JPH054913B2 - - Google Patents
Info
- Publication number
- JPH054913B2 JPH054913B2 JP60142599A JP14259985A JPH054913B2 JP H054913 B2 JPH054913 B2 JP H054913B2 JP 60142599 A JP60142599 A JP 60142599A JP 14259985 A JP14259985 A JP 14259985A JP H054913 B2 JPH054913 B2 JP H054913B2
- Authority
- JP
- Japan
- Prior art keywords
- diisocyanate
- reactant
- heat
- sensitive recording
- colored
- 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
- -1 imino compound Chemical class 0.000 claims description 15
- 239000000376 reactant Substances 0.000 claims description 15
- 239000012948 isocyanate Substances 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 9
- 239000012790 adhesive layer Substances 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 description 9
- 238000004040 coloring Methods 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- 239000004014 plasticizer Substances 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZUXXEBDVLVNWTK-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3-iminoisoindol-1-amine Chemical compound ClC1=C(Cl)C(Cl)=C2C(=N)NC(=N)C2=C1Cl ZUXXEBDVLVNWTK-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 description 2
- 238000001454 recorded image Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000003232 water-soluble binding agent Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- HMVKMAMIRAVXAN-UHFFFAOYSA-N 1,3-dichloro-2-isocyanatobenzene Chemical compound ClC1=CC=CC(Cl)=C1N=C=O HMVKMAMIRAVXAN-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- SIZPGZFVROGOIR-UHFFFAOYSA-N 1,4-diisocyanatonaphthalene Chemical compound C1=CC=C2C(N=C=O)=CC=C(N=C=O)C2=C1 SIZPGZFVROGOIR-UHFFFAOYSA-N 0.000 description 1
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- ICLCCFKUSALICQ-UHFFFAOYSA-N 1-isocyanato-4-(4-isocyanato-3-methylphenyl)-2-methylbenzene Chemical compound C1=C(N=C=O)C(C)=CC(C=2C=C(C)C(N=C=O)=CC=2)=C1 ICLCCFKUSALICQ-UHFFFAOYSA-N 0.000 description 1
- WCOXQTXVACYMLM-UHFFFAOYSA-N 2,3-bis(12-hydroxyoctadecanoyloxy)propyl 12-hydroxyoctadecanoate Chemical compound CCCCCCC(O)CCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCC(O)CCCCCC)COC(=O)CCCCCCCCCCC(O)CCCCCC WCOXQTXVACYMLM-UHFFFAOYSA-N 0.000 description 1
- LLIPDRQCCIZQPL-UHFFFAOYSA-N 2,5-dichloro-5-isocyanatocyclohexa-1,3-diene Chemical compound ClC1=CCC(Cl)(N=C=O)C=C1 LLIPDRQCCIZQPL-UHFFFAOYSA-N 0.000 description 1
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- UKMBAYGWYFUXEF-UHFFFAOYSA-N 3-amino-4,5,6,7-tetrabromoisoindol-1-one Chemical compound BrC1=C(Br)C(Br)=C(Br)C2=C1C(N)=NC2=O UKMBAYGWYFUXEF-UHFFFAOYSA-N 0.000 description 1
- LOZJNNNVLREXGU-UHFFFAOYSA-N 3-amino-4,5,6,7-tetrachloroisoindol-1-one Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C2=C1C(N)=NC2=O LOZJNNNVLREXGU-UHFFFAOYSA-N 0.000 description 1
- FOHPCQTYGFYWHT-UHFFFAOYSA-N 3-amino-4,5,6,7-tetrafluoroisoindol-1-one Chemical compound FC1=C(F)C(F)=C(F)C2=C1C(N)=NC2=O FOHPCQTYGFYWHT-UHFFFAOYSA-N 0.000 description 1
- NOFJASWEFDKODU-UHFFFAOYSA-N 3-amino-5,6-dichloroisoindol-1-one Chemical compound ClC1=C(Cl)C=C2C(N)=NC(=O)C2=C1 NOFJASWEFDKODU-UHFFFAOYSA-N 0.000 description 1
- MMBYJYAFFGKUDC-UHFFFAOYSA-N 3-aminoisoindol-1-one Chemical compound C1=CC=C2C(N)=NC(=O)C2=C1 MMBYJYAFFGKUDC-UHFFFAOYSA-N 0.000 description 1
- RZVCEPSDYHAHLX-UHFFFAOYSA-N 3-iminoisoindol-1-amine Chemical compound C1=CC=C2C(N)=NC(=N)C2=C1 RZVCEPSDYHAHLX-UHFFFAOYSA-N 0.000 description 1
- YZEHDFBYSOKBED-UHFFFAOYSA-N 4-isocyanato-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(N=C=O)C=C1 YZEHDFBYSOKBED-UHFFFAOYSA-N 0.000 description 1
- BSBYDDMVXYUYDT-UHFFFAOYSA-N 5,6-dichloro-3-iminoisoindol-1-amine Chemical compound C1=C(Cl)C(Cl)=CC2=C1C(=N)NC2=N BSBYDDMVXYUYDT-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 241000254158 Lampyridae Species 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000013053 water resistant agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/323—Organic colour formers, e.g. leuco dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
（産業上の利用分野）
本発明は、発色記録画像の保存安定性に優れた
２成分発色型の感熱記録用ラベルに関するもので
ある。
（従来の技術）
感熱記録用ラベルPOS（販売時点情報管理）シ
ステム用のバーコードラベル、価格表示ラベル、
配送・出荷ラベルなど印字後貼付を必要とする用
途に用いられている。特にスーパーマーケツトや
デパート等の大型量販売店をはじめ、チエーン展
開をしている専門店、レストラン等において
POSシステムの普及が著しい。消費者のニーズ
を明確に把握し、合理的な経営戦略を立てるため
に、商品の売上情報を集計、分析することが目的
であり、その一つとして、店頭で販売される商品
に表示されたバーコードやOCR文字をスキヤナ
ーで光学的に読み取る方法が現在急速に伸びてき
ている。
これらの記録方式の主流は、２成分系で、反応
体と共反応体とを含有する発色層を支持体上に設
けてなる感熱記録用ラベルを用い、これに熱を加
えることにより、反応体と共反応体を相互に接触
させ、発色画像として記録する方法である。中で
も、反応体、共反応体として、染料前駆体である
ロイコ染料と酸性物質である顕色剤を用いるもの
が多い。これら従来公知のロイコ染料を用いた感
熱記録用ラベルは、白色度が高い、外観、感触が
普通紙に近い、発色感度等の記録適性が良い等、
多くの優れた特性を備えていることから、その用
途を拡大してきた。反面、これらロイコ染料を用
いた感熱記録用ラベルは、例えばクリスタルバイ
オレツトラクトンと４，4′−イソプロピリテンジ
フエノール（ビスフエノールＡ）を発色剤とする
感熱紙（米国特許第3539375号など参照）と同じ
ように、発色して得られる記録部分の耐薬品性が
劣ることから、プラスチツクシートや消しゴムに
含まれる可塑剤あるいは食品や化粧品に含まれる
薬品に接触して記録が容易に消失したり、また、
記録部分の耐光性が劣ることから、比較的短期間
の日光曝露で記録が退色したり、さらには消失す
るなど、記録の保存安定性に劣るという欠点を有
している。
そこで、発色画像を保護するため、あらかじめ
発色層の上に保護層を形成させ、可塑剤等の浸透
を防ぎ、発色剤による発色画像の保存安定性を向
上させている。しかしながら、保護層にピンホー
ル等の不連続部分が生じていると、可塑剤等の接
触により、その部分から可塑剤等が浸透し、記録
部の劣化、消色が起る。また、保護層を厚くし、
可塑剤等の浸透を完全に防止しようとすると、発
色層への熱の伝達が低下し、感度低下等の原因と
なる。
（発明が解決しようとする問題点）
前記のように、従来の感熱記録用ラベルにおい
ては、発色記録画像の保存安定性に劣り、あらか
じめ発色層の上に保護層を形成させたものでは、
充分な保存安定性が得られていない。したがつ
て、発色層による発色画像が保護層をまつたく必
要としないで、またはきわめて薄い保護層で十分
な画像保存性をもつこと、さらに、熱応答性に優
れ、低エネルギーでも充分な発色画像が得られる
ことが望まれている。
（問題点を解決するための手段）
本発明は、発色画像の保存安定性に優れた感熱
記録用ラベルを提供することを目的とするもの
で、支持体の表面に無色または淡色の反応体と、
加熱時に該反応体と反応する共反応体とを発色成
分として含有する感熱発色層を形成し、支持体の
裏面に粘着層を設けた感熱記録用ラベルにおい
て、該反応体が下記一般式で示されるイミノ化合
物であり、
（式中、Ｘはハロゲン原子、ｎは０から４の整
数、ＡはＣ＝ＯまたはＣ＝NHを表わす。）
該共反応体が芳香族性イソシアナート化合物で
あることを特徴とする感熱記録用ラベルである。
本発明に用いられる少なくとも１個のＣ＝
NH基を有するイミノ化合物とは、一般式
(Industrial Application Field) The present invention relates to a two-component color-forming heat-sensitive recording label that has excellent storage stability of color-forming recorded images. (Prior technology) Thermal recording labels, barcode labels for POS (point of sale) systems, price display labels,
It is used for applications that require printing and pasting, such as shipping and shipping labels. Especially in large volume retailers such as supermarkets and department stores, as well as chain specialty stores and restaurants.
The popularity of POS systems is remarkable. The purpose is to aggregate and analyze product sales information in order to clearly understand consumer needs and formulate rational business strategies. The use of optical scanners to read barcodes and OCR characters is rapidly growing. The mainstream of these recording methods is a two-component system, in which a heat-sensitive recording label is provided on a support with a coloring layer containing a reactant and a co-reactant. This is a method of bringing a co-reactant and a co-reactant into contact with each other and recording a colored image. Among these, many use a leuco dye, which is a dye precursor, and a color developer, which is an acidic substance, as reactants and co-reactants. These heat-sensitive recording labels using conventionally known leuco dyes have high whiteness, appearance and feel similar to plain paper, and good recording suitability such as color development sensitivity.
Because it has many excellent properties, its uses have been expanded. On the other hand, thermal recording labels using these leuco dyes are, for example, thermal paper using crystal violet lactone and 4,4'-isopropyritene diphenol (bisphenol A) as coloring agents (see U.S. Pat. No. 3,539,375, etc.). Similarly, the chemical resistance of the recorded area obtained by coloring is poor, so the record can easily be erased when it comes into contact with plasticizers contained in plastic sheets and erasers, or chemicals contained in foods and cosmetics. Also,
Since the light resistance of the recorded portion is poor, the record has the disadvantage of poor storage stability, such as fading or even disappearance of the record after exposure to sunlight for a relatively short period of time. Therefore, in order to protect the colored image, a protective layer is formed on the colored layer in advance to prevent the penetration of plasticizers and the like, thereby improving the storage stability of the colored image created by the coloring agent. However, if a discontinuous portion such as a pinhole occurs in the protective layer, the plasticizer or the like will permeate through that portion upon contact with the protective layer, causing deterioration and discoloration of the recorded portion. In addition, the protective layer is thickened,
If an attempt is made to completely prevent the penetration of plasticizers, etc., the transfer of heat to the coloring layer will decrease, causing a decrease in sensitivity. (Problems to be Solved by the Invention) As mentioned above, in conventional heat-sensitive recording labels, the storage stability of colored recorded images is poor, and those in which a protective layer is formed on the colored layer in advance,
Sufficient storage stability has not been obtained. Therefore, the colored image produced by the coloring layer has sufficient image storage stability without the need for a protective layer or even with an extremely thin protective layer, and furthermore, it has excellent thermal responsiveness and can produce a sufficiently colored image even with low energy. It is hoped that this will be achieved. (Means for Solving the Problems) The object of the present invention is to provide a heat-sensitive recording label with excellent storage stability of colored images, and the present invention is to provide a heat-sensitive recording label with a colored image having excellent storage stability. ,
In a heat-sensitive recording label in which a heat-sensitive coloring layer containing a co-reactant that reacts with the reactant as a color-forming component when heated, and an adhesive layer provided on the back side of the support, the reactant is represented by the following general formula. It is an imino compound that (In the formula, X is a halogen atom, n is an integer from 0 to 4, and A represents C═O or C═NH.) A thermosensitive recording characterized in that the co-reactant is an aromatic isocyanate compound. This is a label for use. At least one C= used in the present invention
An imino compound having an NH group has the general formula
【式】
（φは隣接するＣ＝Ｎと共役系を形成しうる芳香
族性化合物残基）で表わされる如き化合物で、常
温固形の無色または淡色の化合物である。以下に
具体例を示す。目的に応じて２種以上のイミノ化
合物を併用することも可能である。
３−イミノイソインドリン−１−オン、３−イ
ミノ−４，５，６，７−テトラクロロイソインド
リン−１−オン、３−イミノ−４，５，６，７−
テトラブロモイソインドリン−１−オン、３−イ
ミノ−４，５，６，７−テトラフルオロイソイン
ドリン−１−オン、３−イミノ−５，６−ジクロ
ロイソインドリン−１−オン，１，３−ジイミノ
イソインドリン、１，３−ジイミノ−４，５，
６，７−テトラクロロイソインドリン、１，３−
ジイミノ−４，５，６，７−テトラフロロイソイ
ンドリン、１，３−ジイミノ−５，６−ジクロロ
イソインドリン等がある。
本発明に用いられる芳香族性イソシアナート
は、常温固体の無色または淡色の芳香族イソシア
ナートまたは複素環イソシアナートであり、例え
ば、下記の１種以上が用いられる。
２，６−ジクロロフエニルイソシアナート、ｐ
−ジクロロフエニルイソシアナート、１，３−フ
エニレンジイソシアナート、１，４−フエニレン
ジイソシアナート、１，３−ジメチルベンゼン−
４，６−ジイソシアナート、１，４−ジメチルベ
ンゼン−２，５−ジイソシアナート、１−メトキ
シベンゼン−２，４−ジイソシアナート、１−メ
トキシベンゼン−２，５−ジイソシアナート、１
−エトキシベンゼン−２，４−ジイソシアナー
ト、２，５−ジメトキベンゼン−１，４−ジイソ
シアナート、２，５−ジエトキシベンゼン−１，
４−ジイソシアナート、２，５−ジブトキシベン
ゼン−１，４−ジイソシアナート、アゾベンゼン
−４，4′−ジイソシアナート、ジフエニルエーテ
ル−４，4′−ジイソシアナート、ナフタリン−
１，４−ジイソシアナート、ナフタリン−１，５
−ジイソシアナート、ナフタリン−２，６−ジイ
ソシアナート、ナフタリン−２，７−ジイソシア
ナート、３，3′−ジメチル−ビフエニル−４，
4′−ジイソシアナート、３，3′−ジメトキシビフ
エニル−４，4′−ジイソシアナート−ジフエニル
メタン−４，4′−ジイソシアナート、ジフエニル
ジメチルメタン−４，4′−ジイソシアナート、ベ
ンゾフエノン−３，3′−ジイソシアナート、フル
オレン−２，７−ジイソシアナート、アンスラキ
ノン−２，６−ジイソシアナート、９−エチルカ
ルバゾール−３，６−ジイソシアナート、ピレン
３，８−ジイソシアナート、ナフタレン−１，
３，７−トリイソシアナート、ビフエニル−２，
４，4′−トリイソシアナート、ｐ−ジメチルアミ
ノフエニルイソシアナート、トリス（４−フエニ
ルイソシアナート）チオフオスフエート等があ
る。これらのイソシアナートは、必要に応じて、
フエノール類、ラクタム類、オキシム類等との付
加化合物である、いわゆるブロツクイソシアナー
トのかたちで用いてもよく、ジイソシアナートの
２量体、例えば１−メチルベンゼン−２，４−ジ
イソシアナートの２量体、および３量体であるイ
ソシアヌレートのかたちで用いてもよく、また、
各種のポリオール等でアダクト化したボリイソシ
アナートとして用いることも可能である。
これらのイミノ化合物とイソシアナート化合物
の加熱による接触反応により、発色画像が得られ
る。この発色画像の色相は、これら２成分の組合
せにより、赤色系、黄色系等広範囲に変化させる
ことができる。特に、近年、発色画像として黒色
系が好まれているが、一般に、発色画像の色相
は、赤味を帯びた黒が多く、紫味を帯びた黒の発
色画像は得られにくかつた。
本発明によるイソシアナート化合物として、特
に、下記式
で示される２，５−ジメトキシ−４，4′，4″−ト
リイソシアナート−トリフエニルアミンを用いる
ことにより、紫味の色相をもつ発色画像が得られ
ることがわかつた。このイソシアナートは、必要
に応じて、フエノール類、ラクタム類、オキシム
類等との付加化合物である、いわゆるブロツクイ
ソシアナートのかたちでも用いることができる。
本発明の感熱記録用ラベルにおいて、感熱発色
層中に発色成分の他に必要に応じさらに添加され
る主な成分について具体的に述べる。
バインダーとしては、デンプン類、ヒドロキシ
エチルセルロース、メチルセルロース、カルボキ
シメチルセルロース、ゼラチン、カゼイン、ポリ
ビニルアルコール、変性ポリビニルアルコール、
スチレン−無水マレイン酸共重合体、エチレン−
無水マレイン酸共重合体などの水溶性バインダ
ー、スチレン−ブタジエン共重合体、アクリロニ
トリル−ブタジエン共重合体、アクリル酸メチル
−ブタジエン共重合体などのラテツクス系水溶性
バインダーなどが挙げられる。
顔料としては、ケイソウ土、タルク、カオリ
ン、焼成カオリン、炭酸カルシウム、炭酸マグネ
シウム、酸化チタン、酸化亜鉛、酸化ケイ素、水
酸化アルミニウム、尿素−ホルマリン樹脂などが
挙げられる。
その他に、ヘツド摩耗防止、ステイツキング防
止などの目的でステアリン酸亜鉛、ステアリン酸
カルシウム等の高級脂肪酸金属塩、パラフイン、
酸化パラフイン、ポリエチレン、酸化ポリエチレ
ン、ステアリン酸アミド、カスターワツクス等の
ワツクス類を、また、ジオクチルスルホコハク酸
ナトリウム等の分散剤、ベンゾフエノン系、ベン
ゾトリアゾール系などの紫外線吸収剤、さらに界
面活性剤、螢光染料などが挙げられる。
本発明の感熱記録用ラベルは、発色画像の画像
保存性に優れているため、支持体の表面に発色層
だけを形成させることで充分であるが、必要に応
じて、さらに発色層の上に保護層を設けてもよ
い。保護層の主成分としては、各種の水溶性樹
脂、ラテツクス、光硬化型樹脂が用いられる。ま
た、必要に応じて、顔料、耐水化剤、撥水剤、消
泡剤、紫外線吸収剤等を添加することができる。
また、支持体の裏面には、別の固体表面と接着で
きる粘着層を設ける。この粘着層の表面には離型
紙が設けられる。
本発明の感熱記録用ラベルに用いられる支持体
としては、紙が主として用いられるが、各種不織
布、プラスチツクフイルム、合成紙、金属箔等あ
るいはこれらを組合わせた複合シートを任意に用
いることができる。
（実施例）
次に、本発明を実施例によりさらに詳細に説明
する。
実施例 １
１，３−ジイミノ−４，５，６，７−テトラク
ロロイソインドリン10ｇを１％ポリビニルアルコ
ール水溶液40ｇと共に、ボールミルで24時間分散
した。一方、２，５−ジメトキシ−４，4′4″−ト
リイソシアナート−トリフエニルアミン10ｇを１
％ポリビニルアルコール水溶液40ｇと共に、ボー
ルミルで24時間分散した。これら２種類の分散液
を混合した後、炭酸カルシウムの50％分散液60ｇ
を加え、さらに、ステアリン酸亜鉛の25％分散液
40ｇ、10％ポリビニルアルコール水溶液140ｇ、
水60ｇを加え、十分撹拌して塗液とした。この塗
液を秤量55ｇ／m3の原紙上に、固型分塗布量とし
て６ｇ／m3となるように塗布乾燥した。得られた
塗布紙の裏面に、粘着層を有する剥離紙を設けて
感熱記録用ラベルを得た。
実施例 ２
実施例１で用いた１，３−ジイミノー４，５，
６，７−テトラクロロイソインドリンの代りに３
−イミノ−４，５，６，７−テトラクロロイソイ
ンドリン−１−オンを用いた以外は、実施例１と
同様にして感熱記録用ラベルを得た。
実施例 ３
実施例２で用いた２，５−ジメトキシ−４，
4′，4″−トリイソシアナート−トリフエニルアミ
ンの代りにトリジンジイソシアナートを用いた以
外は、実施例２と同様にして感熱記録用ラベルを
得た。
比較例 １
実施例１で用いた１，３−ジイミノ−４，５，
６，７−テトラクロロイソインドリン代りに２−
アニリノ−３−メチル−６−ジエチルアミノフル
オランを、また、２，５−ジメトキシ−４，4′，
4″−トリイソシアナート−トリフエニルアミンの
代りに４，4′−イソプロピリデンジフエノールを
用いた以外は、実施例１と同様にして感熱記録用
ラベルを得た。
試 験
実施例１〜３、比較例１で得た感熱記録用ラベ
ルを、それぞれ感熱ラベルプリンターで、印加パ
ルス2.8ｍsec、印加電圧22.7Vの条件で印字し、
得られた発色画像の色相を目視で判定し、その結
果を表に示した。
また、発色画像に可塑剤として用いられている
ジオクチルフタレートを１滴おとし、１分後の画
像の変化を調べ、結果を同様に表に示した。It is a compound represented by the formula: (φ is the residue of an aromatic compound capable of forming a conjugated system with adjacent C═N), and is a colorless or light-colored compound that is solid at room temperature. A specific example is shown below. It is also possible to use two or more types of imino compounds in combination depending on the purpose. 3-iminoisoindolin-1-one, 3-imino-4,5,6,7-tetrachloroisoindolin-1-one, 3-imino-4,5,6,7-
Tetrabromoisoindolin-1-one, 3-imino-4,5,6,7-tetrafluoroisoindolin-1-one, 3-imino-5,6-dichloroisoindolin-1-one, 1,3- Diiminoisoindoline, 1,3-diimino-4,5,
6,7-tetrachloroisoindoline, 1,3-
Examples include diimino-4,5,6,7-tetrafluoroisoindoline and 1,3-diimino-5,6-dichloroisoindoline. The aromatic isocyanate used in the present invention is a colorless or light-colored aromatic isocyanate or a heterocyclic isocyanate that is solid at room temperature, and for example, one or more of the following are used. 2,6-dichlorophenyl isocyanate, p
-dichlorophenyl isocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,3-dimethylbenzene-
4,6-diisocyanate, 1,4-dimethylbenzene-2,5-diisocyanate, 1-methoxybenzene-2,4-diisocyanate, 1-methoxybenzene-2,5-diisocyanate, 1
-Ethoxybenzene-2,4-diisocyanate, 2,5-dimethoxybenzene-1,4-diisocyanate, 2,5-diethoxybenzene-1,
4-diisocyanate, 2,5-dibutoxybenzene-1,4-diisocyanate, azobenzene-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, naphthalene-
1,4-diisocyanate, naphthalene-1,5
-diisocyanate, naphthalene-2,6-diisocyanate, naphthalene-2,7-diisocyanate, 3,3'-dimethyl-biphenyl-4,
4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate-diphenylmethane-4,4'-diisocyanate, diphenyldimethylmethane-4,4'-diisocyanate, Benzophenone-3,3'-diisocyanate, fluorene-2,7-diisocyanate, anthraquinone-2,6-diisocyanate, 9-ethylcarbazole-3,6-diisocyanate, pyrene 3,8-diisocyanate Diisocyanate, naphthalene-1,
3,7-triisocyanate, biphenyl-2,
Examples include 4,4'-triisocyanate, p-dimethylaminophenyl isocyanate, and tris(4-phenyl isocyanate) thiophosphate. These isocyanates are optionally
It may also be used in the form of so-called blocked isocyanates, which are addition compounds with phenols, lactams, oximes, etc., and dimers of diisocyanates, such as 1-methylbenzene-2,4-diisocyanate. It may be used in the form of dimeric and trimeric isocyanurates, and
It can also be used as a polyisocyanate adducted with various polyols. A colored image is obtained by a contact reaction between these imino compounds and an isocyanate compound by heating. The hue of this colored image can be varied over a wide range, such as red or yellow, by combining these two components. In particular, in recent years, black colors have been preferred as colored images, but in general, the hue of colored images is often reddish black, and it has been difficult to obtain colored images with purplish black. As the isocyanate compound according to the present invention, in particular, the following formula is used: It has been found that a colored image with a purplish hue can be obtained by using 2,5-dimethoxy-4,4',4''-triisocyanate-triphenylamine represented by the following isocyanate: If necessary, it can also be used in the form of so-called blocked isocyanate, which is an addition compound with phenols, lactams, oximes, etc. In the heat-sensitive recording label of the present invention, the color-forming component is contained in the heat-sensitive color-forming layer. We will specifically discuss the main ingredients that may be added as needed. Examples of binders include starches, hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, gelatin, casein, polyvinyl alcohol, modified polyvinyl alcohol,
Styrene-maleic anhydride copolymer, ethylene-
Examples include water-soluble binders such as maleic anhydride copolymers, latex-based water-soluble binders such as styrene-butadiene copolymers, acrylonitrile-butadiene copolymers, and methyl acrylate-butadiene copolymers. Examples of pigments include diatomaceous earth, talc, kaolin, calcined kaolin, calcium carbonate, magnesium carbonate, titanium oxide, zinc oxide, silicon oxide, aluminum hydroxide, urea-formalin resin, and the like. In addition, higher fatty acid metal salts such as zinc stearate and calcium stearate, paraffin,
Waxes such as paraffin oxide, polyethylene, polyethylene oxide, stearamide, and castor wax, dispersants such as sodium dioctyl sulfosuccinate, ultraviolet absorbers such as benzophenone and benzotriazole, and surfactants and fireflies. Examples include photodyes. Since the heat-sensitive recording label of the present invention has excellent image storage stability of the colored image, it is sufficient to form only the coloring layer on the surface of the support. A protective layer may also be provided. The main components of the protective layer include various water-soluble resins, latexes, and photocurable resins. Further, pigments, water-resistant agents, water repellents, antifoaming agents, ultraviolet absorbers, etc. can be added as necessary.
Furthermore, an adhesive layer that can adhere to another solid surface is provided on the back surface of the support. A release paper is provided on the surface of this adhesive layer. Paper is mainly used as the support for the heat-sensitive recording label of the present invention, but various nonwoven fabrics, plastic films, synthetic papers, metal foils, etc., or composite sheets of combinations of these may also be used as desired. (Example) Next, the present invention will be explained in more detail with reference to Examples. Example 1 10 g of 1,3-diimino-4,5,6,7-tetrachloroisoindoline was dispersed in a ball mill for 24 hours with 40 g of a 1% polyvinyl alcohol aqueous solution. On the other hand, 10 g of 2,5-dimethoxy-4,4'4''-triisocyanato-triphenylamine was added to 1
% polyvinyl alcohol aqueous solution for 24 hours using a ball mill. After mixing these two types of dispersion, 60g of 50% dispersion of calcium carbonate
plus a 25% dispersion of zinc stearate
40g, 10% polyvinyl alcohol aqueous solution 140g,
60 g of water was added and thoroughly stirred to obtain a coating liquid. This coating liquid was applied and dried on a base paper weighing 55 g/m 3 so that the solid coating amount was 6 g/m 3 . A release paper having an adhesive layer was provided on the back side of the obtained coated paper to obtain a heat-sensitive recording label. Example 2 1,3-diimino 4,5, used in Example 1
3 instead of 6,7-tetrachloroisoindoline
A heat-sensitive recording label was obtained in the same manner as in Example 1 except that -imino-4,5,6,7-tetrachloroisoindolin-1-one was used. Example 3 2,5-dimethoxy-4, used in Example 2
A heat-sensitive recording label was obtained in the same manner as in Example 2, except that tridine diisocyanate was used instead of 4',4''-triisocyanate-triphenylamine. Comparative Example 1 Used in Example 1 1,3-diimino-4,5,
2- instead of 6,7-tetrachloroisoindoline
Anilino-3-methyl-6-diethylaminofluorane, 2,5-dimethoxy-4,4',
A heat-sensitive recording label was obtained in the same manner as in Example 1, except that 4,4'-isopropylidene diphenol was used instead of 4''-triisocyanate-triphenylamine.Test Examples 1 to 3 The thermal recording labels obtained in Comparative Example 1 were printed using a thermal label printer under the conditions of an applied pulse of 2.8 msec and an applied voltage of 22.7 V.
The hue of the obtained colored image was visually determined, and the results are shown in the table. In addition, one drop of dioctyl phthalate, which is used as a plasticizer for colored images, was added, and changes in the image after one minute were examined, and the results are also shown in the table.
【表】
（発明の効果）
表に示したように、発色画像の保存安定性に優
れると共に、色相を選ぶことができる。さらに、
イソシアナート化合物に特定のものを選択するこ
とにより、紫味の黒色が得られる。[Table] (Effects of the invention) As shown in the table, the storage stability of the colored image is excellent and the hue can be selected. moreover,
By selecting a specific isocyanate compound, a purplish black color can be obtained.
Claims (1)
加熱時に該反応体と対応する共反応体とを発色成
分として含有する感熱発色層を形成し、支持体の
裏面に粘着層を設けた感熱記録用ラベルにおい
て、該反応体が下記一般式で示されるイミノ化合
物であり、 （式中、Ｘはハロゲン原子、ｎは０から４の整
数、ＡはＣ＝ＯまたはＣ＝NHを表わす。） 該共反応体が芳香族性イソシアナート化合物で
あることを特徴とする感熱記録用ラベル。 ２ 芳香族性イソシアナート化合物が下記式 で示される化合物である特許請求の範囲第１項記
載の感熱記録用ラベル。[Claims] 1. A colorless or light-colored reactant on the surface of the support,
In a heat-sensitive recording label which forms a heat-sensitive color-forming layer containing the reactant and a corresponding co-reactant as color-forming components when heated, and has an adhesive layer on the back side of the support, the reactant is represented by the following general formula. It is an imino compound that (In the formula, X is a halogen atom, n is an integer from 0 to 4, and A represents C═O or C═NH.) A thermosensitive recording characterized in that the co-reactant is an aromatic isocyanate compound. label. 2 The aromatic isocyanate compound has the following formula The heat-sensitive recording label according to claim 1, which is a compound represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60142599A JPS623984A (en) | 1985-07-01 | 1985-07-01 | Label for thermal recording |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60142599A JPS623984A (en) | 1985-07-01 | 1985-07-01 | Label for thermal recording |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS623984A JPS623984A (en) | 1987-01-09 |
| JPH054913B2 true JPH054913B2 (en) | 1993-01-21 |
Family
ID=15319052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60142599A Granted JPS623984A (en) | 1985-07-01 | 1985-07-01 | Label for thermal recording |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS623984A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0785944B2 (en) * | 1989-11-14 | 1995-09-20 | 三菱製紙株式会社 | Thermal recording material |
-
1985
- 1985-07-01 JP JP60142599A patent/JPS623984A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS623984A (en) | 1987-01-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |