JPH0453716B2 - - Google Patents
Info
- Publication number
- JPH0453716B2 JPH0453716B2 JP61182772A JP18277286A JPH0453716B2 JP H0453716 B2 JPH0453716 B2 JP H0453716B2 JP 61182772 A JP61182772 A JP 61182772A JP 18277286 A JP18277286 A JP 18277286A JP H0453716 B2 JPH0453716 B2 JP H0453716B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- transfer
- biaxially oriented
- ink layer
- less
- 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
- 238000012546 transfer Methods 0.000 claims description 67
- 229920006267 polyester film Polymers 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 29
- 238000009826 distribution Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- 238000012360 testing method Methods 0.000 claims description 3
- -1 Aromatic dicarboxylic acids Chemical class 0.000 description 29
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 27
- 238000010438 heat treatment Methods 0.000 description 17
- 229920000728 polyester Polymers 0.000 description 16
- 238000000576 coating method Methods 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 238000011282 treatment Methods 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- 238000007639 printing Methods 0.000 description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000037303 wrinkles Effects 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000010419 fine particle Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 229920001296 polysiloxane Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000003086 colorant Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 239000004203 carnauba wax Substances 0.000 description 3
- 235000013869 carnauba wax Nutrition 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 230000002040 relaxant effect Effects 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 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 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 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
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 229940099259 vaseline Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- XCSGHNKDXGYELG-UHFFFAOYSA-N 2-phenoxyethoxybenzene Chemical compound C=1C=CC=CC=1OCCOC1=CC=CC=C1 XCSGHNKDXGYELG-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical class [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- AOADSHDCARXSGL-ZMIIQOOPSA-M alkali blue 4B Chemical compound CC1=CC(/C(\C(C=C2)=CC=C2NC2=CC=CC=C2S([O-])(=O)=O)=C(\C=C2)/C=C/C\2=N\C2=CC=CC=C2)=CC=C1N.[Na+] AOADSHDCARXSGL-ZMIIQOOPSA-M 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- FNGGVJIEWDRLFV-UHFFFAOYSA-N anthracene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=CC3=C(C(O)=O)C(C(=O)O)=CC=C3C=C21 FNGGVJIEWDRLFV-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 1
- 150000001558 benzoic acid derivatives 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
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- MAYPHUUCLRDEAZ-UHFFFAOYSA-N chlorine peroxide Chemical compound ClOOCl MAYPHUUCLRDEAZ-UHFFFAOYSA-N 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- YCITZMJNBYYMJO-UHFFFAOYSA-N chloro(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](Cl)C1=CC=CC=C1 YCITZMJNBYYMJO-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000006103 coloring component Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 1
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000009477 glass transition Effects 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
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 238000007757 hot melt coating Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229940031993 lithium benzoate Drugs 0.000 description 1
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- 239000005048 methyldichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- B41M5/10—Duplicating or marking methods; Sheet materials for use therein by using carbon paper or the like
Description
産業上の利用分野
本発明はプリンター用転写材に関し、更に詳し
くは耐久性、転写性、寸法安定性、走行性に優れ
たプリンター用転写材に関する。
従来技術
プリンター用転写材の基本的な構成は、基体と
該基体の片面に塗布したインク層からなる。
従来、この基体として、二軸配向ポリエステル
フイルムが耐薬品性、強度、弾性率、耐熱性、結
晶性、高融点等の優れた性質を有する点から広く
用いられている。
ところで、プリンター用転写材は、繰り返し使
用される使い方が強まり、かつこの繰返し使用の
回転も年々増大の傾向にあり、従来の二軸配向ポ
リエステルフイルムでは、例えばドツトインパン
クト方式による転写時における印字部の打たれ残
りによるフイルムの変形や伸びが生じたり、また
感熱転写方式では熱による変形等が生じる等問題
があつた。更にまた、ポリエステルフイルムに塗
布したインク層が反対面（走行面）に転写してリ
ボンの走行面を汚し、これが走行系のガイドポス
ト等の接触部に徐々にインクを蓄積させる等走行
トラブルがあつた。
発明の目的
本発明の目的は、上述の問題を解消し、繰返し
使用に適する耐久性、転写性、寸法安定性、走行
性に優れたプリンター用転写材を提供することに
ある。
発明の効果・構成
本発明の目的は、本発明によれば、厚さ１〜
25μｍの二軸配向ポリエステルフイルムの片面に
厚さ３〜35μｍの転写インク層を設けたプリンタ
ー用転写材において、該二軸配向ポリエステルフ
イルムが下記(イ)〜(ハ)、
(イ) 縦方向のヤング率が450〜800Kg／mm2である、
(ロ) 縦方向及び横方向の150℃での熱収縮率が７
％以下である、
(ハ) フイルム表面の三次元粗さ計で測定した突起
数（Ｙ：ケ／mm2）と突起高さ（Ｘ：μｍ）との
関係を表わす突起分布曲線がlog10Y＞1.3の領
域において下記式(1)
log10Y＝−1.8X＋3.9 ……(1)
で表わされる線と交差せず、更に該突起分布の
最大値及び該最大値を越えた部分の曲線が下記
式(2)
log10Y≧−3.6X＋2.8 ……(2)
を満足する範囲にある。
を満足するものであり、更に該転写インク層を
設けた面と反対の表面に該転写インク層となじ
みが殆んどない物質を塗設したことを特徴とす
るプリンター用転写材によつて達成される。
本発明におけるポリエステルとは芳香族ジカル
ボン酸を主たる酸成分とし、脂肪族グリコールを
主たるグリコール成分とするポリエステルであ
る。かかるポリエステルは実質的に線状であり、
そしてフイルム形成性特に溶融成形によるフイル
ム形成性を有する。芳香族ジカルボン酸とは、例
えばテレフタル酸、ナフタレンジカルボン酸、イ
ソフタル酸、ジフエノキシエタンジカルボン酸、
ジフエニルジカルボン酸、ジフエニルエーテルジ
カルボン酸、ジフエニルスルホンジカルボン酸、
ジフエニルケトンジカルボン酸、アンスラセンジ
カルボン酸等である。脂肪族グリコールとは、例
えばエチレングリコール、トリメチレングリコー
ル、テトラメチレングリコール、ペンタメチレン
グリコール、ヘキサメチレングリコール、デカメ
チレングリコールの如き炭素数２〜10のポリメチ
レングリコールあるいはシクロヘキサンジメタノ
ールの如き脂環族ジオール等である。
本発明において、ポリエステルとしては例えば
アルキレンテレフタレート及び／又はアルキレン
ナフタレートを主たる構成成分とするものが好ま
しく用いられる。かかるポリエステルのうちでも
例えばポリエチレンテレフタレート、ポリエチレ
ン−２，６−ナフタレートはもちろんのこと、例
えば全ジカルボン酸成分の80モル％以上がテレフ
タル酸及び／又は２，６−ナフタレンジカルボン
酸であり、全グリコール成分の80モル％以上がエ
チレングリコールである共重合体が特に好まし
い。その際全酸成分の20モル％以下のジカルボン
酸は上記芳香族ジカルボン酸であることができ、
また例えばアジピン酸、セバチン酸の如き脂肪族
ジカルボン酸；シクロヘキサン−１，４−ジカル
ボン酸の如き脂肪族ジカルボン酸等であることが
できる。また、全グリコール成分の20モル％以下
は、エチレングリコール以外の上記グリコールで
あることができ、あるいは例えばハイドロキノ
ン、レゾルシノール、２，２−ビス（４−ヒドロ
キシフエニル）プロパンの如き芳香族ジオール；
１，４−ジヒドロキシメチルベンゼンの如き芳香
族を含む脂肪族ジオール；ポリエチレングリコー
ル、ポリプロピレングリコール、ポリテトラメチ
レングリコールの如きポリアルキレングリコール
（ポリオキシアルキレングリコール）等であるこ
ともできる。
また、本発明で用いられるポリエステルには、
例えばヒドロキシ安息香酸の如き芳香族オキシ
酸；ω−ヒドロキシカプロン酸の如き脂肪族オキ
シ酸等のオキシカルボン酸に由来する成分を、ジ
カルボン酸成分およびオキシカルボン酸成分の総
量に対し20モル％以下で含有するものも包含され
る。さらに本発明におけるポリエステルには実質
的に線状である範囲の量、例えば全酸成分に対し
２モル％以下の量で、３官能以上のポリカルボン
酸又はポリヒドロキシ化合物、例えばトリメリツ
ト酸、ペンタエリスリトールを共重合したものも
包含される。
上記ポリエステルは、それ自体公知であり、且
つそれ自体公知の方法で製造することができる。
上記ポリエステルとしては、0−クロロフエノー
ル中の溶液として35℃で測定して求めた固有粘度
が約0.4〜約0.9のものが好ましい。
また、上述のポリエステルは必要に応じて、安
定剤、着色剤、酸化防止剤等の添加剤を含有する
ものであつてもよい。
本発明における二軸配向ポリエステルフイルム
は、上述のポリエステルから製造される二軸配向
フイルムである。このフイルムは縦方向のヤング
率450〜800Kg／mm2、好ましくは500〜750Kg／mm2の
特性を有するものである。なお、フイルムの縦方
向はインキ転写リボンの長手方向と一致する。こ
の縦方向のヤング率が450Kg／mm2未満であると、
フイルムが伸びやすく、弾性回復しにくいため、
複写リボンとして用いて印字すると、印字部は印
字圧力による塑性変形が生じ、必要以上に太く印
字される等印字の鮮明性が悪く、又該変形のため
転写リボンの巻取りの取扱い性が劣る等で好まし
くない。また、縦方向のヤング率が800Kg／mm2を
越えると、剛性が強いため、印字の圧力のために
フイルムが裂けやすくなり、好ましくない。
又、本発明におけるポリエステルフイルムの厚
さは１〜25μｍが汎用的であり、好ましくは２〜
10μｍ、更に好ましくは３〜8μｍである。フイル
ムの厚さが上述の範囲よりも薄いと強度が不足し
て、転写リボンとしたときの適性に欠け、更には
加工適性の面からも劣つたものとなり、一方上述
の範囲よりも厚いと、特に感熱転写方式では熱伝
達に時間がかかり記録速度を速めてしかも鮮明な
転写画像を得るには適さなくなるので好ましくな
い。
本発明における二軸配向ポリエステルフイルム
は、上述の縦方向ヤング率及び厚さを有するが、
更に転写インク層を設ける表面が三次元粗さ計で
測定した突起数（Ｙ：ケ／mm2）と突起高さ（Ｘ：
μｍ）との関係を表わす突起分布曲線がlog10Y
＞1.3の領域において、下記式(1)で表わされる線
と交差せず、更に該突起分布の最大値及び該最大
値を越えた部分の曲線が下記式(2)を満足する範囲
にある表面特性を有する。
log10Y＝−1.8x＋3.9 ……(1)
log10Y≧−3.6X＋2.8 ……(2)
フイルム表面粗さが式log10＝−3.6X＋2.8で表
わされる直線を下まわるか或は最大値を越えた部
分で交差する（特に突起高さが大きい部分が交差
して下側に下る如き）突起分布を呈する場合に
は、インク層を塗工した後にロールに巻いたとき
フイルムの反対面（走行面）に該インクが転写し
やすくなり、リボンの走行面を汚し、これがリボ
ンの走行系のガイドポスト等の接触部に徐々にイ
ンクを蓄積させ、リボンの走行を阻害し、極端な
場合にはリボンが動かなくなる等のトラブルを生
じ、その他、フイルムの滑り性が悪くなる結果、
加工時にフイルムにしわが入つたりするので、好
ましくない。また、フイルムの表面粗さが上記式
(1)と交差する突起分布を呈する程粗れている場合
には、印字の鮮明さが悪くなり、又サーマルヘツ
ドの消耗の原因となり、実用上問題となるので好
ましくない。
上述のフイルム表面は、更に、多重干渉反射式
顕微鏡（Tl単色光）で測定した突起数（ケ／mm2）
と突起高さ（ｈ：μｍ）が
1.5≧ｈ＞1.0 ……10ケ／mm2以下
1.0≧ｈ＞0.75 ……１〜30ケ／mm2
0.75≧ｈ＞0.5 ……15〜120ケ／mm2
0.5≧ｈ＞0.25 ……80ケ／mm2以上
を満足することが好ましい。おの表面特性を満足
することは、インク層のフイルム反対面への転写
を防止する点から、また印字の鮮明性の面から、
特に好ましい。
又、フイルム表面の最大突起高さは3μｍ以下、
更に1.5μｍ以下であることが望ましい。
本発明における二軸配向ポリエステルフイルム
の上述の表面粗さは、フイルム中に不活性無機、
有機微粒子等を添加することによつて形成するの
が好ましい。この不活性微粒子を用いる場合は、
平均粒径が0.01〜10μｍの粒子を0.01〜５重量％、
更には平均粒径が0.03〜4μｍの粒子を0.01〜1.5重
量％添加させるのが好ましい。この際、添加する
不活性無機、有機の微粒子は単成分でもよく、二
成分ないしはそれ以上を同時に用いてもよい。
上述の不活性微粒子としては、本発明において
は、好ましくは二酸化ケイ素（水和物、ケイ藻
土、ケイ砂、石英等を含む）；アルミナ；
SiO2分を30重量％以上含有するケイ酸塩（例え
ば非晶質或は結晶質の粘土鉱物、アルミノシリケ
ート（焼成物や水和物を含む）、温石綿、ジルコ
ン、フライアツシユ等）、Mg、Zn、Zr及びTi
の酸化物；Ca及びBaの硫酸塩；Li、Na及び
Caのリン酸塩（１水素塩や２水素塩を含む）；
Li、Na及びＫの安息香酸塩；Ca、Ba、Zn及
びMnのテレフタル酸塩；Mg、Ca、Zn、Cd、
Sr、Mn、Fe、Co及びNiのチタン酸塩；Ba及
びPbのクロム酸塩；炭素（例えばカーボンブ
ラツク、グラフイト等）；ガラス（例えばガラ
ス粉、ガラスビーズ等）；Ca及びMgの炭酸
塩；ホタル石；及びZnSが例示される。更に
好ましくは、無水ケイ酸、含水ケイ酸、酸化アル
ミニウム、ニウム、ケイ酸アルミニウム（焼成
物、水和物等を含む）、燐酸１リチウム、燐酸３
リチウム、硝酸ナトリウム、燐酸バリウム、酸化
チタン、安息香酸リチウム、これらの化合物の復
塩（水和物を含む）、ガラス粉、粘土（カオリン、
ペントナイト、白土等を含む）、タルク、ケイ藻
土、炭酸カルシウム等が例示される。
これらの不活性微粒子を含有するポリエステル
は、通常ポリエステルを形成するための反応時、
例えばエステル交換法による場合のエステル交換
反応中あるいは重縮合反応中の任意の時期又は直
接重合法による場合の任意の時期に、不活性微粒
子（好ましくはグリコール中のスラリーとして）
を反応系中に添加することにより製造することが
できる。好ましくは、重縮合反応の初期例えば固
有粘度が約0.3に至るまでの間に、不活性微粒子
を反応系中に添加するのが好ましい。
更に、本発明における二軸配向ポリエステルフ
イルムは、150℃で30分熱処理したときの縦及び
横方向の熱収縮率が７％以下であることが好まし
く、更に好ましくは４％以下、特に好ましくは２
％以下である。この熱収縮率が７％より大きい場
合は弛緩処理時の巾収縮が大きくなるだけでなく
プリンター用転写材に加工する段階即ち、塗布、
乾燥等の工程で収縮を起すことによる厚斑の悪
化、歩留の低下等をもたらすので好ましくない。
またこの熱収縮率が０％未満のときは、弛緩を２
つのロール間の速度差で行う方式の場合には加熱
ロール上でしわが発生し、またペースフイルムを
ロール形状のままプリンター用転写材に加工する
迄の間放置することによつてロール表面の縦方向
にしわが発生し、更にはプリンター用転写材加工
工程中での中間製品ロール表面にしわが発生する
ので好ましくない。これらのしわはフイルムの横
方面の熱膨張が熱収縮より大きいときに発生する
ものと推定される。
更に、使用時の問題点としては、熱収縮率が上
述の範囲を外れると特に感熱プリンター用の転写
リボンに用いたときにリボンの変形が激しく、印
字の鮮明性が劣るとともに該変形のため転写リボ
ンの巻取り取扱い性が劣るようになり、またドツ
トインパクト方式においても熱収縮率が７％を越
える程のものは、印字部の変形が生じやすくな
り、好ましくない。
本発明で用いる二軸配向ポリエステルフイルム
は、その製造方法によつて特に制限を受けない
が、通常所定割合の微粒子を含有するポリエステ
ルを溶融し、スリツト状のダイからシート状に押
し出し、キヤステイングドラムで冷却固化して未
延伸シートとなし、続いて該未延伸シートを二軸
方向に延伸して製品（フイルム）となし、更に加
熱処理（ヒートセツト）、横方向の熱収縮率の調
節処理、次いで縦弛緩処理することによつて製造
される。
その際、本発明の要件を好適に満足するには、
例えば延伸温度は一段目延伸温度（例えば縦方向
延伸度：T1）を（Tg−10）〜（Tg＋45）℃の範
囲（但し、Tg：ポリエステルのガラス転移温度）
とし、二段目延伸温度（例えば横方向延伸温度：
T2）を（T1＋15）〜（T1＋40）℃の範囲とし、
延伸倍率は一段目延伸では2.5〜6.0倍、特に3.5〜
5.5倍とし、二段目延伸では2.5〜4.0倍、特に2.8
〜3.7倍とするのが好ましい。更に得られる二軸
延伸フイルムは好ましくは150〜245℃、更に好ま
しくは170〜240℃の範囲の温度で１〜200秒程度
熱固定する。更に、通常テンターにおける熱処理
条件を調節して横方向の熱収縮率を調整し、その
後縦弛緩処理を行う。
横方向の熱収縮率の調節は、通常縦弛緩処理前
に行う。通常テンターに於ける熱処理時に調節さ
れる。例えば横方向の熱収縮率が不足している場
合には上記熱処理時にフイルムを幅方向に延き伸
ばすと良く、また熱収縮率が大きすぎる場合には
上記熱処理時にフイルムを幅方向に弛緩させると
良い。更に具体的には熱処理温度160℃のときに
は全幅に対し９〜13％弛緩させるとよく、170℃
のときには５〜11％弛緩させるとよく、180℃の
ときには１〜８％弛緩させるとよく、200℃のと
きには０〜５％緊張もしくは弛緩させるとよ舎、
205℃のときには３〜−２％延き伸ばし乃至弛緩
させるとよく、また220℃のときには１〜−６％
延き伸ばし乃至弛緩させるとよい。
縦方向に弛緩する方法としては、例えば空気力
による浮遊処理方式で加熱低張力下、非接触状態
で弛緩する方式；夫々ニツプロールを有する加熱
ロールと冷却ロール間で速度差を与えることによ
つて弛緩する方式又は、テンター内でフイルムを
把持したクリツプの進行速度を逐次狭めることに
よつて縦方向に弛緩する方法等があるが、縦方向
に弛緩できる方式であればいずれの方式も用いる
ことができる。
縦方向に弛緩する時の温度は（Tg＋20）℃以
上（熱処理温度−30）℃以下、好ましくは（Tg
＋30）℃以上（熱処理温度−40）℃以下である。
（Tg＋20）℃より低い温度では、Tg近傍に於け
る熱収縮率を充分下げることができず、また（熱
処理温度−30）℃より高い温度では縦方向の弛緩
量は多くなるも横方向の収縮も大きくなり、横方
向の熱収縮率を満足させることができなくなるだ
けでなく、横方向の機械特性を低下させ、更には
厚み斑を悪化させ、また弛緩を２つのロール間の
速度差で行う方式の場合には、加熱ロール上での
巾収縮によりフイルム面上横方向にスクラツチを
発生させる為好ましくない。縦方向の弛緩量は熱
処理温度によつても異るが、弛緩時のフイルム張
力が10Kg／cm2以上80Kg／cm2以下、好ましくは20
Kg／cm2以上60Kg／cm2以下になるように、例えば弛
緩を２つのロール間の速度差で行う方式の場合に
は、加熱ロールに対し冷却ロールの速度を調節す
るのが好ましい。フイルム張力が10Kg／cm2未満の
場合はフイルムがたるみ、しわが発生するし、張
力が80Kg／cm2より大きくなる場合は熱収縮率を充
分下げることができない。
上述の弛緩処理によつて、当該弛緩処理の温度
以上における縦方向の熱収縮率は塗工物の巻きじ
まりに影響を及ぼさなくなる。従来の縦弛緩によ
ると縦方向の弛緩だけでなく横方向にも収縮を起
し、従つて横方向の熱収縮率が小さくなりすぎ
る。横方向の熱収縮率が小さすぎるとフイルムロ
ール表面にしわが発生したり、プリンター転写材
加工段階でのコーテイング時しわが入り、塗り斑
の原因となる。
かくして得られる二軸配向ポリエステルフイル
ムは、通常、表裏面とも同じ表面特性を呈する。
この場合、転写インク層を設ける面は表面でも裏
面でも良い。
本発明において転写インク層は、バインダー成
分、着色成分に加えて、必要に応じて柔軟剤、可
撓剤、分散剤、平滑剤などを適宜添加して構成さ
れる。
インク成分としては例えばカルナウバワツク
ス、パラフインワツクス、ｎ−脂肪酸アルキルエ
ステル等の如きワツクス類、塩ピ系ポリマー、塩
ピ−酢ピ共重合系ポリマー等の如きバインダー成
分、着色剤、その他成分が用いられる。
着色剤としては、通常カーボンブラツクを主体
とし、その他各種の染料、あるいは有機、無機の
顔料が用いられる。他の例としては、着色剤とし
てニグロシン、メチルバイオレツト、アルカリブ
ルー等を用い、水、ヒマシ油、グリセリン、アル
コール、ワセリン、オレイン酸、パラフイン等を
３〜４種適量組合せるものがあげられる。場合に
よつては転写インクには昇華型のものも含んでよ
い。
転写インク層の形成は、通常の方法、例えば溶
剤を添加した状態でグラビユア、リバース、スリ
ツトダイ方式などの溶液塗工方法、あるいはホツ
トメルト塗工などを用いて行うことができる。そ
の際、二軸配向ポリエステルフイルムは、必要に
応じてコロナ放電及理やバインダーの下びきコー
トなどの前処理を行つてもよい。
インク層の厚さは３〜35μｍである。インク層
が厚すぎると、転写材をロール状に巻いたとき該
インク層の転写（転写材表面への転写）が起るの
で好ましくない。
本発明においては、基体の転写インク層を設け
た反対面（走行面）に塗設する該転写インク層と
なじみがない物質後述する”インキ転写性”のテ
ストでインクの付着が全く認められない物であ
り、該物質としては、例えばシリコーン、フツ素
含有高分子化合物、ポリオレフイン、ポリカーボ
ネート、ポリ塩化ビニル、メラニン架橋物及びシ
リコーン、フツ素ポリマー等を含有した各種高分
子化合物等が挙げられる。更に具体的には、シリ
コーンとしては離型用シリコーンと一般に言われ
るトリメチルクロロシラン、ジメチルクロロシラ
ン、メチルジクロルシラン、メチルトリクロロシ
ラン、ジフエニルクロロシラン、フエニルトリク
ロロシラン、メチルビニルジクロロシラン等の成
分を含んだ重合物や、更にこれらの構造体にベン
ゾイルパーオキサイダ、ジクロルパーオキサイド
等の過酸化物や白金触媒等を用いて加硫したシリ
コーン系ゴムあるいは樹脂等のいわゆるシリコー
ン系化合物が好ましい。また、フツ素含有高分子
化合物としては、ポリテトラフルオルエチレン、
テトラフルオロエチレン−ヘキサフルキロプロピ
レン共重合体、ポリビニリデンフロライド、ポリ
クロロトリフルオロエチレン等や、これらを有機
溶剤に可溶な変性を行つた高分子化合物が好まし
い。更にまたポリオレフインとしては、高分子量
ポリエチレン、高分子量ポリプロピレン等が好ま
しく、ポリカーボネートとしては高分子量のポリ
カーボネート樹脂が好ましい。
かかる物質は、通常有機溶媒に溶解させ、溶液
にして塗接する。この溶液には、更にアニオン型
界面活性剤、カチオン型界面活性剤、ノニオン型
界面活性剤等の界面活性剤を必要量添加すること
ができる。かかる界面活性剤としてはポリエステ
ルフイルムの濡れを促進するものが好ましく、例
えば、ポリオキシエチレンアルキルフエニルエー
テル、ポリオキシエチレン−脂肪酸エステル、ソ
ルビタン脂肪酸エステル、グリセリン脂肪酸エス
テル、脂肪酸金属石けん、アルキル硫酸塩、アル
キルスルホン酸塩、アルキルスルホコハク酸塩、
第４級アンモニウムクロライド、アルキルアミン
−塩酸塩等を挙げることができる。更にまた、本
発明の効果を消失させない範囲において例えば帯
電防止剤、紫外線吸収剤、顔料、潤滑剤、ブロツ
キング防止剤、有機フイラー、無機フイラー等の
他の添加剤を混合することができる。
上記溶液は固形分濃度が通常30重量％以下であ
り、好ましくは10重量％以下であるものである。
これらの物質は基体に設けた転写インク層を反対
面（走行面）に付着しにくくし、インク転写材
（リボン）の走行性に良好に保持し、少くとも走
行性を損うものではないことを言うまでもない。
更にまた、これらの物質を塗布したものが、逆に
インク層の表面に転写してプリント時インクが被
印字物に印字され難くなる等一種の離難剤として
の働きを生じることのないような注意が必要であ
り、使用物質の選定と塗工乾燥等での処置をこれ
に適したものとすることは言うまでもない。
これらの物質を塗布する際、二軸配向ポリエス
テルフイルムは、必要に応じてコロナ放電処理
や、バインダーの下びきコートなどの前処理を行
つてもよい。
塗布方法としては、公知の任意の塗工法が適用
できる。例えばロールコート法、グラビアコート
法、ロールブラツシユ法、スプレーコート、エア
ーナイフコート、含浸法及びカーテンコート法な
どを単独又は組み合せて適用するとよい。塗布量
は、フイルム１m3あたり0.05〜20ｇ、更には0.1
〜10ｇが好ましい。
二軸配向ポリエステルフイルムの各々の面に、
転写インク層と上述の溶液とを塗設する手順とし
ては、転写インク層と反対面（走行面）への上述
の溶液とのずれを先に塗工しても基本的には問題
はなく、更に例えば反対面（走行面）に上述の溶
液を塗工した後乾燥し、引き続いて転写インク層
を塗工して乾燥した後ロール状に巻き取つてもよ
く、又これらの工程を別々に、即ち例えば、転写
インク層を二軸配向ポリエステルの片面に塗工し
乾燥させた後、一旦ロール状に巻きとり、その後
上述のロールを巻きもどして基体（フイルム）の
反対面（走行面）に上述の溶液を塗工し乾燥した
後、ロール状に巻き取ることもできる。
本発明における二軸配向ポリエステルフイルム
は、転写インク層を設けない側の表面の摩擦係数
が0.5以下、更には0.45以下、特に0.35〜0.45であ
り、かつ該摩擦係数の連続50回往復走行テスト後
の値が初期値に比して150％未満、更には120％未
満であることが好ましい。この表面は走行面を形
成するから、摩擦係数が大きすぎるとリボンの走
行性が低下し、はなはだしいときにはリボン切れ
を起し、またインクの転写を引き起すようにな
り、好ましくない。
本発明のプリンター用転写材は、繰り返し使用
しても転写斑を生じないインク層と、二軸配向ポ
リエステルフイルムが本来有している優れた諸特
性、すなわち耐薬品性、強度、弾生率、耐熱性、
高融点等に加え、特にインクの転写しにくい走行
表面を有して好適な走行性を保持し、またインパ
クト用に用いれば繰り返し使用しても、印字によ
る打たれ残りなどの塑性変形も殆んどなく、かつ
好転画質に優れた転写材として有用である。
実施例
以下、実施例を揚げて本発明を更に説明する。
なお、本発明における種々の物性値および特性は
以下の如くして測定されたものであり、かつ定義
される。
(1) 突起分布
小板研究所製三次元粗さ計（SE−3CK）を
用いて、針径2μｍＲ、針圧30mg、測定長１mm、
サンプリングピツチ2μｍ、カツトオフ0.25mm、
縦方向拡大倍率２万倍、横方向拡大倍率200倍、
走査本数150本の条件にてフイルム表面の突起
のプロフアイルを三次元的（立体的）にイメー
ジさせる。
そのプロフアイルをフイルムの厚さ方向と直
角方向の平面でカツトした場合に、各突起のプ
ロフアイルの断面積の合計が、フイルムの測定
領域の面積の70％となる平面を基準レベル（０
レベル）とし、その基準レベルの平面と平行に
突起の高さ方向に距離ｘだけ離れた平面でカツ
トしたときにカツトされる突起の数をｙとす
る。ｘは順次増加又は減少させ、そのときのｙ
の数を読みとり、グラフにプロツトすることに
より、突起分布曲線を描くことができる。
(2) ヤング率
フイルムを試料巾10mm、長さ15cmに切り、チ
ヤツク間100mmにして引張速度10mm／分、チヤ
ート速度500mm／分にインストロンタイプの万
能引張試験装置にて引張り、得られる荷重−伸
び曲線の立上り部の接線よりヤング率を計算す
る。
(3) 表面突起数
フイルムの表面に400〜500〓乃至それ以下の
厚みにアルミニウムを均一に真空蒸着し、反対
の非蒸着面（フイルム面）にコロジオンを塗つ
て貼付け、乾燥する。Tl単色光多重干渉反射
顕微鏡（例えば、Carl Zeiss JENA社製）を
用いて100倍の倍率でアルミニウム蒸着面の任
意の100cm2を観察し、顕微鏡視野中の突起物の
突起高さに対応して生じる干渉縞を持つ突起数
を各々カウントする。
(4) 熱収縮率
20mm巾に切り出したフイルムサンプルに300
mm間長の位置に標点を印しておき、70℃又は
150℃に加熱された循環型熱風機に無荷重で吊
して１時間又は30分間保持し、その後取出して
放冷後上記標点間の長さを読みとつて、原長と
の差の原長に対する割合を％で表示する。
熱収縮率（％）＝（原長）−（加熱後長さ）／（原長
）×100
(5) インキ転写性
厚さ10μｍのフイルムの片面に転写インク組
成物を層の厚こ18μｍとなるようにクラビユア
方式で塗工し、得られる転写シート状物で10mm
巾×20cm長のフイルムサンプルを覆い、直径５
cmで１Kgの硬質クロム処理ロールで20回繰返し
押圧した後該サンプルの転写インク層に接触し
た面を、エチルアルコールで湿らせた綿棒でな
ぞり、その綿棒へのインクの付着程度（汚れ程
度）を目視評価にて５段階で判定する。
＜５段階判定＞
◎……インクの付着は全く認められない
○……インクの付着は殆んど認められない
△……インクの付着はいく分認められる
×……インクの付着はかなりの程度認められる
××…インクの付着がはげしく認められる
(6) 走行性
図１に示した装置を用いて下記のように測定
する。図１中、１はロードセル、２は表面粗さ
約0.5μｍのプラスチツク製の固定棒（外径５mm
φ）、３は荷重（100ｇ）、５，５はサンプル固
定具、４はサンプル（リボン）をそれぞれ示
す。
温度20℃、湿度60％RHの環境で巾８mmのサ
ンプル（転写インク層を18μｍの厚さに塗工し
たもの）の転写インクの塗工面の反対面（走行
面）を、２の固定棒に90°で接触させて毎秒30
mmの速さで１のロードセルを水平に30cmの長さ
を往復移動させることにより摩擦係数を読みと
る。
走行性の良否は、測定開始直後に得られる摩
擦係数に対する連続50回往復走行時の摩擦係数
との比較で３段階で判定する。
＜３段階判定＞
○……初期の摩擦係数に対する、50回繰返し往
復走行時の摩擦係数が120％未満であり、摩
擦係数が繰返し走行によりあまり増大しない
△……初期の摩擦係数に対する、50回繰返し往
復走行時の摩擦係数が120％以上150％未満で
あり、摩擦係数の増加が繰返し走行により若
干認められる
×……初期の摩擦係数に対する、50回繰返し往
復走行時の摩擦係数が150％以上であり摩擦
係数の増加が繰返し走行により顕著に認めら
れる
(7) 印字鮮明性
転写インク層を18μｍの厚さに塗工した転写
リボンのインク塗工面を反対側を電動式タイプ
ライターIBM82Cを用いて、アルフアベツトの
「Ｑ」の文字を通常のタイプライター用紙に繰
返し10回打ち、印字された「Ｑ」の鮮明性、印
字の太さ、濃淡の変化の度合を目視にて３段階
で判定する。
＜３段階判定＞
〇……繰返し10回打つても印字は太くならず、
濃淡斑もなく、鮮明である。
△……繰返１回数が増すに従つて印字はやや太
目になつており、かつ濃淡斑はやや目立つ
が、まずまず鮮明さは保持される
×……繰返し回数が増すに従つて印字はかなり
太目になつており、かつ部分的に濃淡の斑が
強く見られ、鮮明さに欠けてくる
(8) フイルム変形度
前記(7)に示した方法で同一ケ所を連続10回打
つてフイルムを打ち跡を目視にて３段階で判定
する。
＜３段階判定＞
○……打め跡は殆んど認められない
△……打ち跡はやや認められる
×……打ち跡ははつきり認められる
実施例 １〜３
エチレングリコール（以下EGと略称する）90
重量部に炭酸カルシウム（平均粒径1.5μｍ）10重
量部を添加した後、混合撹拌を行なつてスラリー
を得た。
次に、ジメチルテレフタレート100重量部と
EG70重量部を酢酸マンガン４水和物0.035重量部
を触媒として常通りエステル交換をせしめた後上
記で得られた炭酸カルシウム（濃度0.4重量％対
ポリマー）を撹拌下添加した。続いてリン酸トリ
メチル0.03重量部及び三酸化アンチモン0.03重量
部を添加した後高温真空下で常法通り重縮合反応
を行い、固有粘度0.620のポリエチレンテレフタ
レートベレツトを得た。
更にこのポリエチレンテレフタレート（以下
PETと略称）ベレツトを170℃、３時間乾燥後押
出機ホツパーに供給し、溶融温度280〜300℃で溶
融し、この溶融ポリマーを１mmのスリツト状ダイ
を通して表面仕上げ0.3S程度、表面温度20℃の回
転冷却ドラム上に成形押出し、厚み約110μｍの
未延伸フイルムを得た。
このようにして得られた未延伸フイルムを75℃
にて予熱してから更に低速、高速ロールの間で15
mm上方より900℃の表面温度のIRヒーター１本に
て加熱し、該低、高速のロール表面速度により
1.7倍延伸し、続いて一旦急冷してから再度上記
温度条件に加熱して1.45倍に延伸し、更にこの急
冷−加熱延伸を繰返し（再延伸の合計倍率3.6倍）
て縦方向に延伸した。この縦方向延伸フイルム
を、次に、熱風中に110℃の温度で横方向に3.9倍
に延伸し、次いで230℃で15秒間熱処理を施して
7.5μｍの厚さの二軸配向フイルムを得た。なお、
この時の延伸速度は20ｍ／分であつた。
次いで、この二軸配向フイルムを加熱ロールで
120℃に放熱後、冷却ロールとの間で、熱処理温
度に応じた収縮に相当する張力を掛けながら弛緩
処理して、70℃で１時間処理したときの縦方向の
熱収縮率が約0.06％のフイルムを得た。
得られたフイルムの特性は次の通りである。
ヤング率（縦方向）（Kg／mm2） 530
熱収縮率（％）
70℃・１時間（縦方向） 0.06
150℃・30分（横方向） 0.20
突起高さと突起数
（μｍ） （個／mm2）
1.5≧ｈ＞1.0 ６
1.0≧ｈ＞0.75 23
0.75≧ｈ＞0.5 75
0.5≧ｈ＞0.25 240
最大突起高さ（μｍ） 1.6
なお、この二軸配向フイルムの三次元粗さ計に
よる突起分布曲線は図−２（曲線Ａ）に示す。
上記特性の二軸配向ポリエステルフイルムの片
面に、表−１に示した組成からインク層になじみ
の殆んどない物質（表−１では、付着防止層組成
物と称する）をグラビユア方式で塗工し、その後
直ちに乾燥してロール状に巻きとつた。
その後、下記組成からなるインクを層の厚さ
18μｍとなるようにグラビユア方式で塗工した。
得られた転写材を８mm巾のリボンにして評価し
た。その結果を表−１に示す。
このようにして得られた複写材の諸性能はいず
れも良好レベルにあつた。
転写インク組成物：
〔Ａ〕タイプ
カーボンブラツク 18重量部
パラフイン・ワツクス（m.p.〜40℃） 50 〃
カルナウバ・ワツクス 15 〃
エチレン−アクリル酸共重合体（90／10）
15 〃
ステアリン酸 ２ 〃
〔Ｂ〕タイプ
パラニトロアニリンレツド 15重量部
パラフイン・ワツクス（m.p.〜40℃） 50 〃
カルナウバ・ワツクス 19 〃
エチンレン−酢ビ共重合体（85／15） 15 〃
架橋ポリエチレンビーズ（粒径0.5μ） １ 〃
〔Ｃ〕タイプ
カーボンブラツク 20重量部
ワセリン 30重量部
グリセリン 30 〃
固型ロジン・ワツクス 10 〃
水 10 〃
INDUSTRIAL APPLICATION FIELD The present invention relates to a transfer material for printers, and more particularly to a transfer material for printers that is excellent in durability, transferability, dimensional stability, and runnability. Prior Art The basic structure of a transfer material for a printer consists of a base and an ink layer coated on one side of the base. Conventionally, biaxially oriented polyester films have been widely used as this substrate because of their excellent properties such as chemical resistance, strength, elastic modulus, heat resistance, crystallinity, and high melting point. By the way, transfer materials for printers are increasingly being used repeatedly, and the rotation of this repeated use is also increasing year by year.With conventional biaxially oriented polyester films, for example, the printing area during transfer using the dot impact method is increasing. There were problems such as deformation and elongation of the film due to unprinted parts, and deformation due to heat in the thermal transfer method. Furthermore, the ink layer applied to the polyester film is transferred to the opposite surface (running surface), staining the running surface of the ribbon, and this causes running problems such as gradual accumulation of ink on contact parts such as guide posts of the running system. Ta. OBJECTS OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and provide a transfer material for printers that is suitable for repeated use and has excellent durability, transferability, dimensional stability, and runnability. Effects/Configuration of the Invention According to the present invention, the object of the present invention is to
In a transfer material for a printer in which a transfer ink layer with a thickness of 3 to 35 μm is provided on one side of a 25 μm biaxially oriented polyester film, the biaxially oriented polyester film has the following (a) to (c), (b) longitudinal direction. Young's modulus is 450-800Kg/ mm2 , (b) Heat shrinkage rate at 150℃ in longitudinal and transverse directions is 7.
(c) The protrusion distribution curve representing the relationship between the number of protrusions (Y: ke/mm 2 ) and the protrusion height (X: μm) measured with a three-dimensional roughness meter on the film surface is log 10 Y >1.3, the line expressed by the following formula (1) log 10 Y = -1.8 is in a range that satisfies the following formula (2): log 10 Y≧−3.6X+2.8 (2). Achieved by a transfer material for a printer, which satisfies the following, and is further characterized in that a substance that is hardly compatible with the transfer ink layer is coated on the surface opposite to the surface on which the transfer ink layer is provided. be done. The polyester in the present invention is a polyester containing an aromatic dicarboxylic acid as a main acid component and an aliphatic glycol as a main glycol component. Such polyester is substantially linear;
It also has film-forming properties, particularly film-forming properties by melt molding. Aromatic dicarboxylic acids include, for example, terephthalic acid, naphthalene dicarboxylic acid, isophthalic acid, diphenoxyethane dicarboxylic acid,
diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenyl sulfone dicarboxylic acid,
These include diphenylketone dicarboxylic acid and anthracene dicarboxylic acid. Aliphatic glycols include, for example, polymethylene glycols having 2 to 10 carbon atoms such as ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, and decamethylene glycol, or alicyclic diols such as cyclohexanedimethanol. etc. In the present invention, polyesters containing, for example, alkylene terephthalate and/or alkylene naphthalate as main constituents are preferably used. Among such polyesters, for example, not only polyethylene terephthalate and polyethylene-2,6-naphthalate, but also terephthalic acid and/or 2,6-naphthalene dicarboxylic acid account for 80 mol% or more of the total dicarboxylic acid component, and the total glycol component Particularly preferred are copolymers in which 80 mol% or more of ethylene glycol is ethylene glycol. In this case, 20 mol% or less of the dicarboxylic acid of the total acid component can be the above-mentioned aromatic dicarboxylic acid,
Further, for example, aliphatic dicarboxylic acids such as adipic acid and sebacic acid; aliphatic dicarboxylic acids such as cyclohexane-1,4-dicarboxylic acid and the like can be used. In addition, up to 20 mol% of the total glycol component can be the above-mentioned glycols other than ethylene glycol, or aromatic diols such as hydroquinone, resorcinol, 2,2-bis(4-hydroxyphenyl)propane;
Aliphatic diols containing aromatics such as 1,4-dihydroxymethylbenzene; polyalkylene glycols (polyoxyalkylene glycols) such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol can also be used. In addition, the polyester used in the present invention includes
For example, components derived from oxycarboxylic acids such as aromatic oxyacids such as hydroxybenzoic acid; aliphatic oxyacids such as ω-hydroxycaproic acid are contained in an amount of 20 mol% or less based on the total amount of dicarboxylic acid components and oxycarboxylic acid components. It also includes those containing. Furthermore, the polyester in the present invention contains a trifunctional or more functional polycarboxylic acid or a polyhydroxy compound, such as trimellitic acid, pentaerythritol, in an amount within a substantially linear range, for example, an amount of 2 mol % or less based on the total acid components. Copolymerized products are also included. The above polyester is known per se, and can be produced by a method known per se. The polyester preferably has an intrinsic viscosity of about 0.4 to about 0.9 as measured as a solution in 0 -chlorophenol at 35°C. Moreover, the above-mentioned polyester may contain additives such as stabilizers, colorants, and antioxidants, as required. The biaxially oriented polyester film in the present invention is a biaxially oriented film manufactured from the above-mentioned polyester. This film has a longitudinal Young's modulus of 450 to 800 Kg/mm 2 , preferably 500 to 750 Kg/mm 2 . Note that the longitudinal direction of the film coincides with the longitudinal direction of the ink transfer ribbon. If the Young's modulus in the longitudinal direction is less than 450Kg/ mm2 ,
Because the film stretches easily and elasticity recovery is difficult,
When used as a copy ribbon for printing, the printing part undergoes plastic deformation due to printing pressure, resulting in poor print clarity such as printing thicker than necessary, and poor handling when winding the transfer ribbon due to this deformation. So it's not desirable. Furthermore, if the Young's modulus in the longitudinal direction exceeds 800 Kg/mm 2 , the rigidity is so strong that the film tends to tear due to printing pressure, which is not preferable. Further, the thickness of the polyester film in the present invention is generally 1 to 25 μm, preferably 2 to 25 μm.
The thickness is 10 μm, more preferably 3 to 8 μm. If the thickness of the film is thinner than the above-mentioned range, the strength will be insufficient, and it will lack suitability when used as a transfer ribbon, and will also be inferior in terms of processing suitability.On the other hand, if the film is thicker than the above-mentioned range, In particular, the thermal transfer method is undesirable because it takes a long time to transfer heat, making it unsuitable for increasing the recording speed and obtaining clear transferred images. The biaxially oriented polyester film in the present invention has the above-mentioned longitudinal Young's modulus and thickness, but
Furthermore, the number of protrusions (Y: x/mm 2 ) and the protrusion height (X:
The protrusion distribution curve representing the relationship between log 10 Y
＞1.3, a surface that does not intersect the line expressed by the following formula (1) and is in a range where the maximum value of the protrusion distribution and the curve of the part exceeding the maximum value satisfy the following formula (2) have characteristics. log 10 Y=-1.8x+3.9...(1) log 10 Y≧-3.6X+2.8...(2) Does the film surface roughness fall below the straight line expressed by the formula log 10 =-3.6X+2.8? Or, if the protrusion distribution is such that the protrusions intersect in areas exceeding the maximum value (particularly in areas with large protrusion heights that intersect and descend downwards), the film may not be as sharp when wound onto a roll after applying the ink layer. The ink is easily transferred to the opposite surface (running surface) of the ribbon, staining the running surface of the ribbon, which gradually accumulates ink at the contact parts such as guide posts of the ribbon running system, and obstructs the running of the ribbon. In extreme cases, problems such as the ribbon not moving may occur, and the film may become less slippery.
This is undesirable because it causes wrinkles in the film during processing. Also, the surface roughness of the film is expressed by the above formula.
If it is so rough that it exhibits a protrusion distribution that intersects (1), it is not preferable because the sharpness of the print becomes poor and it also causes wear and tear on the thermal head, which poses a practical problem. The above-mentioned film surface also has a number of protrusions (k/mm 2 ) measured using a multiple interference reflection microscope (Tl monochromatic light).
and protrusion height (h: μm) is 1.5≧h＞1.0 ...10 pieces/mm 2 or less 1.0≧h>0.75 ...1 to 30 pieces/mm 2 0.75≧h＞0.5 ...15 to 120 pieces/mm 2 0.5≧h＞0.25...It is preferable to satisfy 80 pieces/ mm2 or more. Satisfying each surface property is important from the viewpoint of preventing the transfer of the ink layer to the opposite side of the film and from the viewpoint of print clarity.
Particularly preferred. In addition, the maximum protrusion height on the film surface is 3 μm or less,
Furthermore, it is desirable that the thickness be 1.5 μm or less. The above-mentioned surface roughness of the biaxially oriented polyester film in the present invention is due to the presence of inert inorganic materials in the film.
It is preferable to form by adding organic fine particles or the like. When using this inert fine particle,
0.01 to 5% by weight of particles with an average particle size of 0.01 to 10 μm,
Furthermore, it is preferable to add particles having an average particle size of 0.03 to 4 μm in an amount of 0.01 to 1.5% by weight. At this time, the inert inorganic or organic fine particles added may be a single component, or two or more components may be used simultaneously. In the present invention, the above-mentioned inert fine particles are preferably silicon dioxide (including hydrates, diatomaceous earth, silica sand, quartz, etc.); alumina;
Silicates containing 30% by weight or more of SiO 2 (e.g. amorphous or crystalline clay minerals, aluminosilicates (including calcined products and hydrates), hot asbestos, zircon, fly ash, etc.), Mg, Zn, Zr and Ti
oxides; sulfates of Ca and Ba; Li, Na and
Ca phosphate (including monohydrogen and dihydrogen salts);
Benzoates of Li, Na and K; Terephthalates of Ca, Ba, Zn and Mn; Mg, Ca, Zn, Cd,
Titanates of Sr, Mn, Fe, Co and Ni; Chromates of Ba and Pb; Carbon (e.g. carbon black, graphite, etc.); Glass (e.g. glass powder, glass beads, etc.); Carbonates of Ca and Mg; Fluorite; and ZnS are exemplified. More preferably, anhydrous silicic acid, hydrated silicic acid, aluminum oxide, nium, aluminum silicate (including calcined products, hydrates, etc.), monolithium phosphate, trilithium phosphate, etc.
Lithium, sodium nitrate, barium phosphate, titanium oxide, lithium benzoate, resalts of these compounds (including hydrates), glass powder, clay (kaolin,
(including pentonite, clay, etc.), talc, diatomaceous earth, calcium carbonate, etc. Polyesters containing these inert particulates are usually reacted to form polyesters by
For example, inert fine particles (preferably as a slurry in glycol) may be added at any time during the transesterification reaction or polycondensation reaction when using the transesterification method, or at any time during the polycondensation reaction when using the direct polymerization method.
It can be produced by adding into the reaction system. Preferably, inert fine particles are added to the reaction system at the beginning of the polycondensation reaction, for example, until the intrinsic viscosity reaches about 0.3. Further, the biaxially oriented polyester film of the present invention preferably has a heat shrinkage rate of 7% or less in the longitudinal and lateral directions when heat-treated at 150°C for 30 minutes, more preferably 4% or less, particularly preferably 2.
% or less. If this thermal shrinkage rate is greater than 7%, not only will the width shrinkage during relaxation treatment become large, but also the width shrinkage will increase during the process of processing into a transfer material for printers, that is, coating,
This is undesirable because shrinkage occurs during drying and other processes, resulting in deterioration of thick spots and a decrease in yield.
In addition, when this heat shrinkage rate is less than 0%, the relaxation is
In the case of a method using a speed difference between two rolls, wrinkles occur on the heated roll, and if the paste film is left in the roll shape until it is processed into a transfer material for a printer, the vertical This is undesirable because wrinkles occur in the direction and further wrinkles occur on the surface of the intermediate product roll during the process of processing the transfer material for printers. It is presumed that these wrinkles occur when the thermal expansion of the film in the lateral direction is greater than the thermal contraction. Furthermore, there are problems when using the ribbon, especially when it is used as a transfer ribbon for a thermal printer, if the heat shrinkage rate is outside the above range, the ribbon deforms severely, resulting in poor print clarity and the deformation resulting in poor transfer quality. Ribbon winding and handling properties become poor, and even in the dot impact method, ribbons with a heat shrinkage rate exceeding 7% are undesirable because they tend to cause deformation of the printed area. The biaxially oriented polyester film used in the present invention is not particularly limited by its production method, but usually polyester containing a predetermined proportion of fine particles is melted and extruded into a sheet form through a slit-shaped die, and the film is produced using a casting drum. The unstretched sheet is then cooled and solidified to form an unstretched sheet, and then the unstretched sheet is biaxially stretched to form a product (film), followed by heat treatment (heat setting), adjustment treatment for the heat shrinkage rate in the transverse direction, and then Manufactured by longitudinal relaxation treatment. In this case, in order to suitably satisfy the requirements of the present invention,
For example, the stretching temperature is the first-stage stretching temperature (e.g. longitudinal stretching degree: T 1 ) in the range of (Tg-10) to (Tg+45)°C (Tg: glass transition temperature of polyester)
and the second-stage stretching temperature (e.g. lateral stretching temperature:
T 2 ) is in the range of (T 1 +15) to (T 1 +40)°C,
The stretching ratio is 2.5 to 6.0 times, especially 3.5 to 6.0 times in the first stage stretching.
5.5 times, and 2.5 to 4.0 times in the second stage stretching, especially 2.8
It is preferable to set it to ~3.7 times. Further, the obtained biaxially stretched film is preferably heat set at a temperature in the range of 150 to 245°C, more preferably 170 to 240°C, for about 1 to 200 seconds. Furthermore, the heat treatment conditions in the tenter are usually adjusted to adjust the heat shrinkage rate in the lateral direction, and then a longitudinal relaxation treatment is performed. Adjustment of the heat shrinkage rate in the transverse direction is usually performed before the longitudinal relaxation treatment. It is usually adjusted during heat treatment in a tenter. For example, if the heat shrinkage rate in the lateral direction is insufficient, it is recommended to stretch the film in the width direction during the above heat treatment, and if the heat shrinkage rate is too large, it is recommended to relax the film in the width direction during the above heat treatment. good. More specifically, when the heat treatment temperature is 160℃, it is recommended to relax the entire width by 9 to 13%, and when the heat treatment temperature is 170℃
It is recommended to relax 5-11% when the temperature is 180℃, 1-8% when the temperature is 180℃, and 0-5% tension or relaxation when the temperature is 200℃.
At 205℃, it is best to stretch or relax by 3 to -2%, and at 220℃, it is recommended to stretch or relax by 1 to -6%.
It is best to stretch or relax. Methods for loosening in the longitudinal direction include, for example, a floating treatment method using air force, heating under low tension, and relaxing in a non-contact state; relaxing by giving a speed difference between a heating roll and a cooling roll, each having a nip roll. There are two methods: a method in which the clip holding the film is loosened in the vertical direction by gradually reducing the speed of movement of the clip holding the film in the tenter, but any method can be used as long as it can be relaxed in the vertical direction. . The temperature when relaxing in the longitudinal direction is (Tg + 20) °C or higher (heat treatment temperature - 30) °C or lower, preferably (Tg
+30)℃ or more (heat treatment temperature -40)℃ or less.
At temperatures lower than (Tg + 20) °C, the thermal shrinkage rate near Tg cannot be sufficiently lowered, and at temperatures higher than (heat treatment temperature - 30) °C, although the amount of relaxation in the longitudinal direction increases, the shrinkage in the lateral direction increases. becomes larger, which not only makes it impossible to satisfy the heat shrinkage rate in the transverse direction, but also reduces the mechanical properties in the transverse direction, further worsening uneven thickness, and loosening occurs due to the speed difference between the two rolls. In the case of this method, scratches are generated in the lateral direction on the film surface due to width shrinkage on the heating roll, which is not preferable. The amount of relaxation in the longitudinal direction varies depending on the heat treatment temperature, but the film tension at the time of relaxation is 10 Kg/cm 2 or more and 80 Kg/cm 2 or less, preferably 20 Kg/cm 2 or more.
For example, in the case of a method in which relaxation is performed by a speed difference between two rolls, it is preferable to adjust the speed of the cooling roll relative to the heating roll so that the relaxation is at least Kg/cm 2 and at most 60 Kg/cm 2 . If the film tension is less than 10 Kg/cm 2 , the film will sag and wrinkles will occur, and if the tension is greater than 80 Kg/cm 2 , the heat shrinkage rate cannot be lowered sufficiently. Due to the above-described relaxation treatment, the thermal shrinkage rate in the longitudinal direction at a temperature equal to or higher than the temperature of the relaxation treatment does not affect the curling edge of the coated material. Conventional longitudinal relaxation causes contraction not only in the longitudinal direction but also in the transverse direction, and therefore the heat shrinkage rate in the transverse direction becomes too small. If the heat shrinkage rate in the lateral direction is too low, wrinkles may occur on the surface of the film roll, or wrinkles may appear during coating during the printer transfer material processing stage, causing uneven coating. The biaxially oriented polyester film thus obtained usually exhibits the same surface characteristics on both the front and back sides.
In this case, the surface on which the transfer ink layer is provided may be the front or back surface. In the present invention, the transfer ink layer is constructed by appropriately adding a softener, a flexibilizing agent, a dispersant, a smoothing agent, etc., as necessary, in addition to the binder component and the coloring component. Examples of ink components include waxes such as carnauba wax, paraffin wax, and n-fatty acid alkyl esters, binder components such as salt-piped polymers, salt-piped-acetate-piped copolymer polymers, colorants, and other components. is used. As the colorant, carbon black is usually used as the main ingredient, and various other dyes or organic or inorganic pigments are used. Another example is one in which nigrosine, methyl violet, alkali blue, etc. are used as a coloring agent, and three to four types of water, castor oil, glycerin, alcohol, vaseline, oleic acid, paraffin, etc. are combined in appropriate amounts. In some cases, the transfer ink may also include a sublimation type. The transfer ink layer can be formed by a conventional method, for example, a solution coating method such as gravure, reverse, or slit die method in a state in which a solvent is added, or hot melt coating. At this time, the biaxially oriented polyester film may be subjected to pretreatment such as corona discharge and treatment or subbing coating with a binder, if necessary. The thickness of the ink layer is 3 to 35 μm. If the ink layer is too thick, the ink layer will be transferred (transferred to the surface of the transfer material) when the transfer material is wound into a roll, which is not preferable. In the present invention, a substance that is not compatible with the transfer ink layer applied to the surface opposite to the transfer ink layer (running surface) of the substrate shows no ink adhesion at all in the "ink transferability" test described below. Examples of such substances include silicone, fluorine-containing polymer compounds, polyolefins, polycarbonates, polyvinyl chloride, melanin crosslinked products, and various polymer compounds containing silicones, fluorine polymers, and the like. More specifically, the silicone includes components such as trimethylchlorosilane, dimethylchlorosilane, methyldichlorosilane, methyltrichlorosilane, diphenylchlorosilane, phenyltrichlorosilane, and methylvinyldichlorosilane, which are generally referred to as mold release silicones. Preferred are so-called silicone compounds such as silicone rubbers or resins obtained by vulcanizing these structures using peroxides such as benzoyl peroxide or dichloroperoxide, or platinum catalysts. In addition, examples of fluorine-containing polymer compounds include polytetrafluoroethylene,
Preferred are tetrafluoroethylene-hexafluoropropylene copolymer, polyvinylidene fluoride, polychlorotrifluoroethylene, and polymer compounds obtained by modifying these to make them soluble in organic solvents. Furthermore, as the polyolefin, high molecular weight polyethylene, high molecular weight polypropylene, etc. are preferable, and as the polycarbonate, high molecular weight polycarbonate resin is preferable. Such substances are usually dissolved in an organic solvent and applied as a solution. A necessary amount of a surfactant such as an anionic surfactant, a cationic surfactant, or a nonionic surfactant can be added to this solution. Such surfactants are preferably those that promote wetting of the polyester film, such as polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, glycerin fatty acid ester, fatty acid metal soap, alkyl sulfate, Alkyl sulfonate, alkyl sulfosuccinate,
Examples include quaternary ammonium chloride and alkylamine hydrochloride. Furthermore, other additives such as antistatic agents, ultraviolet absorbers, pigments, lubricants, antiblocking agents, organic fillers, and inorganic fillers may be mixed within a range that does not impair the effects of the present invention. The solid content concentration of the above solution is usually 30% by weight or less, preferably 10% by weight or less.
These substances make it difficult for the transfer ink layer provided on the substrate to adhere to the opposite surface (running surface), maintain good running properties of the ink transfer material (ribbon), and at least do not impair running properties. Needless to say.
Furthermore, the material coated with these substances should not be transferred to the surface of the ink layer and act as a kind of release agent, such as making it difficult for the ink to print on the printed object during printing. It goes without saying that care must be taken, and that the selection of materials used and treatments such as coating and drying are appropriate. When applying these substances, the biaxially oriented polyester film may be subjected to a pretreatment such as a corona discharge treatment or a subbing coat of a binder, if necessary. Any known coating method can be used as the coating method. For example, a roll coating method, a gravure coating method, a roll brushing method, a spray coating, an air knife coating, an impregnation method, a curtain coating method, etc. may be applied alone or in combination. The coating amount is 0.05 to 20g per 1m3 of film, and even 0.1g per 1m3 of film.
~10g is preferred. On each side of the biaxially oriented polyester film,
As for the procedure for applying the transfer ink layer and the above-mentioned solution, there is basically no problem in applying the above-mentioned solution to the surface opposite to the transfer ink layer (running surface) first. Furthermore, for example, the above-mentioned solution may be applied to the opposite surface (running surface) and then dried, and then a transfer ink layer may be applied, dried, and then wound into a roll, or these steps may be performed separately. That is, for example, a transfer ink layer is coated on one side of biaxially oriented polyester, dried, and then wound up into a roll, and then the above-mentioned roll is rewound and the above-mentioned transfer ink layer is applied to the opposite side (running surface) of the substrate (film). After coating the solution and drying it, it can also be wound up into a roll. The biaxially oriented polyester film of the present invention has a friction coefficient of 0.5 or less, more preferably 0.45 or less, particularly 0.35 to 0.45 on the surface on which the transfer ink layer is not provided, and that the friction coefficient is after 50 consecutive reciprocating tests. It is preferable that the value is less than 150%, more preferably less than 120%, compared to the initial value. Since this surface forms a running surface, if the coefficient of friction is too large, the running properties of the ribbon will be reduced, and if severe, it will cause ribbon breakage and ink transfer, which is not desirable. The transfer material for printers of the present invention has an ink layer that does not cause transfer unevenness even after repeated use, and the excellent properties inherent to the biaxially oriented polyester film, such as chemical resistance, strength, elastic modulus, Heat-resistant,
In addition to having a high melting point, it has a running surface that is particularly difficult for ink to transfer, maintaining suitable running properties, and when used for impact applications, there is almost no plastic deformation such as leftover impressions due to printing even after repeated use. It is useful as a transfer material with excellent image quality. Examples Hereinafter, the present invention will be further explained with reference to Examples.
Note that various physical property values and characteristics in the present invention were measured and defined as follows. (1) Protrusion distribution Using a three-dimensional roughness meter (SE-3CK) manufactured by Koita Research Institute, needle diameter 2μmR, needle pressure 30mg, measurement length 1mm,
Sampling pitch 2μm, cutoff 0.25mm,
20,000x vertical magnification, 200x horizontal magnification,
The profile of protrusions on the film surface is imaged three-dimensionally (stereoscopically) under the condition of 150 scans. When the profile is cut in a plane perpendicular to the thickness direction of the film, the plane where the total cross-sectional area of the profile of each protrusion is 70% of the area of the measurement area of the film is set as the reference level (0
level), and let y be the number of protrusions that are cut when the plane is parallel to the plane of the reference level and separated by a distance x in the height direction of the protrusions. x is increased or decreased sequentially, and y at that time
By reading the number of and plotting it on a graph, a protrusion distribution curve can be drawn. (2) Young's modulus Cut the film into 10 mm wide and 15 cm long pieces and pull them using an Instron type universal tensile tester at a chuck spacing of 100 mm at a tensile speed of 10 mm/min and a chatch speed of 500 mm/min. Calculate Young's modulus from the tangent to the rising part of the elongation curve. (3) Number of surface projections Aluminum is uniformly vacuum-deposited on the surface of the film to a thickness of 400 to 500 mm or less, and collodion is applied to the opposite non-deposited surface (film surface) and then dried. Observe an arbitrary 100 cm of the aluminum deposited surface at 100x magnification using a Tl monochromatic light multiple interference reflection microscope (e.g., manufactured by Carl Zeiss JENA), and measure the height of the protrusions in the microscope field. The number of protrusions each having interference fringes produced is counted. (4) Heat shrinkage rate: 300 for a film sample cut to a width of 20 mm
Mark a gauge at the length of 70℃ or
Hang it with no load in a circulating hot air fan heated to 150℃ and hold it for 1 hour or 30 minutes, then take it out and leave it to cool, then read the length between the gauge points above and find the cause of the difference from the original length. Displays the ratio to the length as a percentage. Thermal shrinkage rate (%) = (original length) - (length after heating) / (original length) x 100 (5) Ink transferability Transfer ink composition was applied to one side of a 10 μm thick film in a layer thickness of 18 μm. 10mm in the resulting transfer sheet.
Cover a film sample with a width of 20 cm and a diameter of 5 cm.
After repeatedly pressing the sample 20 times with a 1 kg hard chrome-treated roll, trace the surface of the sample in contact with the transfer ink layer with a cotton swab moistened with ethyl alcohol to determine the degree of ink adhesion (staining) to the cotton swab. Judgment is made by visual evaluation on a 5-level scale. <5-level evaluation> ◎...No ink adhesion is observed.○...Ink adhesion is almost not observed.△...Ink adhesion is somewhat observed.×...Ink adhesion is considerable. Appeared XX... Severe ink adhesion is observed (6) Runnability Measure as follows using the apparatus shown in Figure 1. In Figure 1, 1 is a load cell, and 2 is a plastic fixing rod with a surface roughness of approximately 0.5 μm (outer diameter 5 mm).
φ), 3 indicates the load (100 g), 5 and 5 indicate the sample fixture, and 4 indicates the sample (ribbon). In an environment with a temperature of 20℃ and a humidity of 60% RH, attach the opposite side (running surface) of the transfer ink-coated surface of a sample with a width of 8 mm (transfer ink layer coated to a thickness of 18 μm) to the fixing rod No. 2. 30 per second with 90° contact
The coefficient of friction is read by moving the load cell 1 horizontally back and forth over a length of 30 cm at a speed of mm. The running performance is judged in three stages by comparing the friction coefficient obtained immediately after the start of measurement with the friction coefficient obtained during 50 consecutive reciprocating runs. <Three stage judgment> ○...Friction coefficient after 50 repeated back and forth runs is less than 120% of the initial friction coefficient, and the friction coefficient does not increase much with repeated running △...50 times compared to the initial friction coefficient The friction coefficient during repeated back and forth running is 120% or more and less than 150%, and a slight increase in the friction coefficient is observed due to repeated running. (7) Print clarity The ink-coated side of the transfer ribbon coated with a transfer ink layer with a thickness of 18 μm was printed on the opposite side using an electric typewriter IBM82C. , the letter "Q" in alphabetical alphabet is repeatedly typed 10 times on regular typewriter paper, and the sharpness of the printed "Q", the thickness of the print, and the degree of change in shading are visually judged in three stages. <Three stage judgment> 〇...The print does not become thicker even if you press it 10 times.
It is clear and has no dark or dark spots. △...As the number of repetitions increases, the print becomes a little thicker, and the shading is a little more noticeable, but the clarity is maintained to be fair. ×...The print becomes considerably thicker as the number of repetitions increases. (8) Degree of film deformation: The same spot is struck 10 times in a row using the method shown in (7) above. is visually judged in three stages. <Three-stage judgment> ○... Hardly any scratches are observed △... Some scratches are observed ×... Some scratches are observed Examples 1 to 3 Ethylene glycol (hereinafter abbreviated as EG) ) 90
After adding 10 parts by weight of calcium carbonate (average particle size 1.5 μm) to the parts by weight, mixing and stirring were performed to obtain a slurry. Next, 100 parts by weight of dimethyl terephthalate and
After 70 parts by weight of EG was subjected to transesterification as usual using 0.035 parts by weight of manganese acetate tetrahydrate as a catalyst, the calcium carbonate obtained above (concentration 0.4% by weight to polymer) was added under stirring. Subsequently, 0.03 parts by weight of trimethyl phosphate and 0.03 parts by weight of antimony trioxide were added, and then a polycondensation reaction was carried out in a conventional manner under high temperature vacuum to obtain a polyethylene terephthalate beret having an intrinsic viscosity of 0.620. Furthermore, this polyethylene terephthalate (hereinafter
PET (abbreviated as PET) is dried at 170℃ for 3 hours, then fed into the extruder hopper and melted at a melting temperature of 280 to 300℃.The molten polymer is passed through a 1 mm slit die with a surface finish of about 0.3S and a surface temperature of 20℃. The film was formed and extruded on a rotating cooling drum to obtain an unstretched film with a thickness of about 110 μm. The unstretched film thus obtained was heated at 75°C.
After preheating with
Heated with one IR heater with a surface temperature of 900℃ from above mm, and at the low and high roll surface speed.
Stretched by 1.7 times, then once rapidly cooled, heated again to the above temperature conditions, stretched to 1.45 times, and then repeated this rapid cooling-heat stretching process (total re-stretching ratio: 3.6 times)
The film was stretched in the longitudinal direction. This longitudinally stretched film was then stretched 3.9 times in the transverse direction at a temperature of 110°C in hot air, and then heat treated at 230°C for 15 seconds.
A biaxially oriented film with a thickness of 7.5 μm was obtained. In addition,
The stretching speed at this time was 20 m/min. Next, this biaxially oriented film is heated with a heated roll.
After radiating heat to 120℃, it is subjected to relaxation treatment while applying tension corresponding to the shrinkage according to the heat treatment temperature between it and a cooling roll, and when treated at 70℃ for 1 hour, the longitudinal heat shrinkage rate is approximately 0.06%. I got the film. The properties of the obtained film are as follows. Young's modulus (longitudinal direction) (Kg/mm 2 ) 530 Heat shrinkage rate (%) 70℃・1 hour (longitudinal direction) 0.06 150℃・30 minutes (horizontal direction) 0.20 Protrusion height and number of protrusions (μm) (pieces/ mm 2 ) 1.5≧h＞1.0 6 1.0≧h＞0.75 23 0.75≧h＞0.5 75 0.5≧h＞0.25 240 Maximum protrusion height (μm) 1.6 Furthermore, the protrusion of this biaxially oriented film measured by a three-dimensional roughness meter The distribution curve is shown in Figure 2 (curve A). On one side of the biaxially oriented polyester film having the above properties, a substance having a composition shown in Table 1 that is hardly compatible with the ink layer (referred to as the anti-adhesion layer composition in Table 1) is coated by gravure method. Thereafter, it was immediately dried and wound into a roll. After that, ink consisting of the following composition is applied to the thickness of the layer.
It was coated using the gravure method to a thickness of 18 μm.
The obtained transfer material was made into a ribbon with a width of 8 mm and evaluated. The results are shown in Table-1. The various properties of the copying material thus obtained were all at a good level. Transfer ink composition: [A] Type carbon black 18 parts by weight Paraffin wax (mp ~ 40°C) 50 Carnauba wax 15 Ethylene-acrylic acid copolymer (90/10)
15 〃 Stearic acid 2 〃 [B] Type paranitroaniline reed 15 parts by weight Paraffin wax (mp ~ 40℃) 50 〃 Carnauba wax 19 〃 Ethylene-vinyl acetate copolymer (85/15) 15 〃 Cross-linked polyethylene Beads (particle size 0.5μ) 1 [C] type carbon black 20 parts by weight Vaseline 30 parts by weight glycerin 30 Solid rosin wax 10 Water 10
【表】
比較例 １〜３
実施例１〜実施例３における二軸配向ポリエス
テルフイルム製造条件のうち、縦の再延伸の合計
倍率を3.3倍とし、かつ横の延伸倍率を3.8倍とし
た他は上記同じ条件で実施して厚さ7.6μｍの二軸
配工フイルムを得た。
この二軸配工ポリエステルフイルムの物性は次
の通りである。
ヤング率（縦方向）（Kg／mm2） 410
熱収縮率（％）
70℃・１時間（縦方向） 0.09
150℃・30分（横方向） 0.45
突起高さと突起数
（μｍ） （個／mm2）
1.5≧ｈ＞1.0 ３
1.0≧ｈ＞0.75 14
0.75≧ｈ＞0.5 56
0.5≧ｈ＞0.25 250
最大突起高さ（μｍ） 1.2
なお、この二軸配向フイルムの突起分布曲線は
図−２の曲線−Ａに近似するものであつた。
上記物性の二軸配向ポリエステルフイルムの両
面に実施例１〜３で用いたと同様の組合せの転写
インク層組成物と付着防止層組成物とを塗工し
た。
このようにして得られた転写材の諸性能は表−
に示す如く、フイルム変形度が不満足であつ
た。[Table] Comparative Examples 1 to 3 Among the manufacturing conditions for biaxially oriented polyester films in Examples 1 to 3, the total magnification for longitudinal re-stretching was 3.3 times, and the horizontal stretching magnification was 3.8 times. A biaxially arranged film with a thickness of 7.6 μm was obtained under the same conditions as above. The physical properties of this biaxially arranged polyester film are as follows. Young's modulus (longitudinal direction) (Kg/mm 2 ) 410 Heat shrinkage rate (%) 70℃・1 hour (longitudinal direction) 0.09 150℃・30 minutes (horizontal direction) 0.45 Protrusion height and number of protrusions (μm) (pieces/ mm 2 ) 1.5≧h＞1.0 3 1.0≧h＞0.75 14 0.75≧h＞0.5 56 0.5≧h＞0.25 250 Maximum projection height (μm) 1.2 The projection distribution curve of this biaxially oriented film is shown in Figure-2. It was similar to curve-A. A transfer ink layer composition and an anti-adhesion layer composition in the same combination as used in Examples 1 to 3 were coated on both sides of a biaxially oriented polyester film having the above physical properties. The various performances of the transfer material obtained in this way are shown in the table below.
As shown, the degree of film deformation was unsatisfactory.
【表】
比較例 ４
添加剤として炭酸カルシウム（平均粒径1.5μ
ｍ）を対ポリマー当り0.4重量％添加させて得た
高さ150μｍの未延伸フイルムを、比較例１の条
件のうち、赤外線ヒーターとしての表面温度750
℃の赤外線ヒーターを用い、低速、高速ロールの
表面速度比で縦方向に3.0倍に延伸し、次いで95
℃の熱風中で3.7倍の延伸倍率で横方向に延伸し、
更に再度縦方向に表面温度1000℃の赤外線ヒータ
ーで加熱して延伸倍率1.8倍で延伸し、その後220
℃で熱固定して厚さ7.5μｍの二軸配向ポリエステ
ルフイルムを得た。
この二軸配向ポリエステルフイルムの物性は次
の通りである。
ヤング率（縦方向）（Kg／mm2） 870
熱収縮率（％）
70℃・１時間（縦方向） 0.12
150℃・30分（横方向） 1.9
突起高さと突起数
（μｍ） （個／mm2）
1.5≧ｈ＞1.0 ４
1.0≧ｈ＞0.75 27
0.75≧ｈ＞0.5 90
0.5≧ｈ＞0.25 270
最大突起高さ（μｍ） 1.4
なお、この二軸配向ポリエステルフイルムの突
起分布曲線は図−２の曲線−Ａに近似するもので
あつた。
上記物性の二軸配向ポリエステルフイルムの片
面に実施例１に用いたのと同一構成の組成物を塗
工し、得られた複写剤を８mm巾のリボンにして評
価した。
このようにして得られた転写材の諸性能は表−
に示す如くであり、プリンターで印字したとき
印字圧力でフイルムが縦方向に裂けてしまい、鮮
明な印字ができなかつた。
比較例 ５
炭酸カルシウム（平均粒径1.5μｍ）の代りにカ
オリン（平均粒径0.5μｍ）を対ポリマー0.5重量
％添加した以外は実施例２と同様に製膜して7.5μ
ｍの二軸配向フイルムを得た。
得られたフイルムの特性は次の通りである。
ヤング率（縦方向）（Kg／mm2） 540
熱収縮率（％）
70℃・１時間（縦方向） 0.06
150℃・30分（横方向） 0.21
突起高さと突起数
（μｍ） （個／mm2）
1.5≧ｈ＞1.0 ０
1.0≧ｈ＞0.75 ０
0.75≧ｈ＞0.5 ７
0.5≧ｈ＞0.25 320
最大突起高さ 0.8
なお、この二軸配向フイルムの突起分布曲線は
図−２の曲線Ｂに示す。
上記特性の二軸配向ポリエステルフイルムに実
施例２の転写インク層組成物及び付着防止層組成
物を各々塗工した。
このようにして得られた転写材の諸性能は表−
に示す如くであり、インク転写性は十分でな
く、走行性は不満足であつた。[Table] Comparative example 4 Calcium carbonate (average particle size 1.5μ) as an additive
An unstretched film with a height of 150 μm obtained by adding 0.4% by weight of m) to the polymer was heated at a surface temperature of 750 μm as an infrared heater under the conditions of Comparative Example 1.
Using an infrared heater at 95 °C, stretch in the machine direction by 3.0 times at a surface speed ratio of low speed and high speed rolls, then 95 °C.
Stretched in the transverse direction at a stretching ratio of 3.7 times in hot air at ℃,
Furthermore, it was heated again in the longitudinal direction with an infrared heater with a surface temperature of 1000°C and stretched at a stretching ratio of 1.8x, and then stretched at a stretching ratio of 220°C.
A biaxially oriented polyester film having a thickness of 7.5 μm was obtained by heat setting at ℃. The physical properties of this biaxially oriented polyester film are as follows. Young's modulus (longitudinal direction) (Kg/mm 2 ) 870 Heat shrinkage rate (%) 70℃・1 hour (longitudinal direction) 0.12 150℃・30 minutes (horizontal direction) 1.9 Protrusion height and number of protrusions (μm) (pcs/ mm 2 ) 1.5≧h＞1.0 4 1.0≧h＞0.75 27 0.75≧h＞0.5 90 0.5≧h＞0.25 270 Maximum projection height (μm) 1.4 The projection distribution curve of this biaxially oriented polyester film is shown in Figure- It was similar to curve A of No. 2. A composition having the same composition as that used in Example 1 was coated on one side of a biaxially oriented polyester film having the above-mentioned physical properties, and the resulting copying agent was made into a ribbon having a width of 8 mm and evaluated. The various performances of the transfer material obtained in this way are shown in the table below.
As shown in Figure 2, when printing with a printer, the printing pressure caused the film to tear in the vertical direction, making it impossible to print clearly. Comparative Example 5 A film of 7.5 μm was formed in the same manner as in Example 2 except that 0.5% by weight of kaolin (average particle size 0.5 μm) based on the polymer was added instead of calcium carbonate (average particle size 1.5 μm).
A biaxially oriented film of m was obtained. The properties of the obtained film are as follows. Young's modulus (longitudinal direction) (Kg/mm 2 ) 540 Heat shrinkage rate (%) 70℃・1 hour (longitudinal direction) 0.06 150℃・30 minutes (horizontal direction) 0.21 Protrusion height and number of protrusions (μm) (pieces/ mm 2 ) 1.5≧h＞1.0 0 1.0≧h＞0.75 0 0.75≧h＞0.5 7 0.5≧h＞0.25 320 Maximum protrusion height 0.8 The protrusion distribution curve of this biaxially oriented film is curve B in Figure 2. Shown below. The transfer ink layer composition and anti-adhesion layer composition of Example 2 were each applied to a biaxially oriented polyester film having the above characteristics. The various performances of the transfer material obtained in this way are shown in the table below.
The ink transfer properties were not sufficient and the running properties were unsatisfactory.
図−１は転写リボンの走行性の測定装置の模式
図である。図−２は三次元粗さ計で求めたフイル
ム表面の突起高さ（Ｙ：μｍ）と突起の数（Ｘ：
ケ／mm2）の関係を示す図である。
FIG. 1 is a schematic diagram of a device for measuring the runnability of a transfer ribbon. Figure 2 shows the protrusion height (Y: μm) and the number of protrusions (X: μm) on the film surface determined using a three-dimensional roughness meter.
FIG .
Claims (1)
ルムの片面に厚さ３〜35μｍの転写インク層を設
けたプリンター用転写材において、該二軸配向ポ
リエステルフイルムが下記(イ)〜(ハ)、 (イ) 縦方向のヤング率が450〜800Kg／mm2である、 (ロ) 縦方向及び横方向の150℃での熱収縮率が７
％以下である、 (ハ) フイルム表面の三次元粗さで計で測定した突
起数（Ｙ：ケ／mm2）と突起高さ（Ｘ：μｍ）と
の関係を表わす突起分布曲線がlog10Y＞1.3の
領域において下記式(1) log10Y＝−1.8X＋3.9 ……(1) で表わされる線と交差せず、更に該突起分布の
最大値及び該最大値を越えた部分の曲線が下記
式(2) log10Y≧−3.6X＋2.8 ……(2) を満足する範囲にある を満足するものであり、更に該転写インク層を設
けた面と反対の表面に該転写インク層となじみが
殆んどない物質を塗設したことを特徴とするプリ
ンター用転写材。 ２ 二軸配向ポリエステルフイルム表面の多重干
渉反射式顕微鏡（Tl 単色光）で測定した突起
数（ケ／mm2）と突起高さ（ｈ：μｍ）が 1.5≧ｈ＞1.0 ……10ケ／mm2以下 1.0≧ｈ＞0.75 ……１〜30ケ／mm2 0.75≧ｈ＞0.5 ……15〜120ケ／mm2 0.5≧ｈ＞0.25 ……80ケ／mm2以上 を満足することを特徴とする特許請求の範囲第１
項記載のプリンター用転写材。 ３ ポリエステルフイルムの転写インク層となじ
みが殆んどない物質を塗設した面は摩擦係数が
0.5以下であり、かつ該摩擦係数の連続50回往復
走行テスト後の値が初期値に比し150％未満であ
ることを特徴とする特許請求の範囲第１項又は第
２項記載のプリンター用転写材。[Scope of Claims] 1. A transfer material for a printer comprising a biaxially oriented polyester film having a thickness of 1 to 25 μm and a transfer ink layer having a thickness of 3 to 35 μm on one side, wherein the biaxially oriented polyester film has the following (a): ~(c), (a) Young's modulus in the longitudinal direction is 450 to 800 Kg/ mm2 , (b) Thermal shrinkage rate at 150℃ in the longitudinal and transverse directions is 7.
% or less, (c) The protrusion distribution curve representing the relationship between the number of protrusions (Y: ke/mm 2 ) and the protrusion height (X: μm) measured by a total of three-dimensional roughness of the film surface is log 10 In the region of Y > 1.3, the line expressed by the following formula (1) log 10 Y = -1.8 The curve satisfies the following formula (2) log 10 Y ≧ −3.6 A transfer material for printers characterized by being coated with a substance that has almost no compatibility with the ink layer. 2 The number of protrusions (ke/mm 2 ) and protrusion height (h: μm) measured using a multiple interference reflection microscope (Tl monochromatic light) on the surface of a biaxially oriented polyester film are 1.5≧h＞1.0...10 protrusions/mm 2 or less 1.0≧h＞0.75 ...1 to 30 pieces/mm 2 0.75≧h＞0.5 ...15 to 120 pieces/mm 2 0.5≧h>0.25 ...80 pieces/mm 2 or more Claim 1
Transfer material for printers described in section. 3 The surface coated with a material that is almost incompatible with the transfer ink layer of the polyester film has a low coefficient of friction.
0.5 or less, and the value of the friction coefficient after 50 consecutive reciprocating tests is less than 150% of the initial value. Transfer material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61182772A JPS6339374A (en) | 1986-08-05 | 1986-08-05 | Transfer material for printer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61182772A JPS6339374A (en) | 1986-08-05 | 1986-08-05 | Transfer material for printer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6339374A JPS6339374A (en) | 1988-02-19 |
| JPH0453716B2 true JPH0453716B2 (en) | 1992-08-27 |
Family
ID=16124149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61182772A Granted JPS6339374A (en) | 1986-08-05 | 1986-08-05 | Transfer material for printer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6339374A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH029687A (en) * | 1988-06-28 | 1990-01-12 | Diafoil Co Ltd | Polyester film for thermal transfer |
| JP2566624B2 (en) * | 1988-07-14 | 1996-12-25 | ダイアホイルヘキスト株式会社 | Thermal transfer film |
| JPH0238089A (en) * | 1988-07-29 | 1990-02-07 | Oji Paper Co Ltd | Base sheet for thermal transfer image-receiving sheet |
| JPH0247094A (en) * | 1988-08-10 | 1990-02-16 | Diafoil Co Ltd | Transfer material for printer |
| JPH0248994A (en) * | 1988-08-11 | 1990-02-19 | Diafoil Co Ltd | Thermal transfer material for printer |
| JPH02219695A (en) * | 1989-02-21 | 1990-09-03 | Diafoil Co Ltd | Polyester film for thermosensitive transfer |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6025786A (en) * | 1983-07-22 | 1985-02-08 | Oji Paper Co Ltd | Heat transfer material |
| JPS60104395A (en) * | 1983-11-11 | 1985-06-08 | Konishiroku Photo Ind Co Ltd | Thermal transfer recording medium |
| JPS60104393A (en) * | 1983-11-11 | 1985-06-08 | Konishiroku Photo Ind Co Ltd | Thermal transfer recording medium |
| JPS60104392A (en) * | 1983-11-10 | 1985-06-08 | Konishiroku Photo Ind Co Ltd | Thermal transfer recording medium |
| JPS60174694A (en) * | 1984-02-20 | 1985-09-07 | Toray Ind Inc | Thermal transfer material |
| JPS60192628A (en) * | 1984-03-14 | 1985-10-01 | ダイアホイルヘキスト株式会社 | Biaxial oriented polyester film |
| EP0158344A2 (en) * | 1984-04-13 | 1985-10-16 | Toray Industries, Inc. | Ink transfer material for printer |
| JPS6133767A (en) * | 1984-07-27 | 1986-02-17 | Hitachi Ltd | Circuit for discriminating oscillating direction of arc |
| JPS6188181A (en) * | 1984-10-03 | 1986-05-06 | Seiko Epson Corp | Electronic time piece |
-
1986
- 1986-08-05 JP JP61182772A patent/JPS6339374A/en active Granted
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6025786A (en) * | 1983-07-22 | 1985-02-08 | Oji Paper Co Ltd | Heat transfer material |
| JPS60104392A (en) * | 1983-11-10 | 1985-06-08 | Konishiroku Photo Ind Co Ltd | Thermal transfer recording medium |
| JPS60104395A (en) * | 1983-11-11 | 1985-06-08 | Konishiroku Photo Ind Co Ltd | Thermal transfer recording medium |
| JPS60104393A (en) * | 1983-11-11 | 1985-06-08 | Konishiroku Photo Ind Co Ltd | Thermal transfer recording medium |
| JPS60174694A (en) * | 1984-02-20 | 1985-09-07 | Toray Ind Inc | Thermal transfer material |
| JPS60192628A (en) * | 1984-03-14 | 1985-10-01 | ダイアホイルヘキスト株式会社 | Biaxial oriented polyester film |
| EP0158344A2 (en) * | 1984-04-13 | 1985-10-16 | Toray Industries, Inc. | Ink transfer material for printer |
| JPS60217194A (en) * | 1984-04-13 | 1985-10-30 | Toray Ind Inc | Transfer material for printer |
| JPS6133767A (en) * | 1984-07-27 | 1986-02-17 | Hitachi Ltd | Circuit for discriminating oscillating direction of arc |
| JPS6188181A (en) * | 1984-10-03 | 1986-05-06 | Seiko Epson Corp | Electronic time piece |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6339374A (en) | 1988-02-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |