JPH0453198B2 - - Google Patents
Info
- Publication number
- JPH0453198B2 JPH0453198B2 JP61088181A JP8818186A JPH0453198B2 JP H0453198 B2 JPH0453198 B2 JP H0453198B2 JP 61088181 A JP61088181 A JP 61088181A JP 8818186 A JP8818186 A JP 8818186A JP H0453198 B2 JPH0453198 B2 JP H0453198B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- transfer
- biaxially oriented
- less
- ink
- 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 65
- 239000000463 material Substances 0.000 claims description 31
- 239000010419 fine particle Substances 0.000 claims description 28
- 229920006267 polyester film Polymers 0.000 claims description 27
- 238000009826 distribution Methods 0.000 claims description 11
- 239000010410 layer Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 21
- 238000010438 heat treatment Methods 0.000 description 20
- -1 polypropylene Polymers 0.000 description 19
- 239000002245 particle Substances 0.000 description 16
- 229920000728 polyester Polymers 0.000 description 15
- 239000011347 resin Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000007639 printing Methods 0.000 description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000037303 wrinkles Effects 0.000 description 8
- 238000000576 coating method Methods 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
- 238000012545 processing Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 235000012239 silicon dioxide Nutrition 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 4
- 229910052788 barium Inorganic materials 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- 229910010272 inorganic material 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
- 239000008188 pellet Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000002040 relaxant effect Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000010186 staining Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 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
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 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
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 150000001875 compounds Chemical class 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
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 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
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 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
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 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
- 238000004804 winding Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-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
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-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
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 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
- 235000012211 aluminium silicate Nutrition 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
- 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
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229940050390 benzoate Drugs 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 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
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 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
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 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
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 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
- 238000010586 diagram Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195729 fatty acid Natural products 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
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 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
- 238000010191 image analysis Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 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
- 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 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
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 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
- 238000002156 mixing Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 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
- 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
- 239000003973 paint Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- SNGARVZXPNQWEY-UHFFFAOYSA-N phenylmethanediol Chemical compound OC(O)C1=CC=CC=C1 SNGARVZXPNQWEY-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 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
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 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
- 239000000758 substrate Substances 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
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 229910052845 zircon 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
- B41M5/025—Duplicating or marking methods; Sheet materials for use therein by transferring ink from the master sheet
Landscapes
- Impression-Transfer Materials And Handling Thereof (AREA)
- Thermal Transfer Or Thermal Recording In General (AREA)
- Duplication Or Marking (AREA)
- Laminated Bodies (AREA)
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
回数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
したインク層がリボンの反対面（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。このトラブルとフイル
ム表面性との関連性は大きく、従つて、この改善
が望まれている。
一方、インク層については繰返し使用に適する
ためにインク塗布層を全体的に厚くしたり、イン
ク組成に工夫をこらすなどしているが、繰返し使
用の回数がふえるにつれて転写に濃淡が見られ、
このため、きれいな印字を得るための改善が望ま
れている。
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。
発明の構成・効果
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
ー用転写材であつて、該フイルムは縦方向のヤン
グ率が450〜800Kg／mm2であり、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り、70℃で１時間無荷重下で
熱処理したときのフイルムの縦方向の熱収縮率が
0.10％以下であり、かつ150℃で30分間熱処理し
たときのフイルムの横方向の熱収縮率が７％以下
であり、さらに前記インク層に体積形状係数
（ｆ）が0.30〜π／６の範囲にある平均直径0.05
〜1.0μmの微粒子を３〜35重量％分散含有させた
ことを特徴とするプリンター用転写材。
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、特定の体積形状係数を有
する微粒子を主成分とすることが特徴であり、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。
この微粒子は体積形状係数（ｆ）が0.30〜π／
６の範囲にあり、かつ平均直径0.05〜1.0μmの不
活性な微粒子である必要がある。この体積形状係
数（ｆ）は0.35〜π／６、更には0.40〜π／６で
あることが好ましい。換言すれば、微粒子は真球
に近いほど好ましい。また平均直径は0.10〜
0.5μm、更には0.15〜0.30であることが好ましい。
微粒子の平均直径0.05μm未満の場合は、粒径が
小さくすぎるためにかなりの量を添加しても１回
のストライクでインク層が多量に転写されてしま
い、又繰返し打ちによつて濃淡斑が発生し、添加
効果が得られない。一方、この平均直径が1.0μm
を越えると、粒径が大きすぎてインクが均一に転
写されにくく、転写の鮮明性が劣る等の問題が発
生するので好ましくない。
ここで、本明細書で云う“体積形状係数（ｆ）”
は、次式で求められる。
ｆ＝Ｖ／D2
〔ここで、Ｖは微粒子の体積（μm3）であり、Ｄ
は微粒子の最大径（μm）である。〕
微粒子としては、バインダー成分や、柔軟剤、
可撓剤その他の目的でインク層に用いられる有機
剤と反応しないものであれば、有機系樹脂、無機
系化合物のいずれでも差しつかえない。有機系樹
脂としては。ナイロン−６樹脂、ナイロン−６−
６樹脂、ベンゾグアナミン樹脂、架橋ポリスチレ
ン樹脂、架橋アクリル樹脂、ポリメチルメタクリ
レート樹脂、ポリプロピレン樹脂、フツ化エチレ
ン樹脂、フツ化塩化エチレン樹脂、フツ化エチレ
ン−フツ化プロピレン共重合樹脂、フツ素ゴム等
が好適なものとして例示される。これらはインク
組成中で微粒子状で存在し、この点でバインダー
成分として用いられる樹脂とは異なる。また、無
機系化合物としては二硫化モリブデン、二酸化チ
タン、硫酸バリウム、炭酸カルシウム等が好適な
ものとして例示される。これら微粒子は単独使用
でもよく、また２種以上用いてもよい。
これら微粒子は下記の作用により、その効果を
発現すると推測される。
インク層に分散する微粒子は１ストロークで一
時に多量のインクが転写されることがないように
作用し、１ストローク当りのインク転写量を調
節、均一化する。次に該微粒子がチクソトロピー
の働きを担うことにより、インパクトによつて転
写されて部分的に厚薄を生じたインク層を均一化
する方向に作用し、繰返し打ちをすることに対し
て転写斑（濃淡の発生）が生じにくい方向に働
く。
微粒子の添加量は３〜35重量％であり、好まし
くは５〜30重量％である。この添加量が３重量％
未満の場合には微粒子添加の効果が得られず、反
面35重量％より多い場合には、インク層中に均一
に分散されず、部分的に凝集物を生じる等品質上
の問題が生じる。
本発明におけるインク層は上述の微粒子を分散
混合させる点以外は、従来から知られ、或いは用
いられているインク層で形成することができる。
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、塩ビ系ポリマー、塩ビ−
酢ビ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。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（転写材裏面への転写）が起るの
で好ましくない。
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、
エチレングリコーク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を
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、ο−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、
更に好ましくは520〜700Kg／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、転写リボンとし
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正に欠け、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
な転写画質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必要
があるが、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ことが必要であ
る。
log10Ｙ＝−1.8×＋3.9 ……(1)
log10Ｙ≧−3.6×＋2.8 ……(2)
フイルム表面粗さが式log10＝−3.6×＋2.8で表
わされる直線を下まわるか或いは最大値を越えた
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
ドの摩耗の原因となり、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。この表面特性を満足
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
は、また、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，ZnZr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テレフタル酸塩；Mg，Ca，Ba，Zn，
Cd，Pb，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、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、燐酸ナトリウム、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
複塩（水和物を含む）、ガラス粉、粘土（カオリ
ン、ベントナイト、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。
本発明における二軸配向ポリエステルフイルム
は、更に、無荷重の状態で70℃の熱風中に１時間
曝した時の熱収縮率が縦方向で0.10％以下であ
り、好ましくは0.08％以下である。このフイルム
の縦方向の熱収縮率が0.10％を越えると、インク
層塗工の工程、特に塗工後の乾燥時またはその後
のエージング期間中にロール状に巻き取つた状態
の加工原反が巻芯方向に収縮を生じ、これがフイ
ルムの表面性との兼ね合いでインク層を塗工しな
い反対のフイルム面（走行面）にインク層が転写
して転写材（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、リボンの走行を阻害し、極端な場合に
はリボンが動かなる等のトラブルが生じる大きな
原因となる。
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横方向
の熱収縮率が７％以下であり、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等の巾収縮が
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
たベ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向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圧
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
延伸温度：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、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℃、更には
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
合には上記熱処理等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く、
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なるが、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、プリンター用転写
リボン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、弾性率、耐熱性、
高融点等に加え、インクの転写しにくい表面性を
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、かつ転写画
質に優れた転写材として有用である。
実施例
以下、実施例を掲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
小坂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ｙとする。ｘを順次増加又
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400〜500Å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300mm
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）×1
00
(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
物を層の厚さ18μmとなるようにグラビユア方式
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５cmで１
Kg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５mmφ）
３は荷重（100ｇｒ）、５，６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30mm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の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を目視にて３段階で判定す
る。
＜３段階判定＞
○…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
△…繰返し回数が増すに従つて印字はやや太めに
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め
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
てフイルムの打ち跡を目視にて３段階で判定す
る。
＜３段階判定＞
○…打ち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
(9) 体積形状係数（ｆ）
体積形状係数（ｆ）は次式によつて求める。
ｆ＝Ｖ／D3
ここで、Ｖは微粒子の体積（μm3）であり、該
体積は下記のの方法で求められた平均粒径
（ｄ：μm）を用いかつ式Ｖ＝π／６・d3から算出し
た値である。またＤは微粒子の最大径の平均値
（μm）であり、該平均値は走査型電子顕微鏡によ
つて微粒子の写真（5000倍で10視野）を撮影し、
画像解析処理装置ルーゼツクス500（日本レギユレ
ーター製）を用いて求めた最大径の平均値であ
る。
微粒子の平均粒径
島津製作所CP−50型セントリフユグルパーテ
イクル サイズ アナライザー（Centrifugal
Partiele Size Analyser）を用いて測定した。得
られた延伸沈降曲線を基に算出した各粒径の粒子
とその存在量との累積曲線から、50マスパーセン
ト（mass percent）に相当する粒径を読み取り、
この値を上記平均粒径とする。
実施例１〜実施例10
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、混合攪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
を触媒として常法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）を攪拌下添加した。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
タレートペレツトを得た。
更にこのポリエチレンテレフタレート（以下
PETと略称）ペレツトを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圧し、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110℃の温度で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℃に加熱後、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転写材の諸性能はいず
れも良好レベルにあつた。
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 number of times they are used repeatedly is also increasing year by year.For example, with conventional biaxially oriented polyester film, the print area during transfer using the dot impact method is There were problems such as deformation and elongation of the film due to unprinted areas, 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) of the ribbon, 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. It was hot. This problem is closely related to the surface properties of the film, and therefore, an improvement in this problem is desired. On the other hand, in order to make the ink layer suitable for repeated use, efforts have been made to make the ink coating layer thicker overall and to improve the composition of the ink, but as the number of repeated uses increases, shading appears in the transfer.
Therefore, improvements are desired to obtain clear printing. 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. Structure and Effects of the Invention According to the present invention, the object of the present invention is to
This is a transfer material for printers that has a transfer ink layer of 3 to 35 μm thick on one side of a 25 μm biaxially oriented polyester film, and the film has a Young's modulus in the longitudinal direction of 450 to 800 Kg/mm 2 and In the area where 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 of log 10 Y > 1.3, the following formula (1) is used. log 10 Y = −1.8 -3.6
0.10% or less, and the film has a lateral heat shrinkage rate of 7% or less when heat treated at 150°C for 30 minutes, and the ink layer has a volume shape factor (f) in the range of 0.30 to π/6. Average diameter at 0.05
A transfer material for printers, characterized in that it contains fine particles of ~1.0 μm dispersed in an amount of 3 to 35% by weight. In the present invention, the transfer ink layer is characterized in that, in addition to a binder component and a coloring component, the main component is fine particles having a specific volume shape coefficient, and if necessary, a softener, a flexibilizer, a dispersant, Constructed by adding a smoothing agent and the like as appropriate. These fine particles have a volume shape factor (f) of 0.30 to π/
6 and an average diameter of 0.05 to 1.0 μm. The volumetric shape factor (f) is preferably 0.35 to π/6, more preferably 0.40 to π/6. In other words, it is preferable that the fine particles be as close to a perfect sphere as possible. Also, the average diameter is 0.10~
It is preferably 0.5 μm, more preferably 0.15 to 0.30.
If the average diameter of the fine particles is less than 0.05 μm, the particle size is too small, so even if a considerable amount is added, a large amount of the ink layer will be transferred in one strike, and repeated strikes will cause unevenness. occurs, and the effect of the addition cannot be obtained. On the other hand, this average diameter is 1.0μm
If the particle size exceeds 100, the particle size is too large, making it difficult to transfer the ink uniformly and causing problems such as poor transfer clarity, which is not preferable. Here, the "volume shape factor (f)" referred to in this specification
is calculated using the following formula. f=V/D 2 [Here, V is the volume of the fine particles (μm 3 ), and D
is the maximum diameter (μm) of the fine particles. ] Fine particles include binder components, softeners,
Any organic resin or inorganic compound may be used as long as it does not react with the organic agent used in the ink layer as a flexibilizer or for other purposes. As an organic resin. Nylon-6 resin, Nylon-6-
6 resin, benzoguanamine resin, crosslinked polystyrene resin, crosslinked acrylic resin, polymethyl methacrylate resin, polypropylene resin, fluorinated ethylene resin, fluorinated chlorinated ethylene resin, fluorinated ethylene-fluorinated propylene copolymer resin, fluorocarbon rubber, etc. are suitable. It is exemplified as an example. These exist in the form of fine particles in the ink composition, and are different from resins used as binder components in this respect. In addition, suitable examples of inorganic compounds include molybdenum disulfide, titanium dioxide, barium sulfate, and calcium carbonate. These fine particles may be used alone or in combination of two or more kinds. It is presumed that these fine particles exert their effects through the following actions. The fine particles dispersed in the ink layer prevent a large amount of ink from being transferred at once in one stroke, and adjust and make the amount of ink transferred per stroke uniform. Next, the fine particles act as thixotropy, which acts to homogenize the ink layer that has been partially thickened and thinned due to the transfer due to the impact. (occurrence of) will work in a direction that makes it less likely to occur. The amount of fine particles added is 3 to 35% by weight, preferably 5 to 30% by weight. This amount added is 3% by weight.
If the amount is less than 35% by weight, the effect of adding the fine particles will not be obtained. On the other hand, if it is more than 35% by weight, quality problems such as not being uniformly dispersed in the ink layer and the formation of aggregates will occur in some parts. The ink layer in the present invention can be formed of a conventionally known or used ink layer, except that the above-mentioned fine particles are dispersed and mixed.
Examples of ink ingredients include carnauba wax,
Waxes such as paraffin wax, n-fatty acid alkyl ester, vinyl chloride polymer, vinyl chloride
Binder components such as vinyl acetate copolymer, etc.
Colorants and other ingredients are used. The colorant is mainly carbon black,
Various other dyes or organic or inorganic pigments may be used. In some cases, the transfer ink may also include a sublimation type. The transfer ink layer is formed by a conventional method, for example,
It can be carried out using solution coating methods such as gravure, reverse, and slit die methods, or hot melt coating in a state in which a solvent is added.
At that 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 3-35 μm. If the ink layer is too thick, the ink layer will be transferred (transferred to the back side of the transfer material) when the transfer material is wound into a roll, which is not preferable. 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 80 mol% of the total glycol component. Particularly preferred are copolymers in which mol % or more is ethylene glycol.
In this case, up to 20 mol% of the dicarboxylic acid of the total acid component can be the above-mentioned aromatic dicarboxylic acids; for example, aliphatic dicarboxylic acids such as adipic acid and sebacic acid; fatty acids such as cyclohexane-1,4-dicarboxylic acid. dicarboxylic acids and the like. In addition, less than 20 mol% of the total glycol component is
Can be the above glycols other than ethylene glycoke, or aromatic diols such as hydroquinone, resorcinol, 2,2-bis(4-hydroxyphenyl)propane; 1,4
-Aliphatic diols containing aromatics such as dihydroxymethylbenzene; polyalkylene glycols (polyoxyallene glycols) such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; and the like. 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 included. The above polyester is known per se, and can be produced by a method known per se. The above-mentioned polyester preferably has an intrinsic viscosity of about 0.4 to about 0.9 measured as a solution in o-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 ,
More preferably, it has a property of 520 to 700 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 450 kg/mm 2 , the film tends to stretch and is difficult to recover elastically. Therefore, when used as a transfer ribbon for printing, the printed area will be plastically deformed due to printing pressure, making it thicker than necessary. This is undesirable because the clarity of the print is poor, and the deformation makes it difficult to handle when winding up the transfer ribbon. Also,
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 μm.
~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 not be suitable for use as a transfer ribbon, and will also be inferior in 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 image quality. The biaxially oriented polyester film in the present invention needs to have the above-mentioned longitudinal Young's modulus and thickness, but furthermore, the surface on which the transfer ink layer is provided has the number of protrusions (Y: ke/mm) measured with a three-dimensional roughness meter. 2 ) and the protrusion height (X: μm) does not intersect the line expressed by the following formula (1) in the area of log 10 Y > 1.3, and the maximum value of the protrusion distribution It is also necessary that the curve in the portion exceeding the maximum value has surface characteristics within a range that satisfies the following formula (2). log 10 Y=-1.8×+3.9 ……(1) log 10 Y≧−3.6×+2.8 ……(2) Draw a straight line whose film surface roughness is expressed by the formula log 10 =-3.6×+2.8. If the distribution of protrusions is downward or intersects in areas exceeding the maximum value (particularly where areas with large protrusions intersect and descend downwards), the ink layer should be wound on a roll after being applied. At this time, the ink is easily transferred to the opposite side (running surface) of the film, staining the running surface of the ribbon, and this gradually accumulates ink at the contact parts such as guide posts of the ribbon running system, inhibiting the running of the ribbon. However, in extreme cases, problems such as the ribbon not moving may occur, and the slipperiness of the film may become worse.
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 of 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 this 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 3μm or less,
Furthermore, it is desirable that the thickness be 1.5 μm or less. The biaxially oriented polyester film of the present invention also has a friction coefficient of 0.5 or less on the surface on which the transfer ink layer is not provided, further 0.45 or less, particularly 0.35-
0.45, and the value of the friction coefficient after 50 consecutive reciprocating tests is preferably 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 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 SiO2 (e.g. amorphous or crystalline clay minerals, aluminosilicate (including calcined products and hydrated products), warm asbestos, zircon, fly ash, etc.), Mg, Oxides of ZnZr and Ti; Sulfates of Ca and Ba; Phosphates of Li, Na, and Ca (including monohydrogen salts and dihydrogen salts);
Benzoate of Li, Na and K; Ca, Ba, Zn,
and Mn terephthalate; Mg, Ca, Ba, Zn,
Titanates of Cd, Pb, 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.) Ca, and
Examples include Mg carbonate; fluorite; and ZnS. More preferably, anhydrous silicic acid, hydrated silicic acid, aluminum oxide, aluminum silicate (including calcined products, hydrates, etc.), monolithium phosphate, trilithium phosphate, sodium phosphate, barium phosphate, titanium oxide, and lithium benzoate. , double salts of these compounds (including hydrates), glass powder, clay (including kaolin, bentonite, 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 used 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. Furthermore, the biaxially oriented polyester film of the present invention has a heat shrinkage rate in the longitudinal direction of 0.10% or less, preferably 0.08% or less when exposed to hot air at 70° C. for 1 hour under no load. If the thermal shrinkage rate of this film in the longitudinal direction exceeds 0.10%, the processed material in a rolled state will be unwound during the ink layer coating process, especially during the drying period after coating or during the subsequent aging period. Shrinkage occurs in the direction of the core, and due to the surface properties of the film, the ink layer is transferred to the opposite side of the film (running surface) on which the ink layer is not applied, staining the running surface of the transfer material (ribbon), and this causes the running surface of the transfer material (ribbon) to become dirty. Ink gradually accumulates on contact parts such as guide posts of the system, obstructs the running of the ribbon, and in extreme cases becomes a major cause of problems such as ribbon movement. Further, the biaxially oriented polyester film of the present invention has a transverse heat shrinkage rate of 7% or less, preferably 4% or less, particularly preferably 2% or less when heat treated at 150° C. for 30 minutes. If this thermal shrinkage rate is greater than 7%, not only will width shrinkage increase during relaxation treatment, but also thick spots will worsen due to shrinkage during processing into printer transfer materials, that is, coating, drying, etc. This is not preferable because it causes a decrease in yield and the like. In addition, if this thermal shrinkage rate is less than 0%, wrinkles will occur on the heating roll in the case of a method in which relaxation is performed by the speed difference between two rolls, and the base film will remain in the roll shape as a transfer material for printers. If the roll is left to stand until it is processed, wrinkles will occur in the vertical direction on the roll surface, and furthermore, wrinkles will occur on the surface of the intermediate product roll during the process of processing the transfer material for printers, which is not preferable. It is presumed that these wrinkles occur when the lateral thermal expansion of the film 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 manufacturing method, but
Usually, polyester containing a predetermined proportion of fine particles is melted, pressed into a sheet through a slit-shaped die, cooled and solidified in a casting drum to form an unstretched sheet, and then the unstretched sheet is stretched biaxially. A product (film) is produced by further subjecting it to heat treatment (heat setting), adjustment treatment for the heat shrinkage rate in the transverse direction, and then longitudinal relaxation treatment. In this case, in order to suitably satisfy the requirements of the present invention,
For example, the stretching temperature is such that the first-stage stretching temperature (e.g. longitudinal stretching temperature: T 1 ) is in the range of (Tg-10) to (Tg+45)°C (where Tg is the glass transition temperature of polyester), and the second-stage stretching temperature ( For example, the transverse direction stretching temperature: T 2 ) is set in the range of (T 1 −15) to (T 1 +40)°C, and the stretching ratio is 2.5 to 6.0 times, especially in the first stage stretching.
3.5 to 5.5 times, and 2.5 to 4.0 in the second stage, especially
It is preferable to set it as 2.8 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 lateral heat shrinkage rate.
After that, 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 better to stretch the film in the width direction during the above heat treatment, and if the heat shrinkage rate is too large, the film may be relaxed 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℃
When the temperature is 180℃, it is recommended to relax 5 to 11%, when the temperature is 180℃, it is recommended to relax 1 to 8%, and when the temperature is 200℃, it is recommended to tense or relax 0 to 5%.
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 processing stage of printer transfer ribbon.
Causes paint spots. 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. The transfer material for printers of the present invention has an ink layer that does not cause transfer spots even after repeated use, and the excellent properties inherent to the biaxially oriented polyester film, including chemical resistance, strength, elastic modulus, and heat resistance. sex,
In addition to its high melting point, it has a surface that makes it difficult for ink to transfer, and maintains suitable running properties.If used for impact applications, even after repeated use, there will be almost no plastic deformation such as leftover marks due to printing. It is useful as a transfer material with excellent transfer 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 Kosaka Laboratory, needle diameter 2μmR, needle pressure 30mg, measurement length 1mm, sampling pitch 2μm, cutoff 0.25mm, vertical magnification 20,000 times. , the profile of the protrusions on the film surface is imaged three-dimensionally (stereoscopically) under the conditions of 200x lateral magnification and 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). )
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. A protrusion distribution curve can be drawn by sequentially increasing or decreasing x, reading the number of y at that time, and plotting it on a graph. (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 protrusions Aluminum is uniformly vacuum-deposited on the surface of the film to a thickness of 400 to 500 Å or less, and collodion is applied to the opposite non-vapor-deposited surface (film surface) and attached, followed by drying. 100 Tl using a monochromatic light multiple interference reflectance microscope (e.g. Carl Zeiss JENA).
An arbitrary 100 cm 2 of the aluminum-deposited surface is observed at double magnification, and the number of protrusions with interference fringes generated corresponding to the protrusion heights in the microscope field is counted. (4) Heat shrinkage rate 300mm for a film sample cut out to a width of 20mm
Mark a gauge at the distance, and heat it to 70℃ or 150℃.
Hang it with no load on a circulating hot air blower heated to Display the percentage as a percentage. Heat shrinkage rate (%) = (original length) - (length after heating) / (original length) x 1
00 (5) Ink transferability The transfer ink composition is coated on one side of a 10μm thick film using the gravure method so that the layer thickness is 18μm, and the resulting transfer sheet is 10mm wide x
Cover a 20cm long film sample and 1.
After repeatedly pressing 20 times with a 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, and visually evaluate the degree of ink adhesion (stain level) to the cotton swab. Judgment is made in 5 stages. <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 the load cell and 2 is the surface roughness.
0.5μm plastic fixing rod (outer diameter 5mmφ)
3 is the load (100gr), 5 and 6 are sample fixtures,
4 indicates a sample (ribbon). The opposite side of the transfer ink-coated surface (running surface) of a sample with a width of 8 mm (transfer ink layer coated to a thickness of 18 μm) in an environment with a temperature of 20°C and a humidity of 60% RH.
The friction coefficient is read by touching the fixed rod 2 at 90 degrees and moving the load cell 1 horizontally back and forth over a length of 30 cm at a speed of 30 mm per second. 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 reciprocations with respect to the initial friction coefficient is less than 120%, and the friction coefficient does not increase much due to repeated running △...50 repeated reciprocations with respect to the initial friction coefficient The friction coefficient during running is 120% or more and less than 150%,
A slight increase in the friction coefficient is observed due to repeated running ×...The friction coefficient after 50 repeated back and forth runs is 150% or more compared to the initial friction coefficient, and a significant increase in the friction coefficient is observed due to repeated running (7) Print clarity Using an electric typewriter IBM82C, the opposite side of the ink-coated side of the transfer ribbon coated with a transfer ink layer with a thickness of 18 μm was printed using Alphabet's "Q".
Repeatedly type the letter "Q" 10 times on regular typewriter paper, and check the clarity of the printed "Q", the thickness of the print,
The degree of change in shading is visually determined in three stages. <Three-level judgment> ○...The print does not become thick even after 10 repetitions, there are no shading spots, and it is clear. △...The printing becomes slightly thicker as the number of repetitions increases, and the shading spots are slightly It is noticeable, but the sharpness is maintained to a certain degree ×...As the number of repetitions increases, the print becomes considerably thicker, and there are strong shading spots in some parts, and the sharpness is lacking (8) Film Degree of deformation The same spot is hit 10 times in a row using the method shown in (7) above, and the marks on the film are visually judged in 3 stages. <Three-stage judgment> ○...Hardly noticeable marks △...Slightly noticeable marks ×...Small marks found (9) Volume shape factor (f) Volume shape factor (f) is It is calculated using the following formula. f=V/D 3 Here, V is the volume of the fine particles (μm 3 ), and the volume is calculated using the average particle diameter (d: μm) determined by the method below and the formula V=π/6・This is the value calculated from d3 . In addition, D is the average value (μm) of the maximum diameter of the fine particles, and the average value is determined by taking photographs of the fine particles (10 fields of view at 5000x magnification) using a scanning electron microscope.
This is the average value of the maximum diameter determined using the image analysis processing device Luzetx 500 (manufactured by Nippon Regulator). Average particle size of fine particles Shimadzu CP-50 type Centrifugal particle size analyzer (Centrifugal
Partiele Size Analyzer). From the cumulative curve of particles of each particle size and their abundance calculated based on the obtained stretching sedimentation curve, read the particle size corresponding to 50 mass percent,
This value is defined as the above average particle diameter. Examples 1 to 10 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 transesterifying 70 parts by weight of EG in a conventional manner using 0.035 parts by weight of manganese acetate tetrahydrate as a catalyst, the calcium carbonate obtained above (concentration 0.4% by weight) was transesterified.
(copolymer) 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 polyethylene terephthalate pellets having an intrinsic viscosity of 0.620. Furthermore, this polyethylene terephthalate (hereinafter
After drying the pellets (abbreviated as PET) at 170℃ for 3 hours, the pellets are fed to 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 molded and pressed onto 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 hot air at a temperature of 110°C.
Next, heat treatment was performed at 230° C. for 15 seconds to obtain a biaxially oriented film with a thickness of 7.5 μm. Note that the stretching speed at this time was 20 m/min. Next, this biaxially oriented film is heated with a heated roll.
After heating to 120℃, relaxation treatment is applied between a cooling roll while applying tension corresponding to the shrinkage according to the heat treatment temperature, 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. An ink having the composition shown in Table 1 was coated on one side of a biaxially oriented polyester film having the above characteristics to a layer thickness of 18 μm using a gravure method. 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 performances of the transfer material thus obtained were all at a good level.
【表】
フツ素ゴム：同上；ダイエル
ベンゾグアナミン樹脂：日本触媒工業(株)製；エ
ポスターS
ポリメチルメタクリレート樹脂：東洋ケミカルズ
(株)製；MP−1000
比較例１〜比較例４
実施例１〜10で用いたと同じ二軸配向ポリエス
テルフイルムを用いて、該フイルムの片面に表−
２に示した組成インクを、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−２に示す。
このようにして得られた転写材の諸性能はいず
れも印字鮮明性が悪く、更に比較例１及び２にお
いてはインクがフイルムの反対面（走行面）に転
写して走行性を悪化させる為の欠等が生じた。
比較例５〜比較例６
実施例１〜実施例10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
配向フイルムを得た。
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） 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
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
面に表−２に示した組成のインクを用いる以外は
実施例１〜10と同様に塗工して転写材を得た。
このようにして得られた転写材の諸性能は表−
２に示す如く、フイルム変形度が不満足であつ
た。
比較例 ７
添加剤として炭酸カルシウム（平均粒径
1.5μm）を対ポリマー当り0.4重量％添加させて得
た厚さ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
面に表−２に示した組成インクを、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−２
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 ８
実施例１〜４で用いたのと同じ二軸配向ポリエ
ステルフイルムを用い、該フイルムの片面に表−
２に示した組成のインクを比較例１〜４と同じよ
うにして塗工した。この転写材を８mm巾のリボン
にして評価した。その結果を表−２に示す。
このようにして得られた転写材は印字鮮明性、
反対面へのインク転写性及び走行性が悪いもので
あつた。[Table] Fluororubber: Same as above; Daiel Benzoguanamine resin: Manufactured by Nippon Shokubai Kogyo Co., Ltd.; Eposter S
Polymethyl methacrylate resin: Toyo Chemicals
Manufactured by Co., Ltd.; MP-1000
Comparative Examples 1 to 4 The same biaxially oriented polyester film used in Examples 1 to 10 was used, and one side of the film was
The ink having the composition shown in 2 was coated using the gravure method so that the layer thickness was 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-2. The various performances of the transfer materials obtained in this way were all poor in print clarity, and furthermore, in Comparative Examples 1 and 2, the ink was transferred to the opposite surface (running surface) of the film, worsening the running performance. A shortage occurred. Comparative Example 5 to Comparative Example 6 Among the manufacturing conditions for the biaxially oriented polyester film in Examples 1 to 10, the total magnification for longitudinal re-stretching was 3.3 times, and the horizontal stretching magnification was 3.8 times, except for the above conditions. A biaxially oriented film with a thickness of 7.6 μm was obtained under the same conditions. The physical properties of this biaxially oriented 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 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 protrusion height (μm) 1.2 The protrusion distribution curve of this biaxially oriented film approximated the curve in Figure 2. . Transfer materials were obtained by coating in the same manner as in Examples 1 to 10, except that an ink having the composition shown in Table 2 was used on one side 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 in Figure 2, the degree of film deformation was unsatisfactory. Comparative Example 7 Calcium carbonate (average particle size
An unstretched film with a thickness of 150 μm obtained by adding 0.4% by weight of 1.5 μm) to the polymer was heated at a surface temperature of 750°C as an infrared heater under the conditions of Comparative Example 1.
Using an infrared heater of
Stretched in the transverse direction at a stretching ratio of 3.7 times in hot air,
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 with a thickness of 7.5 μm was obtained by heat setting at °C. 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) (pieces/ 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 protrusion height (μm) 1.4 The protrusion distribution curve of this biaxially oriented polyester film is shown in Figure- It was similar to the curve No. 2. An ink composition shown in Table 2 is applied to one side of a biaxially oriented polyester film having the above physical properties, and the thickness of the layer is
It was coated using the gravure method to a thickness of 18 μm.
The obtained transfer material was made into an 8 mm ribbon and evaluated. Table 2 shows the various performances of the transfer material obtained in this way.
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 8 The same biaxially oriented polyester film as used in Examples 1 to 4 was used, and one side of the film was
The ink having the composition shown in No. 2 was applied in the same manner as in Comparative Examples 1 to 4. This transfer material was made into a ribbon with a width of 8 mm and evaluated. The results are shown in Table-2. The transfer material obtained in this way has excellent printing clarity and
The ink transferability and runnability to the opposite side were poor.
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であつて、該フイルムは
縦方向のヤング率が450〜800Kg／mm2であり、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超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り、70℃で１時間無荷重下で
熱処理したときのフイルムの縦方向の熱収縮率が
0.10％以下であり、かつ150℃で30分間熱処理し
たときのフイルムの横方向の熱収縮率が７％以下
であり、さらに前記インク層に体積形状係数
（ｆ）が0.30〜π／６の範囲にある平均直径0.05
〜1.0μmの微粒子を３〜35重量％分散含有させた
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が、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 を満足する特性を有する特許請求の範囲第１項記
載のプリンター用転写材。[Scope of Claims] 1. A transfer material for printers, comprising a biaxially oriented polyester film with a thickness of 1 to 25 μm and a transfer ink layer with a thickness of 3 to 35 μm on one side, the film having a Young's modulus in the longitudinal direction. The number of protrusions (Y:
In the region where the protrusion distribution curve representing the relationship between the protrusion height (X: μm ) and the protrusion height (X: μm) is expressed by the following formula (1) log 10 Y =-1.8X+3.9...(1) A range in which the maximum value of the protrusion distribution and the curve of the portion exceeding the maximum value satisfy the following formula (2) log 10 Y≧−3.6X+2.8 ……(2) without intersecting the line represented by The longitudinal heat shrinkage rate of the film when heat treated at 70℃ for 1 hour under no load is
0.10% or less, and the film has a lateral heat shrinkage rate of 7% or less when heat treated at 150°C for 30 minutes, and the ink layer has a volume shape factor (f) in the range of 0.30 to π/6. Average diameter at 0.05
A transfer material for printers, characterized in that it contains fine particles of ~1.0 μm dispersed in an amount of 3 to 35% by weight. 2 The number of protrusions (k/mm 2 ) and protrusion height (h: μm) measured using a multiple interference reflection microscope (Tl monochromatic light) on the film surface of a biaxially oriented polyester film.
is 1.5≧h＞1.0 …10 pcs/mm 2 or less 1.0≧h＞0.75 …1 to 30 pcs/mm 2 0.75≧h＞0.5 …15 to 120 pcs/mm 2 0.5≧h＞0.25 ……80 2. The transfer material for printers according to claim 1, which has a property satisfying a property of 1.5 mm/mm 2 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61088181A JPS62244691A (en) | 1986-04-18 | 1986-04-18 | Transfer material for printer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61088181A JPS62244691A (en) | 1986-04-18 | 1986-04-18 | Transfer material for printer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62244691A JPS62244691A (en) | 1987-10-26 |
| JPH0453198B2 true JPH0453198B2 (en) | 1992-08-25 |
Family
ID=13935735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61088181A Granted JPS62244691A (en) | 1986-04-18 | 1986-04-18 | Transfer material for printer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62244691A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0247093A (en) * | 1988-08-10 | 1990-02-16 | Diafoil Co Ltd | Transfer material for printer |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57160691A (en) * | 1981-03-31 | 1982-10-04 | Fujitsu Ltd | Ink composition for heat transfer recording and heat transfer recording ink sheet employing said composition |
| JPS58138684A (en) * | 1982-02-13 | 1983-08-17 | Fuji Kagakushi Kogyo Co Ltd | Recording medium for color heat transfer |
| JPS6025786A (en) * | 1983-07-22 | 1985-02-08 | Oji Paper Co Ltd | Heat transfer material |
| JPS60104393A (en) * | 1983-11-11 | 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 |
| JPS60104392A (en) * | 1983-11-10 | 1985-06-08 | Konishiroku Photo Ind Co Ltd | Thermal transfer recording medium |
| JPS60172587A (en) * | 1984-02-17 | 1985-09-06 | Victor Co Of Japan Ltd | Thermal transfer recording ink sheet |
| JPS60174694A (en) * | 1984-02-20 | 1985-09-07 | Toray Ind Inc | Thermal transfer material |
| 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 |
-
1986
- 1986-04-18 JP JP61088181A patent/JPS62244691A/en active Granted
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57160691A (en) * | 1981-03-31 | 1982-10-04 | Fujitsu Ltd | Ink composition for heat transfer recording and heat transfer recording ink sheet employing said composition |
| JPS58138684A (en) * | 1982-02-13 | 1983-08-17 | Fuji Kagakushi Kogyo Co Ltd | Recording medium for color heat transfer |
| 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 |
| JPS60104393A (en) * | 1983-11-11 | 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 |
| JPS60172587A (en) * | 1984-02-17 | 1985-09-06 | Victor Co Of Japan Ltd | Thermal transfer recording ink sheet |
| JPS60174694A (en) * | 1984-02-20 | 1985-09-07 | Toray Ind Inc | Thermal transfer material |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62244691A (en) | 1987-10-26 |
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