JPS63309494A - Thermal transfer recording medium - Google Patents
Thermal transfer recording mediumInfo
- Publication number
- JPS63309494A JPS63309494A JP62146502A JP14650287A JPS63309494A JP S63309494 A JPS63309494 A JP S63309494A JP 62146502 A JP62146502 A JP 62146502A JP 14650287 A JP14650287 A JP 14650287A JP S63309494 A JPS63309494 A JP S63309494A
- Authority
- JP
- Japan
- Prior art keywords
- transfer recording
- recording medium
- thermal transfer
- copolymer
- cationic dye
- 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
- 229920001577 copolymer Polymers 0.000 claims abstract description 45
- 125000002091 cationic group Chemical group 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 239000011347 resin Substances 0.000 claims abstract description 15
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical group OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002844 melting Methods 0.000 claims description 40
- 239000001993 wax Substances 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003086 colorant Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 4
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 239000012943 hotmelt Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 25
- 239000000203 mixture Substances 0.000 abstract description 15
- 125000005396 acrylic acid ester group Chemical group 0.000 abstract 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 44
- 239000010410 layer Substances 0.000 description 26
- 230000008018 melting Effects 0.000 description 25
- 239000000975 dye Substances 0.000 description 21
- -1 acrylic ester Chemical class 0.000 description 20
- 238000006116 polymerization reaction Methods 0.000 description 16
- 239000000243 solution Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 11
- 238000004043 dyeing Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000010408 film Substances 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 239000000049 pigment Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004040 coloring Methods 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000012188 paraffin wax Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 4
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000019198 oils Nutrition 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- NWKBFCIAPOSTKG-UHFFFAOYSA-M trimethyl-[3-[(3-methyl-5-oxo-1-phenyl-4h-pyrazol-4-yl)diazenyl]phenyl]azanium;chloride Chemical compound [Cl-].CC1=NN(C=2C=CC=CC=2)C(=O)C1N=NC1=CC=CC([N+](C)(C)C)=C1 NWKBFCIAPOSTKG-UHFFFAOYSA-M 0.000 description 2
- VSKRSEHLMRRKOS-QJWNTBNXSA-N (z,12r)-12-hydroxyoctadec-9-enamide Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(N)=O VSKRSEHLMRRKOS-QJWNTBNXSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- FKOZPUORKCHONH-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid Chemical compound CC(C)CS(O)(=O)=O FKOZPUORKCHONH-UHFFFAOYSA-N 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- GQTFHSAAODFMHB-UHFFFAOYSA-N 2-prop-2-enoyloxyethanesulfonic acid Chemical compound OS(=O)(=O)CCOC(=O)C=C GQTFHSAAODFMHB-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- KFNGWPXYNSJXOP-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propane-1-sulfonic acid Chemical compound CC(=C)C(=O)OCCCS(O)(=O)=O KFNGWPXYNSJXOP-UHFFFAOYSA-N 0.000 description 1
- VZOOHWGPNLPIHR-UHFFFAOYSA-N 3-[2-[[4-[bis(2-chloroethyl)amino]phenyl]diazenyl]-6-methoxy-1,3-benzothiazol-3-ium-3-yl]propanamide;chloride Chemical compound [Cl-].S1C2=CC(OC)=CC=C2[N+](CCC(N)=O)=C1N=NC1=CC=C(N(CCCl)CCCl)C=C1 VZOOHWGPNLPIHR-UHFFFAOYSA-N 0.000 description 1
- NJIRSTSECXKPCO-UHFFFAOYSA-M 3-[n-methyl-4-[2-(1,3,3-trimethylindol-1-ium-2-yl)ethenyl]anilino]propanenitrile;chloride Chemical compound [Cl-].C1=CC(N(CCC#N)C)=CC=C1\C=C\C1=[N+](C)C2=CC=CC=C2C1(C)C NJIRSTSECXKPCO-UHFFFAOYSA-M 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- QZAFRWHFVILODC-UHFFFAOYSA-N C=CCCCCCCCCCCCCCC.CC(C(=O)O)=C Chemical compound C=CCCCCCCCCCCCCCC.CC(C(=O)O)=C QZAFRWHFVILODC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241001227713 Chiron Species 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- IURGIPVDZKDLIX-UHFFFAOYSA-M [7-(diethylamino)phenoxazin-3-ylidene]-diethylazanium;chloride Chemical compound [Cl-].C1=CC(=[N+](CC)CC)C=C2OC3=CC(N(CC)CC)=CC=C3N=C21 IURGIPVDZKDLIX-UHFFFAOYSA-M 0.000 description 1
- STWYYQVVABMBIZ-UHFFFAOYSA-N [hydroxy(2-hydroxyethoxy)phosphoryl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OP(O)(=O)OCCO STWYYQVVABMBIZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 239000012164 animal wax Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- 229940092738 beeswax Drugs 0.000 description 1
- 239000004204 candelilla wax Substances 0.000 description 1
- 235000013868 candelilla wax Nutrition 0.000 description 1
- 229940073532 candelilla wax Drugs 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- IUJAMGNYPWYUPM-UHFFFAOYSA-N hentriacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC IUJAMGNYPWYUPM-UHFFFAOYSA-N 0.000 description 1
- ZNAOFAIBVOMLPV-UHFFFAOYSA-N hexadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(C)=C ZNAOFAIBVOMLPV-UHFFFAOYSA-N 0.000 description 1
- PZDUWXKXFAIFOR-UHFFFAOYSA-N hexadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C=C PZDUWXKXFAIFOR-UHFFFAOYSA-N 0.000 description 1
- 235000019388 lanolin Nutrition 0.000 description 1
- 229940039717 lanolin Drugs 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- 239000004006 olive oil Substances 0.000 description 1
- 235000008390 olive oil Nutrition 0.000 description 1
- PWGIEBRSWMQVCO-UHFFFAOYSA-N phosphono prop-2-enoate Chemical compound OP(O)(=O)OC(=O)C=C PWGIEBRSWMQVCO-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012176 shellac wax Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- 239000012178 vegetable wax Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000010698 whale oil 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
- B41M5/382—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
Landscapes
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はタイプライタ−やコンピュータープリンターな
どの印像形成装置において、サーマルヘッドの加熱によ
り熱溶融性インクを記録用紙に転移して印像を形成する
ために使用する前記熱溶融性インクを保持する感熱転写
記録媒体に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is an image forming apparatus such as a typewriter or a computer printer, in which heat-melting ink is transferred to recording paper by heating a thermal head to form an image. The present invention relates to a heat-sensitive transfer recording medium that holds the heat-melting ink used for forming the heat-sensitive transfer recording medium.
（従来の技術〕
従来、熱溶融性インク層を形成させた感熱転写記録媒体
は、ワックスなどのバインダー材に顔料を分散混合して
着色材とし、常温で固体の熱溶融性インク層を樹脂フィ
ルムや高密度紙などの基材に塗布形成したものであり、
この熱溶融性インク層を記録用紙に圧接してサーマルヘ
ッドにより加熱し、加熱された箇所のインクを記録紙に
溶融転移させるものである。(Prior art) Conventionally, heat-sensitive transfer recording media on which a heat-melt ink layer is formed are made by dispersing and mixing pigments in a binder material such as wax as a coloring material, and the heat-melt ink layer, which is solid at room temperature, is transferred to a resin film. It is formed by coating on a base material such as or high-density paper.
This heat-melting ink layer is brought into pressure contact with a recording paper and heated by a thermal head, so that the ink at the heated portions is melted and transferred to the recording paper.
この様な従来技術による感熱転写記録媒体に用いる熱溶
融性インクは、顔料や染料が着色材として使用され又バ
インダーとしてワックス類が使用されて来た。In the heat-melting inks used in such conventional thermal transfer recording media, pigments and dyes have been used as colorants, and waxes have been used as binders.
しかしながら、従来バインダーとして使用されてきたワ
ックス類への顔料の分散には、多く゛の困雑性を有して
おり、実際上程々の剪断力による分散機を用いて分散し
ようとしても分散不良ないし分散の不安定化を生じるこ
とが多く、又顔料であるが故に透明度の高い鮮明な着色
が冑にくいという問題点があった。However, there are many difficulties in dispersing pigments into waxes, which have traditionally been used as binders. It often causes unstable dispersion, and because it is a pigment, it is difficult to achieve clear coloring with high transparency.
又染料による着色方法では、顔料による着色に比べ透明
度の高い着色は得られるものの不十分であり、逆に染料
の移行による用紙の汚染などの問題点があった。Furthermore, the coloring method using dyes provides coloring with higher transparency compared to coloring using pigments, but it is insufficient, and conversely, there are problems such as staining of the paper due to migration of the dye.
本発明は、鮮明なカラー印像が得られ、かつ従来の顔料
分散の様な操作や問題点を解消することができる熱溶融
性インクを有する感熱転写記録媒体の開発を目的として
なされたものである。The present invention was made for the purpose of developing a thermal transfer recording medium having a heat-melting ink that can produce clear color images and eliminate the problems associated with conventional pigment dispersion operations. be.
（問題点を解決するための手段〕
本発明の要旨とする所は支持体の片面上に熱溶融性イン
ク層を形成してなる感熱転写記録媒体において、該イン
ク層総吊１００重量部に対し、アクリル酸エステルおよ
び／またはメタクリル酸エステルの１種又はそれ以上の
６０モル％以上とカチオン染料可染ダイサイトを有する
モノマー（但し、スチレンスルホン酸又はその塩を除く
。）の１種又はそれ以上の１モル％以上から成る共重合
体のカチオン染料による染色物１０重量部以上、ワック
ス類９０重Φ部以下および樹脂類５０重量部以下を含有
することを特徴とする感熱転写記録媒体に存し、これに
より所期の目的を達成したものである。(Means for Solving the Problems) The gist of the present invention is to provide a heat-sensitive transfer recording medium in which a heat-melting ink layer is formed on one side of a support, based on 100 parts by weight of the total ink layer. , 60 mol% or more of one or more of acrylic esters and/or methacrylic esters, and one or more monomers having cationic dye-dyeable dicite (excluding styrene sulfonic acid or its salts). A thermal transfer recording medium characterized in that it contains 10 parts by weight or more of a dyed product using a cationic dye of a copolymer consisting of 1 mol% or more of , thereby achieving the intended purpose.
以下に本発明についてさらに詳細に説明する。 The present invention will be explained in more detail below.
本発明における前記のアクリル酸エステルおよび／また
はメタクリル酸エステルとの共重合体の染色物は、雨上
ツマ−を共重合した後、カチオン染料で染色することに
よって製造できる。The dyed product of the copolymer with an acrylic ester and/or a methacrylic ester in the present invention can be produced by copolymerizing the raindrops and then dyeing the copolymer with a cationic dye.
前記のアクリル酸エステルおよび／またはメタクリル酸
エステルとしては炭素数１２〜２２の飽和および／また
は不飽和の脂肪族アルコールとアクリル酸、メタクリル
酸とのエステル類が好ましく、炭素数が１２未満では油
脂類、ワックス類に相溶しなくなる。The acrylic ester and/or methacrylic ester are preferably esters of saturated and/or unsaturated aliphatic alcohols having 12 to 22 carbon atoms and acrylic acid or methacrylic acid; , it becomes incompatible with waxes.
また特に炭素数が１４未満では、得られる共重合体の染
色物の溶融温度が室温前後になりべとつきやすくなるこ
とから、通常の使用にあたっては特に炭素数１４以上の
エステル類が好ましい。Further, especially when the number of carbon atoms is less than 14, the melting temperature of the dyed product of the obtained copolymer will be around room temperature and it will become sticky, so esters having 14 or more carbon atoms are particularly preferred for normal use.
これを具体的に示せば、アクリル酸ドデシルエステル、
メタクリル酸ドデシルエステル、アクリル酸テトラデシ
ルエステル、メタクリル酸テトラデシルエステル、アク
リル酸ヘキサデシルエステル、アクリル酸へキサデセン
エステル。Specifically, acrylic acid dodecyl ester,
Methacrylic acid dodecyl ester, acrylic acid tetradecyl ester, methacrylic acid tetradecyl ester, acrylic acid hexadecyl ester, acrylic acid hexadecene ester.
メタクリル酸ヘキサデシルエステル、メタクリル酸へキ
サデセンエステル、アクリル酸オクタデシルエステル、
アクリル酸オクタデセンエステル、メタクリル酸オクタ
デシルエステル、メタクリル酸オクタデセンエステル、
アクリル酸エイコサンエステル、メタクリル酸エイコサ
ンエステル、アクリル酸トコサンエステル、メタクリル
酸トコサンエステルなどをあげることが出来る。Hexadecyl methacrylate, hexadecene methacrylate, octadecyl acrylate,
Acrylic acid octadecene ester, methacrylic acid octadecyl ester, methacrylic acid octadecene ester,
Examples include eicosane acrylate ester, eicosane methacrylate ester, tocosane acrylate ester, and tocosane methacrylate ester.
本発明におけるカチオン染料可染ダイサイトを有するモ
ノマーとしては、スチレンスルホン酸以外のスルホン酸
基、リンｒ！ｉ基、カルボン酸基又はこれらの塩を有す
るモノマーがあげられ、例えばスチレンスルホン酸以外
のスルホン酸基を有するモノマーとしては、ビニルスル
ホン酸。In the present invention, monomers having dicite that can be dyed with cationic dyes include sulfonic acid groups other than styrene sulfonic acid, phosphorus r! Examples include monomers having an i group, a carboxylic acid group, or a salt thereof; examples of monomers having a sulfonic acid group other than styrene sulfonic acid include vinylsulfonic acid.
アリルスルホン酸、メタリルスルホン酸、アクリロイル
オキシエチルスルホン酸、メタクリロイルオキシプロピ
ルスルホン酸、２−アクリルアミド−２−メチルプロパ
ンスルホン酸等、リン酸基を有するモノマーとしては、
２−ヒドロキシェヂルアクリロイルホスフェート、２−
ヒドロキシエチルメタクリロイルホスフェート、３−ク
ロロ−２−アシッドホスホキシプロピルメタクリレート
等、カルボン酸基を有するモノマーとしては、アクリル
酸、メタクリル酸、マレイン酸、フマル酸、イタコン酸
等、又これらの塩、例えばリチウム塩、ナトリウム塩、
カリウム塩、アンモニウム塩等をあげることが出来る。Monomers having a phosphoric acid group include allylsulfonic acid, methallylsulfonic acid, acryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, etc.
2-hydroxyedyl acryloyl phosphate, 2-
Examples of monomers having a carboxylic acid group such as hydroxyethyl methacryloyl phosphate and 3-chloro-2-acid phosphoxypropyl methacrylate include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, and salts thereof, such as lithium. salt, sodium salt,
Examples include potassium salts and ammonium salts.
アクリル酸エステルおよび／またはメタクリル酸エステ
ルとカチオン染料可染ダイサイトを有するモノマーとの
共重合比率は、得られる染色物の溶融温度、油脂類、ワ
ックス類との相溶性１色濃度などによって選択出来るが
、アクリル酸エステルおよび／またはメタクリル酸エス
テルが６０モル％未満では油脂類、ワックス類との相溶
性が不十分となる傾向を示し、カチオン染料可染ダイサ
イトを有するモノマーが１モル％未満では充分な色濃度
が得られない。The copolymerization ratio of the acrylic ester and/or methacrylic ester and the cationic dye-dyeable dicite-containing monomer can be selected depending on the melting temperature of the dyed product obtained, compatibility with oils, fats, and waxes, and the concentration of one color. However, if the acrylic ester and/or methacrylic ester is less than 60 mol%, the compatibility with oils, fats, and waxes tends to be insufficient, and if the monomer containing cationic dye-dyeable dicite is less than 1 mol%, Sufficient color density cannot be obtained.
これらアクリル酸エステルおよび／またはメタクリル酸
エステルとカチオン染料可染ダイサイトを有するモノマ
ーと溶媒中で重合開始剤を使用して重合するが、重合に
使用する溶媒は特に限定されず、ジメチルホルムアミド
、ジエチルホルムアミド、Ｎ−メチルピロリドン、■ヂ
レンカーボネート、プロピレンカーボネートなどで良い
。These acrylic esters and/or methacrylic esters are polymerized using a polymerization initiator in a solvent with a monomer having dicite that can be dyed with a cationic dye. Formamide, N-methylpyrrolidone, dylene carbonate, propylene carbonate, etc. may be used.
又重合に際して溶媒中のモノマー濃度は１〜３０手ω％
、好ましくは５〜２０重Ｍ％の範囲内で実施出来る。Also, during polymerization, the monomer concentration in the solvent is 1 to 30% ω%.
, preferably within the range of 5 to 20% by weight.
溶媒中の七ツマー濃度が高すぎると重合中の凝析物が多
くなり又重合反応熱の除去が困難となるなどの点で好ま
しくなく、又あまりの低濃度では経済的に不利である。If the concentration of heptamer in the solvent is too high, the amount of coagulated substances during polymerization increases and it becomes difficult to remove the heat of the polymerization reaction, which is undesirable, and if the concentration is too low, it is economically disadvantageous.
ざらに、使用される重合開始剤としてはＡＩＢＮ、ｔ−
ブチルハイドロペルオキシド。In general, the polymerization initiators used are AIBN, t-
Butyl hydroperoxide.
キュメンハイドロペルオキシドの様な通常のラジカル重
合開始剤でよい。A conventional radical polymerization initiator such as cumene hydroperoxide may be used.
この様な重合開始剤を使用して通常の重合反応で採用さ
れている重合温度で重合するのであるが、重合温度は１
０〜１００℃、通常４０〜９０℃で実施すれば良い。Using such a polymerization initiator, polymerization is carried out at the polymerization temperature used in ordinary polymerization reactions, but the polymerization temperature is 1.
What is necessary is just to carry out at 0-100 degreeC, usually 40-90 degreeC.
本発明は、この様な共重合体の製造方法によって何ら限
定されろものではない。The present invention is not limited in any way by the method for producing such a copolymer.
次で得られた共重合体をカチオン染料で染色するが、使
用されるカチオン染料としては通常の塩基性染料及びカ
チオン染料を包含する。The copolymer obtained in the next step is dyed with a cationic dye, and the cationic dye used includes ordinary basic dyes and cationic dyes.
染色方法は特に限定されないが、例えばカチオン染料の
水溶液と本発明の前出の共重合体溶液を接触処理するこ
とにより基本的に達成される。Although the dyeing method is not particularly limited, it is basically achieved by, for example, contacting an aqueous solution of a cationic dye with the above-mentioned copolymer solution of the present invention.
染色処理条件としては、特に限定されないが、室温〜１
００℃、通常３０〜８０℃で良い。かかる染色処理のの
ち本発明の共重合体の染色物は染色溶液から分離される
が、分離方法としては例えば蒸留などの方法により溶媒
を除ぐか、直接大ｍの水中に投入して析出する着色物を
濾過分離する方法などがある。The dyeing treatment conditions are not particularly limited, but from room temperature to 1
00°C, usually 30 to 80°C. After such dyeing treatment, the dyed product of the copolymer of the present invention is separated from the dyeing solution, and the separation method is, for example, by removing the solvent by a method such as distillation, or by directly pouring it into a large volume of water to precipitate it. There are methods to separate colored substances by filtration.
かかる染色条件、分離、ｖ３製方法などによって本発明
は限定されない。The present invention is not limited by such staining conditions, separation, v3 production method, etc.
本発明における共重合体の染色物の溶融温度は特に限定
されないが、好ましくは３０〜１５０℃、特に好ましく
は５０〜８０℃のものが良い。インク組成物中の共重合
体の染色物の含量が高い場合、この温度範囲未満では室
温付近でインク自体が粘着しやすく、またこの温度範囲
を越えると熱溶融時に高いエネルギーを要し、さらに熱
転移インク母も同じエネルギー量では少なくなり、実用
的ではない。また本発明における共重合体の染色物の溶
融粘度は本発明のインク組成物中に占める含母や他の添
加成分により自由に選択でき、特に限定することはでき
ないが、より良い溶融転移性を発現するには、溶融粘度
があまりに大き過ぎないものが好適に使用され、好まし
くは１２０℃における溶融粘度（フローテスタ−１１０
０Ｎｇ／ｒｍにて測定）が１００ＯＰ ａ −Ｓ以下、
特に５００ｐａ−ｓ以下のものが好ましい。The melting temperature of the dyed product of the copolymer in the present invention is not particularly limited, but is preferably 30 to 150°C, particularly preferably 50 to 80°C. If the content of the dyed copolymer in the ink composition is high, if the temperature is below this temperature range, the ink itself will tend to stick around room temperature, and if it exceeds this temperature range, high energy will be required for thermal melting, and The transfer ink mother also decreases with the same amount of energy, making it impractical. Furthermore, the melt viscosity of the dyed product of the copolymer of the present invention can be freely selected depending on the mother content and other additive components present in the ink composition of the present invention, and cannot be particularly limited. For this purpose, a material whose melt viscosity is not too large is suitably used, preferably melt viscosity at 120°C (Flow Tester-110
(measured at 0 Ng/rm) is 100 OP a -S or less,
Particularly preferred is one of 500 pa-s or less.
尚、本発明における共重合体の分子量としては特に限定
されないが、インク組成物中の共重合体の染色物の含量
が高い場合、共重合体の分子♀が大きすぎると、溶融転
移しがたくなり、印像の解像度が低下する傾向を示すの
で、重量平均分子量で５０万以下のものが好ましく、特
に２０万以下のものが好ましい。Although the molecular weight of the copolymer in the present invention is not particularly limited, if the content of the copolymer dyed material in the ink composition is high, if the molecule of the copolymer is too large, it will be difficult to melt and transfer. Since this tends to lower the resolution of the printed image, those having a weight average molecular weight of 500,000 or less are preferred, and those with a weight average molecular weight of 200,000 or less are particularly preferred.
本発明の感熱転写記録媒体は、支持体上の片面に少くと
も一層の熱溶融性インク層を有する。The heat-sensitive transfer recording medium of the present invention has at least one heat-melting ink layer on one side of the support.
該インク層には、少くとも１種の本発明の共重合体のカ
チオン染料染色物が含有される。The ink layer contains a cationic dye dyeing of at least one copolymer of the invention.
本発明の感熱転写記録媒体の形態は特に限定されない。The form of the thermal transfer recording medium of the present invention is not particularly limited.
その形態の一つとして少くともイエロー、マゼンタ、シ
アンの各色より成り、本発明の特定の共重合体のカチオ
ン染料染色物は、すくなくともこれらの各色を与えるも
のが使用され、これらを含有する熱溶融性インクが同一
支持体上に部分塗工されている感熱転写記録媒体があげ
られる。One of its forms consists of at least yellow, magenta, and cyan colors, and the specific copolymer cationic dyeing of the present invention is one that gives at least each of these colors, and a hot-melting dye containing these is used. Examples include a thermal transfer recording medium in which a transparent ink is partially coated on the same support.
本発明の感熱転写記録媒体の支持体上の熱溶融性インク
層は前出の共重合体の染色物のみでもよいが、より好ま
しくはこれにワックス類の様な他の熱溶融性物質を共存
させるのが良い。The heat-fusible ink layer on the support of the heat-sensitive transfer recording medium of the present invention may be a dyed product of the above-mentioned copolymer alone, but it is more preferable that other heat-fusible substances such as waxes coexist therein. It's better to let them.
本発明に使用されるワックス類としては、融点が５０〜
２００℃、好ましくは６０〜１５０℃のワックス類が良
好で、融点が５０’ＣＪζりも低すぎると解像度が低下
する傾向を示し、逆に融点が２００℃より高い場合には
、サーマルヘッドに高エネルギーを要し、又熱転写イン
ク量も少くなり、実用的ではない。The waxes used in the present invention have a melting point of 50 to
Waxes with a temperature of 200℃, preferably 60 to 150℃ are good; if the melting point is too low than 50'CJ This method requires energy and requires less thermal transfer ink, making it impractical.
この様なワックス類には、以下に代表的なものを例示す
るが、これらに限定されるものではない。Typical examples of such waxes are listed below, but the waxes are not limited thereto.
ワックス類としてはライスワックス、本ろう。Waxes include rice wax and real wax.
キャンデリラワックス、カルナウバワックスなどの植物
性ワックス、ラノリン、密ろう、セラックワックスなど
の動物性ワックス、モンタンワックスなどの鉱物性ワッ
クス、パラフィンワックス、マイクロクリスタリンワッ
クス、酸化パラフィンワックス、塩素化パラフィンワッ
クス、リシノール酸アマイド、ウラリン酸アマイド、オ
レイン酸アマイドなどの合成ワックスなどをあげること
が出来る。Vegetable waxes such as candelilla wax and carnauba wax, animal waxes such as lanolin, beeswax, and shellac wax, mineral waxes such as montan wax, paraffin wax, microcrystalline wax, oxidized paraffin wax, chlorinated paraffin wax, Examples include synthetic waxes such as ricinoleamide, uraric acid amide, and oleic acid amide.
これらの内、１種又は２種以上を併用してインクとして
の融点が５０〜２００℃の範囲内に調整して使用される
。Among these, one type or a combination of two or more types may be used to adjust the melting point of the ink to be within the range of 50 to 200°C.
インク層でのこれらワックスの使用量は、インク層総量
１００重量部に対し９０重重量以下が良く、９０重量部
以上では希釈による色濃度の低下により画像温度が得ら
れず実用的ではない。The amount of these waxes used in the ink layer is preferably 90 parts by weight or less per 100 parts by weight of the total amount of the ink layer, and if it exceeds 90 parts by weight, the image temperature cannot be obtained due to a decrease in color density due to dilution, which is not practical.
次に本発明のインク層には伯の樹脂類を使用しても良い
。この様な樹脂類としてはスチレン・ブタジェン共重合
体、酢酸ビニル樹脂、酢酸ビニル・エヂレン共重合体樹
脂、酢酸ビニル共重合体樹脂などをあげることが出来る
。これら樹脂の使用量はインク層総ｔｉ１ｏｏ重量部に
対し５０重量部以下が良く、使用するワックス類の融点
に応じて調整するのが良い。即ち併用するワックス類の
融点が低い場合には、樹脂類の使用量の多い方が良く、
ワックス類の融点が高い場合には、樹脂の使用量は少く
て良い。Next, in the ink layer of the present invention, resins of the same type may be used. Examples of such resins include styrene/butadiene copolymer, vinyl acetate resin, vinyl acetate/ethylene copolymer resin, and vinyl acetate copolymer resin. The amount of these resins used is preferably 50 parts by weight or less based on the total weight of the ink layer, and is preferably adjusted depending on the melting point of the wax used. In other words, if the wax used in combination has a low melting point, it is better to use a larger amount of resin.
If the wax has a high melting point, the amount of resin used may be small.
樹脂類の使用量が５０重量部以上の場合には、インクの
転写量が少なくなり好ましくない。If the amount of resin used is 50 parts by weight or more, the amount of ink transferred is undesirable.
以上の様に本発明のインク層の組成比は、インク層総量
１００重量部に対し前出の共重合体のカヂオン染料染色
物１０重聞部以上、ワックス類９０重量部以下、さらに
は樹脂類５０重量部以下から成っている。As described above, the composition ratio of the ink layer of the present invention is such that, based on 100 parts by weight of the total amount of the ink layer, 10 parts by weight or more of the cationic dye dyed product of the above-mentioned copolymer, 90 parts by weight or less of wax, and 90 parts by weight or less of resin. 50 parts by weight or less.
さらに又、本発明のインク層には、上記成分以外に各種
添加剤が含有されても良い。例えばひまし油、あまに油
、オリーブ油などの植物性部、鯨油、牛脂などの動物性
油、鉱物性油、可塑剤などが好適に使用されて良い。又
例えば老化防止剤、安定剤などが配合されても良い。Furthermore, the ink layer of the present invention may contain various additives in addition to the above components. For example, vegetable parts such as castor oil, linseed oil, and olive oil, animal oils such as whale oil and beef tallow, mineral oils, and plasticizers may be suitably used. Further, for example, anti-aging agents, stabilizers, etc. may be added.
本発明の感熱転写記録媒体は、上記の成分を含有する熱
溶融性インクを転写シート支持体に塗工する。In the heat-sensitive transfer recording medium of the present invention, a heat-melting ink containing the above components is applied to a transfer sheet support.
本発明の感熱転写記録媒体に用いられる基材としての支
持体は、耐熱強度を有し、寸法安定性および表面平滑性
の高い支持体が望ましい。The support used as a base material for the thermal transfer recording medium of the present invention preferably has heat-resistant strength, high dimensional stability, and high surface smoothness.
耐熱強度としては、サーマルヘッド等の熱源によって軟
化、可塑化しない支持体としての強靭さと寸法安定性を
必要とし、表面平滑性としては、支持体上の熱溶融性イ
ンク層が良好な転写率を示ずに充分な平滑度が望まれる
。In terms of heat resistance, the support must have toughness and dimensional stability that will not soften or plasticize due to heat sources such as thermal heads, and in terms of surface smoothness, the heat-melting ink layer on the support must have a good transfer rate. Sufficient smoothness is desired without any visible signs.
支持体の好ましい平滑度は、ベック試験機による平滑度
試験（ＪＩＳ Ｐ ８１１９）で１００ＳｅＣ以上のも
のが良い。The preferable smoothness of the support is 100 SeC or more as determined by a smoothness test using a Beck tester (JIS P 8119).
材料としては例えば普通紙、コンデンサー紙。Examples of materials include plain paper and condenser paper.
ラミネート紙、コート紙等の紙類、あるいはポリエチレ
ン、ポリエヂレンテレフタレート、ポリスチレン、ポリ
プロピレン、ポリイミド等の樹脂フィルム類および紙−
樹脂フィルム複合体。Paper such as laminated paper and coated paper, or resin films and paper such as polyethylene, polyethylene terephthalate, polystyrene, polypropylene, and polyimide.
Resin film composite.
アルミ箔等の金属シート等がいずれも好適に使用される
。Metal sheets such as aluminum foil are preferably used.
支持体の厚さは良好な熱伝導性をうる上で通常６０μｍ
以下、特に２〜２０μｍであるのが望ましい。なお本発
明の感熱転写記録媒体はその支持休店面側の構成は任意
である。なお又、中間層（例えば接着性樹脂層）上塗層
（例えば保護層）等のインク層以外の層構成を有してい
ても良い。The thickness of the support is usually 60 μm in order to obtain good thermal conductivity.
Hereinafter, it is particularly desirable that the thickness be 2 to 20 μm. The structure of the supporting surface side of the thermal transfer recording medium of the present invention is arbitrary. Furthermore, it may have a layer structure other than the ink layer, such as an intermediate layer (for example, an adhesive resin layer) and an overcoat layer (for example, a protective layer).
本発明の感熱転写記録媒体において、熱溶融性インク層
を重合体フィルム等の支持体に塗布するのに適した技術
は当業界において公知であり、これらの技術は本発明に
も適用することが出来る。例えばインクの塗工法として
は、一般のボットメルトコーティングやソルベントコー
ティングによって行われるが、水系塗液として塗工する
ことも可能である。塗工機はエアーナイフコーター、ロ
ールコータ−、ブレードコーター、バーコーター等の公
知のコーターで塗工されるし、又フレキソ法、グラビア
法等での公知の印刷機も使用され得る。フルカラー画像
を１７６ためには、少くともイエロー、マピンタ。Techniques suitable for applying the heat-melt ink layer to a support such as a polymer film in the thermal transfer recording medium of the present invention are known in the art, and these techniques can also be applied to the present invention. I can do it. For example, the ink may be applied by general bot-melt coating or solvent coating, but it is also possible to apply it as an aqueous coating liquid. Coating can be carried out using a known coater such as an air knife coater, roll coater, blade coater, or bar coater, and a known printing machine using a flexo method, a gravure method, etc. may also be used. For full color images, at least yellow, mapinta.
シアンの各色のインクを同一支持体上に線順次。Line sequentially apply each color of cyan ink on the same support.
画順次０点順次の方式で部分印刷をして実施される。Partial printing is carried out using an image-sequential 0-point sequential method.
又受像シートとしては紙、プラスチックフィルムあるい
は合成紙などを用いることが出来る。Further, as the image receiving sheet, paper, plastic film, synthetic paper, etc. can be used.
本発明の熱溶融性インク組成物における前出の着色材と
しての特定の共重合体のカチオン染料染色物は、それ自
身、熱溶融性であり、かつワックス類とも良く相溶して
溶融時均−に溶解分散する。この理由については明確で
はないが、本発明の特定の共重合体の染色物中の染料分
子および共重合体鎖中の脂肪族基が関与していると考え
られる。The cationic dye dyed material of the specific copolymer as the coloring material in the heat-melt ink composition of the present invention is itself heat-meltable, and is well compatible with waxes and has a uniform melting time. -Dissolve and disperse in. The reason for this is not clear, but it is thought that the dye molecules and aliphatic groups in the copolymer chain in the dyed product of the specific copolymer of the present invention are involved.
（発明の効果）
本発明によれば、従来の顔料を使用したインクに比べ、
顔料の分散工程が不要となることが効果の第１点にあげ
ることが出来る。(Effects of the Invention) According to the present invention, compared to inks using conventional pigments,
The first advantage is that the pigment dispersion step is not required.
さらに本発明のインク層は熱溶融時に均一な溶融状態を
与えることが出来、印像のドツト精度１芭調の再現性を
向上出来る。Further, the ink layer of the present invention can provide a uniform melting state during thermal melting, and can improve the dot accuracy of the printed image and the reproducibility of one step.
又色調はカチオン染料を使用するため鮮明であり極めて
高い透明感のある印像を与えることが出来る。Furthermore, since a cationic dye is used, the color tone is clear and an image with extremely high transparency can be provided.
以下に実施例をあげて本発明をさらに詳細に説明するが
、本発明の実ＦＭ＠様がこれらに限定されるものではな
い。なお以下に用いる「部」とは全て重量部を示す。The present invention will be explained in more detail with reference to Examples below, but the actual FM@ of the present invention is not limited to these examples. Note that all "parts" used below refer to parts by weight.
本発明の共重合体は以下に述べる方法で製造した。The copolymer of the present invention was produced by the method described below.
１″、１られた共重合体中の七ツマー組成比は、共重合
体の染色物の燃焼法による元素分析を行うことにより求
めた。1'', the seven-mer composition ratio in the copolymer was determined by elemental analysis of the dyed copolymer by the combustion method.
溶融温度は共重合体の染色物を２枚のガラス板に挾み加
温し２枚のガラス板がくっくつ湿度を測定することによ
り求めた。The melting temperature was determined by heating the dyed copolymer between two glass plates and measuring the humidity when the two glass plates were brought together.
製造例１
窒素置換した５００ ｍ１重合フラスコにＮ−メチルピ
ロリドン３６０ｇ、ステアリルメタクリレート３４ｇ、
アクリルアミド−２−メチルプロパンスルホン酸６ｇを
仕込み撹拌しながら９０℃に胃温し、アゾビスイソブヂ
ロニトリル２３を加え重合を開始した。引き続き撹拌を
続け、９０℃で１５時間重合した。Production Example 1 In a 500 ml polymerization flask purged with nitrogen, 360 g of N-methylpyrrolidone, 34 g of stearyl methacrylate,
6 g of acrylamide-2-methylpropanesulfonic acid was charged and heated to 90° C. with stirring, and 23 ml of azobisisobutyronitrile was added to initiate polymerization. Subsequently, stirring was continued, and polymerization was carried out at 90° C. for 15 hours.
得られたポリマー溶液にアイビン力チロンブリリアント
レッド４０Ｈ（カチオン染料Ｃ，！。The obtained polymer solution was added with Aibin Chiron Brilliant Red 40H (cationic dye C,!).
ベーシックレッド１４、保土谷化学工業■製）３０９を
添加し、７０℃で６０分間撹拌した。Basic Red 14 (manufactured by Hodogaya Chemical Industry ■) 309 was added and stirred at 70°C for 60 minutes.
次にこの溶液を大損の水中に投入して着色したポリマー
を析出させ、分離・乾燥して共重合体の染色物３５．３
ｇを得た。得られた共重合体中の七ツマー組成比はステ
アリルメタクリレート７５七ル％、アクリルアミド−２
−メチルプロパンスルホン酸２５モル％であり、染色物
の溶融温度ハ４８〜５３℃テ１２０℃テノ溶融粘度ハ３
００ Ｐ ａ −５であった。Next, this solution is poured into a large pot of water to precipitate the colored polymer, which is then separated and dried to produce a dyed copolymer.35.3
I got g. The resulting copolymer had a composition ratio of 75% stearyl methacrylate and 2% acrylamide.
- Methylpropanesulfonic acid is 25 mol%, and the melting temperature of the dyed product is 48-53℃, and the melt viscosity is 120℃.
00 Pa-5.
製造例２
製造例１においてカチオン染料をアイゼンカチオンブリ
リアントイエロー５ＧＬＨ（Ｃ，Ｉ。Production Example 2 In Production Example 1, the cationic dye was changed to Eisen Cation Brilliant Yellow 5GLH (C,I).
ベーシックイエロー１３．保土谷化学工業■製）２４ｇ
に変えた以外は製造例１と同様にして行い、共重合体の
染色物３３．０ｇを１ｑだ。染色物の溶融温度は４５〜
５０’Ｃで、１２０℃での溶融粘度は３１０ｐａ−ｓで
あった。Basic yellow 13. Manufactured by Hodogaya Chemical Industry ■) 24g
The procedure was carried out in the same manner as in Production Example 1 except that 33.0 g of the dyed copolymer was used in 1 q. The melting temperature of dyed products is 45~
At 50'C, the melt viscosity at 120C was 310 pa-s.
製造例３
製造例１においてカチオン染料をアイビンカチロンピュ
アーブルー５０Ｈ（Ｃ，１，ベーシックブルー３、保土
谷化学工業■製）３２ｇに変えた以外は製造例１と同様
にして行い、共重合体の染色物３１．５ｇを得た。染色
物の溶融温度は４７〜５２℃で、１２０℃での溶融粘度
は３３０Ｐａ−５であった。Production Example 3 A copolymer was produced in the same manner as in Production Example 1 except that the cationic dye in Production Example 1 was changed to 32 g of Ivin Cachilon Pure Blue 50H (C, 1, Basic Blue 3, manufactured by Hodogaya Chemical Industry ■). 31.5 g of dyed product was obtained. The melting temperature of the dyed product was 47-52°C, and the melt viscosity at 120°C was 330 Pa-5.
製ｊｂ例４
ステアリルメタクリレート３４ｇをトリデシルメタクリ
レート３／ＩＪに変えた以外は製造例１と同様に重合、
染色を行い、水中に投入し共重合体の染色物３０．５９
を１９だ。（９られた共重合体中の七ツマー組成比はト
リデシルメタクリレート８０モル％、アクリルアミド−
２−メチルプロパンスルホン酸２０モル％であり、染色
物の溶融温度は３０〜３５℃で、１２０℃での溶融粘度
は１８０Ｐａ・Ｓであった。Production jb Example 4 Polymerization was carried out in the same manner as Production Example 1 except that 34 g of stearyl methacrylate was changed to tridecyl methacrylate 3/IJ.
Dyeing is carried out and the copolymer dyed product is put into water.30.59
It's 19. (The heptamer composition ratio in the copolymer was 80 mol% tridecyl methacrylate, 80 mol% acrylamide,
The content of 2-methylpropanesulfonic acid was 20 mol %, the melting temperature of the dyed product was 30 to 35°C, and the melt viscosity at 120°C was 180 Pa·S.
製造例５
窒素置換した５００ ｄ重合フラスコにＮ−メチルピロ
リドン２０９を仕込み９０℃に昇温した。次にこのフラ
スコ中へ撹拌しながらステアリルメタクリレート１１．
９ｇ、アリルスルホン酸ナトリウム２．１ ｇ、Ｎ−、
メチルピロリドン２００９からなるモノマー溶液および
アゾビスイソブチロニトリル１．３９． Ｎ−メチルピ
ロリドン２３．７ｇからなる触媒溶液を２時間かけて滴
下しながら重合を行い、引き続き１５時間反応を続けた
。Production Example 5 N-methylpyrrolidone 209 was charged into a 500 d polymerization flask purged with nitrogen, and the temperature was raised to 90°C. Next, stearyl methacrylate 11.
9 g, sodium allylsulfonate 2.1 g, N-,
Monomer solution consisting of methylpyrrolidone 2009 and azobisisobutyronitrile 1.39. Polymerization was carried out by dropping a catalyst solution consisting of 23.7 g of N-methylpyrrolidone over 2 hours, and the reaction was then continued for 15 hours.
１ｑられたポリマー溶液にアイゼンカチオンブリリアン
トイエロー５０ Ｌ ）−１２００％（カチオン染料Ｃ
，１，ベーシックイエロー１３、保土谷化学工業■製）
１０ｇを添加し、７０℃で６０分間撹拌した。Add 1q of Eisen Cation Brilliant Yellow 50L)-1200% (Cationic Dye C
, 1, Basic Yellow 13, manufactured by Hodogaya Chemical Industry ■)
10 g was added and stirred at 70° C. for 60 minutes.
次に製造例１と同様に水中に投入し、共重合体の染色物
６．０ｇを得た。得られた共重合体中の七ツマー組成比
はステアリルメタクリレート８０モル％、アリルスルホ
ン酸ナトリウム２０モル％であり、染色物の溶融温度は
４０〜４５℃で、１２０℃での溶融粘度は２００ｐａ−
５であった。Next, it was poured into water in the same manner as in Production Example 1 to obtain 6.0 g of a dyed copolymer. The heptamer composition ratio in the obtained copolymer was 80 mol% of stearyl methacrylate and 20 mol% of sodium allylsulfonate, the melting temperature of the dyed product was 40 to 45°C, and the melt viscosity at 120°C was 200 pa-
It was 5.
製造例６
ステアリルメタクリレート１１．９ｇをトリデシルメタ
クリレート１１．９ｇに変えた以外は製造例５と同様に
重合、染色を行い、水中に投入し共重合体の染色物５．
０９を得た。１ｑられた共重合体中の七ツマー相成比は
トリデシルメタクリレート８０モル％、アリルスルホン
酸ナトリウム２０モル％であり、染色物の溶融温度は２
０〜２５°Ｃで、１２０℃での溶融粘度は１２０ｐａ−
ｓであった。Production Example 6 Polymerization and dyeing were carried out in the same manner as Production Example 5 except that 11.9 g of stearyl methacrylate was replaced with 11.9 g of tridecyl methacrylate, and the dyed copolymer was poured into water.
I got 09. The 7-mer phase composition ratio in the copolymer obtained was 80 mol% tridecyl methacrylate and 20 mol% sodium allylsulfonate, and the melting temperature of the dyed product was 2.
0-25°C, melt viscosity at 120°C is 120 pa-
It was s.
製造例７
”ＩＪＬ例５におけるモノマー溶液をステアリルメタク
リレート２１．３ｇ、ライトエステルＰ−Ａ（２−ヒド
ロキシエヂルアクリロイルボスフェート、共栄社油脂化
学工業■製）３．７ｇ、Ｎ−メチルピロリドン２００９
からなるモノマー溶液に変えた以外は製造例５と同様に
重合を行った。Production Example 7 The monomer solution in IJL Example 5 was mixed with 21.3 g of stearyl methacrylate, 3.7 g of Light Ester PA (2-hydroxyedyl acryloylbosphate, manufactured by Kyoeisha Yushi Kagaku Kogyo ■), and 2009 N-methylpyrrolidone.
Polymerization was carried out in the same manner as in Production Example 5 except that the monomer solution was changed to
ｊｑられたポリマー溶液にアイゼン力チロンブルーＧＬ
Ｉ−１（カチオン染料Ｃ，１，ベーシックブルー６５、
保土谷化学工業Ｉｌ製）１５ｇを添加し、７０℃で６０
分間撹拌した。Eisen force Chiron Blue GL in the polymer solution
I-1 (cationic dye C,1, basic blue 65,
Added 15g of Hodogaya Chemical Industry Il) and heated to 60℃ at 70℃.
Stir for a minute.
次に製造例１と同様に水中に投入し、共重合体の染色物
１１．４ｇを得た。得られた共重合体中の組成比はステ
アリルメタクリレート８０モル％。Next, it was poured into water in the same manner as in Production Example 1 to obtain 11.4 g of a dyed copolymer. The composition ratio in the obtained copolymer was 80 mol% of stearyl methacrylate.
ライトエステルＰ−Ａ２０モル％であり、染色物の溶融
温度は５５〜６０℃で、１２０℃での溶融粘度は２５０
Ｐａ−ｓであった。Light ester P-A is 20 mol%, the melting temperature of the dyed product is 55-60°C, and the melt viscosity at 120°C is 250°C.
It was Pa-s.
製造例８
製造例５におけるモノマー溶液をステアリルメタクリレ
ート２３．Ｏｇ、アクリル酸２．５ ｇ、 Ｎ−メヂル
ピロリドン２００ ｇからなる七ツマー溶液に変えた以
外は製造例５と同様に重合を行った。Production Example 8 The monomer solution in Production Example 5 was mixed with stearyl methacrylate 23. Polymerization was carried out in the same manner as in Production Example 5, except that the solution was changed to a seven-mer solution consisting of Og, 2.5 g of acrylic acid, and 200 g of N-methylpyrrolidone.
１ｑられたポリマー溶液にアイゼン力チロンブルーＧＬ
Ｉ−１２６ｇを添加し、７０℃で６０分間撹拌した。Add 1q of Eisen Chiron Blue GL to the polymer solution.
126 g of I-1 was added and stirred at 70°C for 60 minutes.
次にＷＡ造例１と同様に水中に投入し、共重合体の染色
物１７．０９を得た。得られた共重合体中のモノマー組
成比はステアリルメタクリレート１５モル％、アクリル
酸２５モル％であり、染色物の溶融温度は５０〜５５℃
で、１２０℃での溶融粘度は２４０Ｐａ−３であった。Next, it was poured into water in the same manner as in WA Preparation Example 1 to obtain a copolymer dyed product 17.09. The monomer composition ratio in the obtained copolymer was 15 mol% of stearyl methacrylate and 25 mol% of acrylic acid, and the melting temperature of the dyed product was 50 to 55°C.
The melt viscosity at 120°C was 240 Pa-3.
実施例１〜３
下記の熱溶融性インクを各々厚さ６μｍのポリエチレン
フタレートフィルム支持体上にバーコーターで塗布して
膜厚１０μｍのインク層を有する本発明の感熱転写記録
媒体の試料を得た。Examples 1 to 3 Each of the following heat-melting inks was coated on a polyethylene phthalate film support with a thickness of 6 μm using a bar coater to obtain a sample of a thermal transfer recording medium of the present invention having an ink layer with a thickness of 10 μm. .
製造例１〜３の共重合体染色物 ３０部パラフィ
ンワックス（融点５５℃） ６０部ウつトラセン
ＵＥＯ２０５１０部
（エチレン・ビニルアセテート共重合体）（Ｍ Ｉ ：
１０５０．酢酸ビニル含量： ２５．５ｗｔ％、融点
６８℃、東洋曹達工業（体製）
上記で得られた感熱転写記録媒体試料をサーマルプリン
ター（発熱素子密度８ ｄｏｔ／ｍの薄膜型ラインサー
マルヘッドを搭載した試験機）で普通紙上に印字した所
各々マゼンタ、イエロー。Copolymer dyed products of Production Examples 1 to 3 30 parts Paraffin wax (melting point 55°C) 60 parts Utracene UEO 20510 parts (ethylene-vinyl acetate copolymer) (MI:
1050. Vinyl acetate content: 25.5 wt%, melting point 68°C, manufactured by Toyo Soda Kogyo Co., Ltd. The thermal transfer recording medium sample obtained above was transferred to a thermal printer (equipped with a thin-film line thermal head with a heating element density of 8 dots/m). When printed on plain paper using a testing machine, the colors are magenta and yellow, respectively.
シアンの鮮明な印字が出来た。Clear cyan printing was possible.
実施例４〜８
下記の熱溶融性インクを各々厚さ６μｍのポリエチレン
フタレートフィルム支持体上にｔｌＴｉして膜厚１０μ
ｍのインク層を有する本発明の感熱転写記録媒体の試料
を１７だ。Examples 4 to 8 Each of the following heat-melting inks was tlTied on a 6 μm thick polyethylene phthalate film support to give a film thickness of 10 μm.
Sample No. 17 is a sample of the thermal transfer recording medium of the present invention having an ink layer of m.
製造例４〜８の共重合体染色物 ３０部パラフィ
ンワックス（融点６４〜６６℃＞ ６０部ウルトラセ
ンＵ Ｅ ０２０５ １０部上記で得ら
れた感熱転写記録媒体試料をサーマルプリンター（発熱
素子密度８ ｄｏｔ／ｍの薄膜型ラインサーマルヘッド
を搭載した試験機）で普通紙上に印字した所各々マゼン
タ、イエロー。Copolymer dyed products of Production Examples 4 to 8 30 parts Paraffin wax (melting point 64 to 66°C> 60 parts Ultracene UE 0205 10 parts The thermal transfer recording medium sample obtained above was printed on a thermal printer (heating element density 8 dots) Printed on plain paper using a testing machine equipped with a thin-film line thermal head of 1.5 mm (magenta) and yellow (magenta and yellow, respectively).
シアンの鮮明な印字が出来た。Clear cyan printing was possible.
実施例９〜１１
下記の熱溶融性インクを各々厚さ６μｍのポリエチレン
テレフタレートフイルム支持体上に塗布して膜厚１０μ
尻のインク層を有する感熱転写記録媒体の試料を１１だ
。Examples 9 to 11 Each of the following heat-melting inks was applied onto a polyethylene terephthalate film support with a thickness of 6 μm to obtain a film thickness of 10 μm.
Sample 11 is a thermal transfer recording medium having a bottom ink layer.
」−記で得られた感熱転写記録媒体試料を実施例１〜３
で用いたと同じサーマルプリンターで普通紙上に印字し
た所、各々鮮明な印字が出来た。The thermal transfer recording medium samples obtained in ``-- were used in Examples 1 to 3.
When printed on plain paper using the same thermal printer used in , each print was clear and clear.
Claims (3)
る感熱転写記録媒体において、該インク層総量１００重
量部に対し、アクリル酸エステルおよび／またはメタク
リル酸エステルの１種又はそれ以上の６０モル％以上と
カチオン染料可染ダイサイトを有するモノマー（但し、
スチレンスルホン酸又はその塩を除く。）の１種又はそ
れ以上の１モル％以上から成る共重合体のカチオン染料
による染色物１０重量部以上、ワックス類９０重量部以
下および樹脂類５０重量部以下を含有することを特徴と
する感熱転写記録媒体。(1) In a thermal transfer recording medium in which a heat-melting ink layer is formed on one side of a support, one or more acrylic esters and/or methacrylic esters are used per 100 parts by weight of the total amount of the ink layer. A monomer having 60 mol% or more of cationic dye-dyeable dicite (however,
Excludes styrene sulfonic acid or its salts. A dyed product containing 10 parts by weight or more of a cationic dye of a copolymer containing 1 mol% or more of one or more of the following: 90 parts by weight or less of waxes and 50 parts by weight or less of resins Thermal transfer recording medium.
スチレンスルホン酸以外のスルホン酸基、リン酸基、カ
ルボン酸基又はこれらの塩を有するモノマーである特許
請求の範囲第１項記載の感熱転写記録媒体。(2) The thermal transfer recording according to claim 1, wherein the monomer having cationic dye-dyeable dicite is a monomer having a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, or a salt thereof other than styrene sulfonic acid. Medium.
テルおよび／またはメタクリル酸エステルの１種又はそ
れ以上の６０モル％以上とカチオン染料可染ダイサイト
を有するモノマーの１種又はそれ以上の１モル％以上と
から成る共重合体のカチオン染料による染色物が少くと
もイエロー、マゼンタ、シアンの各色からなり、これら
を含有する熱溶融性インクが同一支持体上に部分塗工さ
れている特許請求の範囲第１項又は第２項記載の感熱転
写記録媒体。(3) 60 mol% or more of one or more acrylic esters and/or methacrylic esters used in the heat-melting ink layer and one or more monomers having cationic dye-dyeable dicite; A patent in which a dyed product using a cationic dye of a copolymer consisting of 1 mol% or more consists of at least yellow, magenta, and cyan colors, and a hot-melt ink containing these colors is partially coated on the same support. A thermal transfer recording medium according to claim 1 or 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62146502A JPS63309494A (en) | 1987-06-12 | 1987-06-12 | Thermal transfer recording medium |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62146502A JPS63309494A (en) | 1987-06-12 | 1987-06-12 | Thermal transfer recording medium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63309494A true JPS63309494A (en) | 1988-12-16 |
Family
ID=15409077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62146502A Pending JPS63309494A (en) | 1987-06-12 | 1987-06-12 | Thermal transfer recording medium |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63309494A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5106695A (en) * | 1990-06-13 | 1992-04-21 | Presstek, Inc. | Method and means for producing color proofs |
| JP2013091178A (en) * | 2011-10-24 | 2013-05-16 | Fujikura Kasei Co Ltd | Anti-blocking agent |
-
1987
- 1987-06-12 JP JP62146502A patent/JPS63309494A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5106695A (en) * | 1990-06-13 | 1992-04-21 | Presstek, Inc. | Method and means for producing color proofs |
| JP2013091178A (en) * | 2011-10-24 | 2013-05-16 | Fujikura Kasei Co Ltd | Anti-blocking agent |
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