾブラック５Ｇ、ミ
クタセルブラッり５ＧＨ（以上はアゾ染料）、ダイレク
トダークグリーンＢ、ダイレクトブラウン阿、ダイレク
トファストブラックＤ（以上は直接染料）、カヤノール
ミリングシアニン５Ｒ（酸性染料）、スミカリルブルー
６Ｇ、アイゼンマラカイトグリーン、ローダミンＢ、ロ
ーダミン６Ｇ、ビクトリアブルー（以上は塩基性染料）
等が挙げられる。That is, the dyes include oil-soluble dyes such as Sumikalon Violet RS and Dianix Fast Violet 3R.
-FS, Kayalon Polyol Brilliant Blue N-B
GM (the above are anthraquinone dyes), Kayalon Polyol Brilliant Blue BM, Kayalon Polyol Dark Blue 28M, Sumikalon Diazo Black 5G, Mictacel Black 5GH (the above are azo dyes), Direct Dark Green B, Direct Brown A, Direct Fast Black D (the above are direct dyes), Kayanol Milling Cyanine 5R (acidic dye), Sumicalil Blue 6G, Eisenmalachite Green, Rhodamine B, Rhodamine 6G, Victoria Blue (the above are basic dyes)
etc.
顔料としてはビクトリアブルーレーキ、無金属フタロシ
アニン、フタロシアニン、ファストスカイブルー、パー
マネントレッド４Ｒ、ブリリアントファストスカーレッ
ト、ブリリアントカーミンＢＳ、パーマネントイーミン
ＦＢ、リソールレッド、パーマネントレッドＦ５Ｒ、ブ
リリアントカーミン６Ｂ、ビグメントスカーレット３Ｂ
、ローダミンレーキＢ、ローダミンレーキＴ、アリザリ
ンレーキ、ファストレッド、ブライトレッデＧトナー、
リオノールレッドＣＰ −Ａ、クロムイエロー（黄鉛）
、ジンクイエロージンククロメート（亜鉛黄）、レモン
イエロー（クロム酸バリウム）、カドミウムイエロー、
ナフトールイエローＢ、ハンザイエロー５Ｇ、ハンザイ
エロー３Ｇ、ハンザイエローＧ、ハンザイエローＡ、ハ
ンザイエローＲＮ、ハンザイエローＲ、ベンジジンイエ
ロー、ベンジジンイエローＧ、ベンジジンイエローＧＲ
、パーマネントイエローＮＣＧ、キノリンイエローレー
キ、ファストイエロー等が挙げられる。本発明では耐光
性、色移行性、耐溶解性等の点か′ら着色剤については
顔料の使用の方が好ましい。Pigments include Victoria Blue Lake, metal-free phthalocyanine, phthalocyanine, Fast Sky Blue, Permanent Red 4R, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent E-Min FB, Lysole Red, Permanent Red F5R, Brilliant Carmine 6B, and Pigment Scarlet 3B.
, Rhodamine Lake B, Rhodamine Lake T, Alizarin Lake, Fast Red, Bright Red G Toner,
Lionor Red CP-A, Chrome Yellow (Yellow)
, zinc yellow zinc chromate (zinc yellow), lemon yellow (barium chromate), cadmium yellow,
Naphthol Yellow B, Hansa Yellow 5G, Hansa Yellow 3G, Hansa Yellow G, Hansa Yellow A, Hansa Yellow RN, Hansa Yellow R, Benzidine Yellow, Benzidine Yellow G, Benzidine Yellow GR
, permanent yellow NCG, quinoline yellow lake, fast yellow, etc. In the present invention, it is preferable to use pigments as the coloring agent in terms of light resistance, color migration properties, dissolution resistance, etc.
ワックス類としてはカルナバワックス、オーキニリーワ
ックス、マイクロクリスタリンワックス、パラフィンワ
ックス、セレシンワックス、モンタンろう、キャンデリ
ラワックス、セラックろう、チュウハクろう、パームろ
う、蜜ろう、低分子量ポリエチレン、ポリステアリン酸
ビニル等の容易に熱溶融し得るワックスが挙げられる。Waxes include carnauba wax, oakeny wax, microcrystalline wax, paraffin wax, ceresin wax, montan wax, candelilla wax, shellac wax, turmeric wax, palm wax, beeswax, low molecular weight polyethylene, polyvinyl stearate, etc. Examples include waxes that can be easily melted by heat.
また、樹脂としてはポリ塩化ビニル、ポリ酢酸ビニル、
ポリ弗化ビニル、ポリビニルブチラール、ポリ塩化ビニ
リデン、ポリビニルアルコール、塩化ビニル−酢酸ビニ
ル共重合体、塩化ビニル−塩化ビニルデン共重合体、ポ
リスチレン、ポリエチレン、エチレン−酢酸ビニル共重
合体、スチレン−ブタジェン共重合体、アクリロニトリ
ル−スチレン−ブタジェン共重合体、セルロースエステ
ル類、セルロースエーテル類、石油類脂等の容易に熱軟
化又は熱溶融し得る樹脂が挙げられる。In addition, the resins include polyvinyl chloride, polyvinyl acetate,
Polyvinyl fluoride, polyvinyl butyral, polyvinylidene chloride, polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl chloride copolymer, polystyrene, polyethylene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer Examples include resins that can be easily heat-softened or heat-melted, such as acrylonitrile-styrene-butadiene copolymers, cellulose esters, cellulose ethers, and petroleum fats.
熱溶融性インク層１１にはその他、柔軟剤を添加するこ
とができる。柔軟剤としては流動パラフィン、鉱物油、
動物油（例えば鯨油）、植物油（例えば菜種油）等が挙
げられる。使用量は熱溶融性インク層１１の全重量の２
％以下が適当である。In addition, a softener can be added to the heat-melting ink layer 11. As softeners, liquid paraffin, mineral oil,
Examples include animal oils (eg, whale oil), vegetable oils (eg, rapeseed oil), and the like. The amount used is 2 of the total weight of the heat-melting ink layer 11.
% or less is appropriate.
耐熱性支持体１０としてはポリエステルフィルム、ポリ
プロピレンフィルム、ポリイミドフィルム、ポリカーボ
ネートフィルム、グラシン紙、コンデンサー紙等が使用
される。厚さは３〜２０μｍ程度が適当である。更に、
本発明の熱転写記録媒体を高速及び／又は高エネルギー
で使用する場合には、耐熱性支持体１０の片面に耐熱処
理を施しても良い。As the heat-resistant support 10, polyester film, polypropylene film, polyimide film, polycarbonate film, glassine paper, condenser paper, etc. are used. Appropriate thickness is about 3 to 20 μm. Furthermore,
When the thermal transfer recording medium of the present invention is used at high speed and/or high energy, one side of the heat-resistant support 10 may be subjected to heat-resistant treatment.
本発明の熱転写記録媒体を作る方法としては、まづ耐熱
性支持体１０上にワックス類及び／又は樹脂を含有する
熱溶融性物質を溶融したもの（以降「アンダー液」と称
することがある）を塗工して０．５〜３μｍ厚程度の熱
溶融性物質層１３を形成した後、その上に蛍光物質及び
着色剤を含む熱溶融性インクを溶融塗布又は分散塗布し
て１〜４μｍ厚程度の熱溶融性にインク層１１を形成す
ることにより、積層型の熱転写記録媒体が得られる。ア
ンダー液或いは熱溶融性インク液には、その他の成分と
して柔軟剤等の添加剤を添加することができる。As a method for producing the thermal transfer recording medium of the present invention, first, a heat-melting substance containing wax and/or resin is melted on a heat-resistant support 10 (hereinafter sometimes referred to as "under liquid"). After forming a heat-fusible material layer 13 with a thickness of about 0.5 to 3 μm, a heat-fusible ink containing a fluorescent material and a coloring agent is melt-coated or dispersed thereon to form a layer 13 with a thickness of 1 to 4 μm. By forming the ink layer 11 with a certain degree of heat melting property, a laminated thermal transfer recording medium can be obtained. Additives such as softeners can be added to the under liquid or the heat-melting ink liquid as other components.
以上のように、本発明の熱転写記録媒体において熱溶融
性物質層１３のワックス類及び／又は樹脂の使用量は熱
溶融性物質層１３全体に対し、ワックス類が６０〜９５
重量％好ましくは７５〜９０重景％くらいで、樹脂が３
〜４０重量％好ましくは５〜２５重量％くらいが適当で
ある。添加剤の使用量は通常、熱溶融性物質層１３の全
体に対し２重量％以下である。As described above, in the thermal transfer recording medium of the present invention, the amount of wax and/or resin used in the heat-fusible material layer 13 is 60 to 95% of the wax and/or resin based on the entire heat-fusible material layer 13.
The weight percent is preferably about 75 to 90 weight percent, and the resin is 3
Approximately 40% by weight, preferably 5 to 25% by weight. The amount of the additive used is usually 2% by weight or less based on the entire heat-fusible material layer 13.
熱溶融性インク層１１においての蛍光物質、着色剤、ワ
ックス類、樹脂などの使用量は熱溶融性インク層１１の
全体に対し夫々５〜４０重量％、１〜３０重量％、４０
〜９０重量％、２〜２０重量％とするのが適当であり、
特に１０〜２５重量％、３〜１５重量％、７５〜８５重
量％、３〜１５重量％とするのが好ましい。添加剤の使
用量は通常、熱溶融性インク層１１の全体に対し２重量
％以下である。The amounts of fluorescent substances, colorants, waxes, resins, etc. used in the heat-melting ink layer 11 are 5 to 40% by weight, 1 to 30% by weight, and 40% by weight, respectively, based on the entire heat-melting ink layer 11.
~90% by weight, 2 to 20% by weight is appropriate,
In particular, it is preferably 10 to 25% by weight, 3 to 15% by weight, 75 to 85% by weight, and 3 to 15% by weight. The amount of additive used is usually 2% by weight or less based on the entire heat-melting ink layer 11.
本発明の熱転写記録媒体を用いて印字記録を行なうには
、従来と同様第２図に示したように、記録媒体の熱溶融
性インク層１１面に記録用紙６を重ね、記録媒体の耐熱
溶性支持体１０側からサーマルヘッド５を当ててその部
分のインク層を記録用紙６上に転写すればよい。第２図
におけるには転写されたインク層即ち画像を表わしてい
る。In order to perform print recording using the thermal transfer recording medium of the present invention, as shown in FIG. The thermal head 5 may be applied from the support 10 side to transfer the ink layer of that portion onto the recording paper 6. FIG. 2 shows the transferred ink layer or image.
以下に本発明を実施例によって説明する。なお、部及び
％は全で重量基準である。The present invention will be explained below by way of examples. Note that all parts and percentages are based on weight.
実施例１〜３
下記の組成からなるアンダー液、熱溶融性インク（蛍光
インクと着色インク）をそれぞれ溶融分散して均一分散
液を調製した。Examples 1 to 3 Uniform dispersion liquids were prepared by melting and dispersing an under liquid and heat-melting ink (fluorescent ink and colored ink) having the following compositions.
アンダー液：
カルナバワックス ２０部キャンデリラ
ワックス １６部パラフィン
５０部石油樹脂 １
３部流動パラフィン １部蛍光イン
ク（赤橙色蛍光）：
製造例６でつくった蛍光物質 ５０．０部キャンデリ
ラワックス ４９．０部流動パラフィン
１．０部着色インク（赤色）：
セイ力ファーストイエロー２０００Ｍ ５部（大日
精化社製）
カルナバワックスＮｏ、 １ １５．８部パラ
フィン（軟化点的６８℃） ６３．２部石油樹脂
５部流動パラフィン
１部次に、約６μｍ厚のポリエステルフィ
ルム上にアンダー液を塗膜厚が下記表−２に示す値とな
るように溶融塗布して熱溶融性物質層を形成した後、そ
の上に蛍光インクと着色インクを混合し塗膜厚が表−２
に示す値となるように溶融塗布して熱溶融性インク層を
形成することにより熱転写記録媒体を作った。Under liquid: Carnauba wax 20 parts Candelilla wax 16 parts Paraffin
50 parts petroleum resin 1
3 parts liquid paraffin 1 part Fluorescent ink (red-orange fluorescent): Fluorescent substance made in Production Example 6 50.0 parts Candelilla wax 49.0 parts Liquid paraffin
1.0 parts Colored ink (red): Seiryoku Fast Yellow 2000M 5 parts (manufactured by Dainichiseika Co., Ltd.) Carnauba wax No. 1 15.8 parts Paraffin (softening point: 68°C) 63.2 parts Petroleum resin 5 parts Fluid paraffin
Part 1 Next, an under liquid was melt-coated onto a polyester film with a thickness of about 6 μm to form a layer of heat-melting material so that the coating thickness would be as shown in Table 2 below, and then a fluorescent ink was applied on top of it. and colored ink are mixed, and the coating film thickness is shown in Table-2.
A thermal transfer recording medium was prepared by melt-coating to form a hot-melt ink layer having the values shown in .
表−２
傘１：蛍光及び着色インク層全体に対する蛍光物質の割
合。Table 2 Umbrella 1: Ratio of fluorescent substance to the entire fluorescent and colored ink layer.
傘２：蛍光及び着色インク層全体に対する着色剤の割合
。Umbrella 2: Percentage of colorant to the entire fluorescent and colored ink layer.
比較例１
蛍光物質としてローダミンＢエキストラ−ローダミン６
ＧＤＮ混合（１：１）染料のトリアジン樹脂固溶体（シ
ンロイヒ社製レッドオレンジカラーＦＡ−４１、軟化点
１５０℃以上）（塊状樹脂枠法により製造されたもの）
を用いた他は実施例１と同じ方法で蛍光インク及び着色
インクを調製した。Comparative Example 1 Rhodamine B Extra-Rhodamine 6 as a fluorescent substance
Triazine resin solid solution of GDN mixed (1:1) dye (red orange color FA-41 manufactured by Shinroihi Co., Ltd., softening point 150°C or higher) (manufactured by bulk resin frame method)
A fluorescent ink and a colored ink were prepared in the same manner as in Example 1 except that the following was used.
次に、両インクを蛍光インク／着色インク＝１／１（重
合）の比率で混合し、実施例１と同濃度の蛍光物質及び
着色剤を含む混合インク（蛍光物質２５．０％、着色剤
７．５％）を調製し、これを約６μｍ厚のポリエステル
フィルム上に、熱溶融性物質を設けることなく直接、塗
膜厚が約４．０μｍとなるよう溶融塗布して熱溶融性イ
ンク層を設けた比較の熱転写記録媒体をつくった。Next, both inks were mixed at a ratio of fluorescent ink/colored ink = 1/1 (polymerization), and a mixed ink containing the same concentration of fluorescent material and colorant as in Example 1 (25.0% fluorescent material, colorant 7.5%) and melt-coated it directly onto a polyester film with a thickness of about 6 μm without providing a heat-melting substance so that the film thickness was about 4.0 μm to form a heat-melting ink layer. A comparative thermal transfer recording medium was prepared.
比較例２
混合インクとして下記組成のもの（蛍光及び着色インク
層全体に対し蛍光物質は５０％、着色剤は７．５％）を
用いた他は比較例１と同じ方法でポリエステルフィルム
上に直接熱溶融性インク層を設けて比較の熱転写記録媒
体をつくった。Comparative Example 2 Directly printed on a polyester film in the same manner as Comparative Example 1 except that the following composition was used as a mixed ink (50% fluorescent material and 7.5% colorant for the entire fluorescent and colored ink layer). A comparative thermal transfer recording medium was prepared by providing a heat-melting ink layer.
混合インク：
レッドオレンジカラーＦＡ−４１５０，０部すノールレ
ッドＣＰ−Ａ ５．０部セイ力ファー
ストイエロー２２００Ｍ ２．５部カルナバワック
ス ７．５部キャンデリラワックス
１４．０部パラフィン（ｍｐ約６８．５℃）
１５．０部石油樹脂
５．０部流動パラフィン １．
０部以上５種の記録媒体を用い、それぞれのインク層面
に市販のｐｐｃ （普通紙複写機）用転写紙を重ねサー
マルヘッドへの印加熱エネルギー０．５０ｍＪ／ドツト
（８ドツト／ｍｍヘッドにおいて）及び押付は圧約５０
０ｇ／ｃｍ２の条件で記録媒体の耐熱性支持体側からサ
ーマルヘッドを当て、その部分の各インク層を転写紙（
普通紙）上に溶融転写した後、１００ｍ５ｅｃ後に記録
媒体を転写紙面に対し鋭角に引剥すことにより、印字記
録を行なった。Mixed ink: Red Orange Color FA-4150, 0 parts Norred CP-A 5.0 parts Seiryoku Fast Yellow 2200M 2.5 parts Carnauba wax 7.5 parts Candelilla wax
14.0 parts paraffin (mp approx. 68.5℃)
15.0 parts petroleum resin
5.0 parts liquid paraffin 1.
Using 0 copies or more of 5 types of recording media, a commercially available PPC (plain paper copying machine) transfer paper is placed on the surface of each ink layer, and heating energy is applied to the thermal head at 0.50 mJ/dot (for an 8 dot/mm head). And the pressure is about 50
A thermal head is applied from the heat-resistant support side of the recording medium under the condition of 0 g/cm2, and each ink layer in that area is transferred to a transfer paper (
After melt-transferring onto plain paper, printing was performed by peeling off the recording medium at an acute angle to the surface of the transfer paper after 100 m5ec.
その結果を表−３に示した。The results are shown in Table-3.
また、これら記録媒体及び印字物について蛍光スペクト
ルを測定し、併せて表−３に示した。Furthermore, the fluorescence spectra of these recording media and printed matter were measured and are also shown in Table 3.
表 −３
１１３：日立製作所社１ｉｉ６５０−６０蛍光スペクト
ロホトメーター（スキャン速度：１２０ｎｍ／分、スリ
ット巾：励起側及び発光側ともｌｎｍ）で測定。Table 3 113: Measured with a Hitachi, Ltd. 1ii650-60 fluorescence spectrophotometer (scan speed: 120 nm/min, slit width: 1 nm on both excitation and emission sides).
拳４：マクベス社製ＲＤ−９１４グリーンフィルターで
の測定値。Fist 4: Measured value using Macbeth's RD-914 green filter.
表−３から明らかなように同じ濃度の蛍光物質を使用し
たにも拘らず、本発明品は比較品に比べて高強度の蛍光
を発している。比較品で実施例１と同強度の蛍光を得る
には比較例２のように蛍光物質がインク層中に約２５％
必要となり、その結果、特に印字の細線部にカスレが発
生する。As is clear from Table 3, even though the same concentration of fluorescent substance was used, the product of the present invention emits a higher intensity of fluorescence than the comparative product. In order to obtain fluorescence with the same intensity as Example 1 with a comparative product, approximately 25% of the fluorescent material must be in the ink layer as in Comparative Example 2.
As a result, fading occurs particularly in the fine line portions of the print.
本発明の熱転写記録媒体は熱溶融性インク層中に蛍光物
質を含有するので、印字画像の偽造が防止できるばかり
でなく、本発明の熱転写記録媒体は耐熱性支持体上に第
一の熱溶融性物質層を設けるとともに蛍光物質及び着色
剤を含む第二の熱溶融性インク層を第一の熱溶融性物質
層の上に設けたことにより、印字転写画像の色濃度及び
蛍光色強度が高くなることに加えて、熱転写性従って印
字品質を向上することができる。Since the thermal transfer recording medium of the present invention contains a fluorescent substance in the heat-fusible ink layer, not only can forgery of printed images be prevented, but also the thermal transfer recording medium of the present invention has a first heat-fusible ink layer on a heat-resistant support. By providing the thermofusible material layer and the second thermofusible ink layer containing the fluorescent material and colorant on the first thermofusible material layer, the color density and fluorescent color intensity of the printed transfer image are high. In addition to this, thermal transferability and therefore print quality can be improved.
第１図は本発明に係る熱転写記録媒体の断面図、第２図
はその記録媒体を用いた印字記録法について説明図、第
３図は従来の熱転写記録媒体の断面図、第４図はその記
録媒体を用いた印字記録法についての説明図である。
１・・・熱転写記録媒体 ２・・・蛍光物質３・・
・着色剤FIG. 1 is a cross-sectional view of a thermal transfer recording medium according to the present invention, FIG. 2 is an explanatory diagram of a print recording method using the recording medium, FIG. 3 is a cross-sectional view of a conventional thermal transfer recording medium, and FIG. FIG. 2 is an explanatory diagram of a print recording method using a recording medium. 1... Thermal transfer recording medium 2... Fluorescent material 3...
・Coloring agent
Claims (1)
分とした熱溶融性物質層と、着色剤、蛍光物質およびワ
ックス類及び／又は樹脂を主成分とした熱溶融性インク
層とを順次設けたことを特徴とする熱転写記録媒体。1. A heat-melt material layer containing waxes and/or resins as the main components and a heat-melt ink layer containing colorants, fluorescent substances, and waxes and/or resins as main components on a heat-resistant support. A thermal transfer recording medium characterized by sequentially provided.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62039522A JPS63205285A (en) | 1987-02-20 | 1987-02-20 | Thermal transfer recording medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62039522A JPS63205285A (en) | 1987-02-20 | 1987-02-20 | Thermal transfer recording medium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63205285A true JPS63205285A (en) | 1988-08-24 |
Family
ID=12555376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62039522A Pending JPS63205285A (en) | 1987-02-20 | 1987-02-20 | Thermal transfer recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63205285A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01258991A (en) * | 1988-04-08 | 1989-10-16 | Dainippon Printing Co Ltd | Thermal transfer sheet |
| CN108528080A (en) * | 2018-03-05 | 2018-09-14 | 库尔兹压烫科技（合肥）有限公司 | A kind of cold wave foil promoting ink adhesion |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60236788A (en) * | 1984-05-10 | 1985-11-25 | Fuji Xerox Co Ltd | Heat transfer recording medium |
| JPS6157390A (en) * | 1984-08-29 | 1986-03-24 | Ricoh Co Ltd | Thermal transfer recording medium |
| JPS61110590A (en) * | 1984-11-06 | 1986-05-28 | Olympus Optical Co Ltd | Heat-meltable transfer sheet |
| JPS61273991A (en) * | 1985-05-30 | 1986-12-04 | Canon Inc | Thermal transfer material |
-
1987
- 1987-02-20 JP JP62039522A patent/JPS63205285A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60236788A (en) * | 1984-05-10 | 1985-11-25 | Fuji Xerox Co Ltd | Heat transfer recording medium |
| JPS6157390A (en) * | 1984-08-29 | 1986-03-24 | Ricoh Co Ltd | Thermal transfer recording medium |
| JPS61110590A (en) * | 1984-11-06 | 1986-05-28 | Olympus Optical Co Ltd | Heat-meltable transfer sheet |
| JPS61273991A (en) * | 1985-05-30 | 1986-12-04 | Canon Inc | Thermal transfer material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01258991A (en) * | 1988-04-08 | 1989-10-16 | Dainippon Printing Co Ltd | Thermal transfer sheet |
| CN108528080A (en) * | 2018-03-05 | 2018-09-14 | 库尔兹压烫科技（合肥）有限公司 | A kind of cold wave foil promoting ink adhesion |
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