WO2022065320A1 - 感熱転写記録シート - Google Patents
感熱転写記録シート Download PDFInfo
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- WO2022065320A1 WO2022065320A1 PCT/JP2021/034648 JP2021034648W WO2022065320A1 WO 2022065320 A1 WO2022065320 A1 WO 2022065320A1 JP 2021034648 W JP2021034648 W JP 2021034648W WO 2022065320 A1 WO2022065320 A1 WO 2022065320A1
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- Prior art keywords
- group
- carbon atoms
- general formula
- alkyl group
- compound represented
- Prior art date
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- 238000012546 transfer Methods 0.000 title claims abstract description 123
- 150000001875 compounds Chemical class 0.000 claims abstract description 247
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 215
- 239000000975 dye Substances 0.000 claims abstract description 202
- 239000000463 material Substances 0.000 claims abstract description 41
- AJDUTMFFZHIJEM-UHFFFAOYSA-N n-(9,10-dioxoanthracen-1-yl)-4-[4-[[4-[4-[(9,10-dioxoanthracen-1-yl)carbamoyl]phenyl]phenyl]diazenyl]phenyl]benzamide Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC(=O)C(C=C1)=CC=C1C(C=C1)=CC=C1N=NC(C=C1)=CC=C1C(C=C1)=CC=C1C(=O)NC1=CC=CC2=C1C(=O)C1=CC=CC=C1C2=O AJDUTMFFZHIJEM-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000001043 yellow dye Substances 0.000 claims abstract description 41
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 34
- 125000004432 carbon atom Chemical group C* 0.000 claims description 328
- 125000003118 aryl group Chemical group 0.000 claims description 64
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 59
- 125000005843 halogen group Chemical group 0.000 claims description 48
- 125000003277 amino group Chemical group 0.000 claims description 45
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 42
- 125000003545 alkoxy group Chemical group 0.000 claims description 33
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 29
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 23
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 15
- 125000004104 aryloxy group Chemical group 0.000 claims description 13
- 125000003342 alkenyl group Chemical group 0.000 claims description 11
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 9
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 7
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 5
- 125000006570 (C5-C6) heteroaryl group Chemical group 0.000 claims description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004040 coloring Methods 0.000 abstract description 5
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 description 222
- 125000001931 aliphatic group Chemical group 0.000 description 207
- -1 silver halide Chemical class 0.000 description 172
- 239000010410 layer Substances 0.000 description 132
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- 229910052731 fluorine Inorganic materials 0.000 description 38
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- 239000011241 protective layer Substances 0.000 description 23
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 21
- 239000002585 base Substances 0.000 description 21
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 description 21
- 238000012360 testing method Methods 0.000 description 21
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 20
- 229920002554 vinyl polymer Polymers 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 19
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- 239000011230 binding agent Substances 0.000 description 16
- 239000003086 colorant Substances 0.000 description 16
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- 125000006598 aminocarbonylamino group Chemical group 0.000 description 10
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 10
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 10
- 125000004391 aryl sulfonyl group Chemical group 0.000 description 10
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 10
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- 239000013065 commercial product Substances 0.000 description 9
- 125000000623 heterocyclic group Chemical group 0.000 description 9
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- 230000000052 comparative effect Effects 0.000 description 8
- 238000006482 condensation reaction Methods 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 8
- 125000001624 naphthyl group Chemical group 0.000 description 8
- 125000005702 oxyalkylene group Chemical group 0.000 description 8
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- 125000005162 aryl oxy carbonyl amino group Chemical group 0.000 description 7
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 6
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 5
- 150000001241 acetals Chemical class 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
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- 239000001913 cellulose Substances 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 5
- 238000006297 dehydration reaction Methods 0.000 description 5
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 150000002513 isocyanates Chemical class 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 5
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- 239000004645 polyester resin Substances 0.000 description 5
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 125000003282 alkyl amino group Chemical group 0.000 description 4
- 125000004448 alkyl carbonyl group Chemical group 0.000 description 4
- 125000004414 alkyl thio group Chemical group 0.000 description 4
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 4
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 4
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- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 150000003014 phosphoric acid esters Chemical class 0.000 description 4
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- VHKVCNJAMDBNQL-UHFFFAOYSA-N 3H-dithiazol-4-yl(1,2-thiazol-3-yl)diazene Chemical compound S1N=C(C=C1)N=NC=1NSSC=1 VHKVCNJAMDBNQL-UHFFFAOYSA-N 0.000 description 3
- SALQMMXSINGXMI-UHFFFAOYSA-N 4-nitrosoaniline Chemical class NC1=CC=C(N=O)C=C1 SALQMMXSINGXMI-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
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- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 3
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- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 3
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- 125000003944 tolyl group Chemical group 0.000 description 3
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- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 2
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
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- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical group C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- CTAPFRYPJLPFDF-UHFFFAOYSA-N isoxazole Chemical group C=1C=NOC=1 CTAPFRYPJLPFDF-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- KXGCNMMJRFDFNR-WDRJZQOASA-N linaclotide Chemical compound C([C@H](NC(=O)[C@@H]1CSSC[C@H]2C(=O)N[C@H]3CSSC[C@H](N)C(=O)N[C@H](C(N[C@@H](CCC(O)=O)C(=O)N[C@@H](CC=4C=CC(O)=CC=4)C(=O)N2)=O)CSSC[C@H](NC(=O)[C@H](C)NC(=O)[C@@H]2CCCN2C(=O)[C@H](CC(N)=O)NC3=O)C(=O)N[C@H](C(NCC(=O)N1)=O)[C@H](O)C)C(O)=O)C1=CC=C(O)C=C1 KXGCNMMJRFDFNR-WDRJZQOASA-N 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000006626 methoxycarbonylamino group Chemical group 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000006216 methylsulfinyl group Chemical group [H]C([H])([H])S(*)=O 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification 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
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000006608 n-octyloxy group Chemical group 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 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
- FMJSMJQBSVNSBF-UHFFFAOYSA-N octocrylene Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC(CC)CCCC)C1=CC=CC=C1 FMJSMJQBSVNSBF-UHFFFAOYSA-N 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
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- 235000010987 pectin Nutrition 0.000 description 1
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- 125000005007 perfluorooctyl group Chemical group FC(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
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- 229920006287 phenoxy resin Polymers 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical group C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
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- 125000001844 prenyl group Chemical group [H]C([*])([H])C([H])=C(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 125000002294 quinazolinyl group Chemical group N1=C(N=CC2=CC=CC=C12)* 0.000 description 1
- IZMJMCDDWKSTTK-UHFFFAOYSA-N quinoline yellow Chemical compound C1=CC=CC2=NC(C3C(C4=CC=CC=C4C3=O)=O)=CC=C21 IZMJMCDDWKSTTK-UHFFFAOYSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
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- 159000000000 sodium salts Chemical class 0.000 description 1
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- 239000008117 stearic acid Substances 0.000 description 1
- 125000003696 stearoyl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229920005792 styrene-acrylic resin Polymers 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000006296 sulfonyl amino group Chemical group [H]N(*)S(*)(=O)=O 0.000 description 1
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- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000001016 thiazine dye Substances 0.000 description 1
- 239000001017 thiazole dye Substances 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- GLQWRXYOTXRDNH-UHFFFAOYSA-N thiophen-2-amine Chemical class NC1=CC=CS1 GLQWRXYOTXRDNH-UHFFFAOYSA-N 0.000 description 1
- RYYWUUFWQRZTIU-UHFFFAOYSA-K thiophosphate Chemical compound [O-]P([O-])([O-])=S RYYWUUFWQRZTIU-UHFFFAOYSA-K 0.000 description 1
- 239000001003 triarylmethane dye Substances 0.000 description 1
- 150000003852 triazoles Chemical group 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
- 239000001018 xanthene dye Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
- B41M5/39—Dyes containing one or more carbon-to-nitrogen double bonds, e.g. azomethine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/382—Contact thermal transfer or sublimation processes
- B41M5/385—Contact thermal transfer or sublimation processes characterised by the transferable dyes or pigments
- B41M5/388—Azo dyes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
- B41M5/42—Intermediate, backcoat, or covering layers
Definitions
- the present invention relates to a thermal transfer recording sheet.
- the sublimation type transfer recording method is attracting attention as a process capable of producing a color hard copy that is closest to the image quality of a silver halide photograph.
- it has the advantages of being dry, being able to visualize images directly from digital data, and being easy to duplicate.
- a thermal transfer recording sheet (hereinafter, also simply referred to as an ink sheet) and a thermal transfer image receiving sheet (hereinafter, also simply referred to as an image receiving sheet) containing a dye (hereinafter, also referred to as a dye) are used.
- a thermal transfer recording sheet (hereinafter, also simply referred to as an ink sheet) and a thermal transfer image receiving sheet (hereinafter, also simply referred to as an image receiving sheet) containing a dye (hereinafter, also referred to as a dye)
- a thermal transfer recording sheet (hereinafter, also simply referred to as an image receiving sheet) containing a dye)
- a dye hereinafter, also referred to as a dye
- Patent Document 1 proposes a thermal transfer recording sheet using an isothiazolylazothiazole dye.
- Patent Document 2 proposes a thermal transfer recording sheet having a magenta dye layer containing an isothiazolylazothiazole dye and a yellow dye layer containing an allylidenepyrazolone dye. According to this thermal transfer recording sheet, it is described that the reproducibility of skin color can be improved.
- a method of expressing black by the sublimation type thermal transfer recording method there are a method of expressing only with a black dye, a method of expressing with process black formed by sequentially transferring three colors of cyan dye, yellow dye, and magenta dye, and the like.
- printing by the above method has come to be used not only for photo printing but also for identification cards (ID cards) such as employee ID cards and student ID cards.
- ID cards identification cards
- the quality (especially the color) of black used for the printed part of the character information and the barcode is very important. Therefore, black is printed using only the black dye, or is printed as a separate process by the heat melting method transfer method.
- a process black formed by sequentially transferring three colors of cyan dye, yellow dye, and magenta dye can express high-quality black sufficient for the above-mentioned application.
- a print color scheme for example, character information printing with a black background color
- the color stands out due to the visual effect of the darkness of the black background (high density of black) (tightening effect of other colors), so that the quality of black continues to be required.
- Patent Document 1 describes a thermal transfer recording sheet containing an isothiazolylazothiazole dye, but does not specifically disclose a combination with a dye having another hue.
- the thermal transfer recording sheet described in Patent Document 2 has room for improvement in terms of the tightening effect of other colors due to the formed process black.
- An object of the present invention is to provide a thermal transfer recording sheet capable of forming a process black having a high concentration, excellent color, and excellent tightening effect of other colors.
- a thermal transfer recording sheet having a base material and a color material layer on the base material.
- the coloring material layer has a yellow dye layer containing a yellow dye, a magenta dye layer containing a magenta dye, and a cyan dye layer containing a cyan dye.
- the magenta dye contains a compound represented by the following general formula (1).
- the yellow dye contains at least one of the compounds represented by any of the following general formulas (2) to (7).
- the cyan dye contains at least one of the compounds represented by any of the following general formulas (8) to (12).
- R 11 represents a phenyl group or an unsubstituted alkyl group having 1 to 4 carbon atoms.
- R 12 represents a phenyl group or an unsubstituted alkyl group having 1 to 4 carbon atoms.
- R 13 and R 14 represent an alkyl group having 1 to 8 carbon atoms.
- R 21 and R 22 represent an alkyl group having 1 to 18 carbon atoms.
- R 23 represents a hydrogen atom or a methyl group.
- R 24 represents a hydrogen atom or an alkyl group.
- R 21 and R 24 may be coupled to each other to form a ring.
- X 31 represents a hydrogen atom or a bromine atom.
- R 31 represents a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms.
- R 32 and R 33 represent an alkyl group having 1 to 6 carbon atoms.
- X 41 represents a hydrogen atom or a chlorine atom.
- R 41 represents an unsubstituted alkoxy group having 1 to 4 carbon atoms or an amino group having 0 to 4 carbon atoms.
- R 42 and R 43 represent an alkyl group having 1 to 4 carbon atoms.
- R 51 represents a hydrogen atom, a halogen atom, or an alkoxycarbonyl group having 2 to 10 carbon atoms.
- R 52 represents an alkyl group having 1 to 6 carbon atoms.
- R 61 and R 62 represent an alkyl group having 1 to 4 carbon atoms.
- R 71 represents an alkoxy group having 1 to 4 carbon atoms or an amino group having 0 to 4 carbon atoms.
- R 72 , R 73 and R 74 represent an alkyl group having 1 to 4 carbon atoms.
- X 81 represents a hydrogen atom or a chlorine atom.
- R 81 and R 82 represent an unsubstituted alkyl group having 1 to 6 carbon atoms.
- R 83 represents a hydrogen atom, an unsubstituted alkyl group having 1 to 4 carbon atoms, or an unsubstituted alkoxy group having 1 to 4 carbon atoms.
- R 84 represents a methyl group or an ethyl group.
- R 85 represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a 5- or 6-membered heteroaryl group.
- R 91 represents an alkyl group having 1 to 4 carbon atoms.
- R 92 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
- R 93 and R 94 represent an alkyl group having 1 to 6 carbon atoms.
- R 101 and R 102 represent an alkyl group having 1 to 8 carbon atoms.
- R 103 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
- R 111 and R 112 represent an alkyl group having 1 to 4 carbon atoms.
- R 113 represents an alkyl group having 1 to 4 carbon atoms.
- R 121 and R 122 represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
- the yellow dye is a compound represented by the general formula (4) and at least one of the compounds represented by any of the general formulas (2), (3), (5), (6) and (7).
- the thermal transfer recording sheet described in one.
- [7] The thermal transfer recording sheet according to any one of [1] to [4], wherein the yellow dye contains a compound represented by the general formula (3) and a compound represented by the general formula (2).
- the thermal transfer recording sheet according to any one.
- R 131 represents a halogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
- R 141 and R 142 represent an aryl group having 6 to 10 carbon atoms.
- R 151 represents an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 1 to 6 carbon atoms.
- R 152 represents an alkyl group having 1 to 4 carbon atoms.
- R 153 and R 154 represent an alkyl group having 1 to 6 carbon atoms.
- R161 represents an alkyl group having 1 to 4 carbon atoms.
- R 162 and R 163 represent an alkyl group having 1 to 10 carbon atoms.
- R 171 represents an alkyl group having 1 to 6 carbon atoms.
- R172 represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.
- R173 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- R 174 and R 175 represent an alkyl group having 1 to 4 carbon atoms.
- R181 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.
- R182 represents an alkyl group having 1 to 12 carbon atoms.
- R183 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- R184 and R185 represent an alkyl group having 1 to 12 carbon atoms.
- R 191 and R 192 represent an alkyl group having 1 to 6 carbon atoms.
- R193 represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.
- R194 represents an alkyl group or an amino group having 0 to 12 carbon atoms.
- R 201 represents an alkoxy group having 1 to 4 carbon atoms or an amino group having 0 to 6 carbon atoms.
- R 202 and R 203 represent an alkyl group having 1 to 4 carbon atoms.
- the heat-sensitive transfer recording sheet of the present invention it is possible to form a process black having a high concentration, excellent color, and excellent tightening effect of other colors.
- the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
- the indication of a compound is used to mean that the compound itself, its salt, and its ion are included.
- it is meant to include a derivative whose structure is partially changed, such as by introducing a substituent, within the range of exhibiting a desired effect.
- the substituent when the substituent has a dissociative hydrogen atom (a group in which a hydrogen atom is dissociated by the action of a base), the substituent includes a form of an ion or a salt.
- substituents, linking groups, etc. for which substitution or non-substitution is not specified in the present specification mean that the group may have an appropriate substituent. Therefore, even if it is simply described as "-group” (for example, “alkyl group”) in the present specification, this "-group” (for example, “alkyl group”) does not have a substituent.
- substituents include the substituent T described later.
- a substituent selected from the substituent T described later is preferably applied.
- the respective substituents or the like may be the same or different from each other. It means good. Further, even if it is not particularly specified, it means that when a plurality of substituents or the like are adjacent to each other, they may be linked to each other or condensed to form a ring.
- the term alkyl group means a linear, branched or cyclic alkyl group.
- the alkyl group in the group containing the alkyl group (alkoxy group, alkoxycarbonyl group, etc.).
- this carbon number means the carbon number of the entire group unless otherwise specified in the present invention or the present specification. That is, when this group is in the form of further having a substituent, it means the total number of carbon atoms including this substituent.
- the amino group having 0 carbon atoms represents a general unsubstituted amino group ( NH2 group).
- the number of carbon atoms of the amino group is 1 or more, the number of carbon atoms means the number of carbon atoms of the entire amino group including the substituent.
- the exemplary compound (7-1) described later has an amino group (dimethylamino group) having 2 carbon atoms as R71 in the general formula (7).
- the heat-sensitive transfer recording sheet of the present invention is a heat-sensitive transfer recording sheet having a base material and a color material layer on the base material, and the color material layer is a yellow dye layer containing a yellow dye and a magenta containing a magenta dye. It has a dye layer and a cyan dye layer containing a cyan dye.
- the heat-sensitive transfer recording sheet of the present invention has a coloring material layer on a substrate, and the coloring material layer has a yellow dye layer, a magenta dye layer, and a cyan dye layer.
- the thermal transfer recording sheet of the present invention may have a black dye layer in addition to these dye layers. It is preferable that these dye layers are sequentially coated on the same substrate in a surface-sequential manner. As an example, the case where the dye layers of each hue of yellow, magenta, and cyan are sequentially painted in the long axis direction of the same base material corresponding to the area of the recording surface of the thermal transfer image receiving sheet is given. Can be done.
- the base material may be made long, and each of the above dye layers may be repeatedly applied in a surface-sequential manner.
- each of the above dye layers may be repeatedly applied in a surface-sequential manner.
- either or both of the dye layer having a black hue and the transferable protective layer are applied separately.
- By coating the images one by one in this manner it is possible to form an image by transferring the dye and further to laminate a protective layer on the image with one thermal transfer recording sheet.
- the present invention is not limited to the method of providing the dye layer as described above.
- thermo transfer ink layer die layer
- thermal melt transfer ink layer a sublimation type thermal transfer ink layer
- thermal melt transfer ink layer a thermal melt transfer ink layer
- changes such as providing a dye layer with a hue other than yellow, magenta, cyan and black.
- the form may be long or may be a single-leaf thermal transfer sheet.
- the dye layer of each color may have a single layer structure or a multi-layer structure, and in the case of the multi-layer structure, the composition of each layer constituting the dye layer may be the same or different.
- the dye layer contains a dye.
- the dye layer usually contains a binder in addition to the dye. Further, if necessary, waxes, silicone resins, fluorine-containing organic compounds and the like can be contained.
- Each dye (dye) is preferably contained in the dye layer in an amount of 10 to 90% by mass, more preferably 20 to 80% by mass.
- the dye layer is applied by a general method such as a roll coat, a bar coat, a gravure coat, and a gravure reverse coat.
- the coating amount of the dye layer is preferably 0.1 to 2.0 g / m 2 (solid content equivalent, hereinafter the coating amount in the present invention is a numerical value in terms of solid content unless otherwise specified), and more preferably. Is 0.2 to 1.2 g / m 2 .
- the film thickness of the dye layer is preferably 0.1 to 2.0 ⁇ m, more preferably 0.2 to 1.2 ⁇ m.
- the magenta dye contains a compound represented by the following general formula (1)
- the yellow dye contains at least one of the compounds represented by any of the following general formulas (2) to (7)
- the cyan dye contains.
- the magenta dye may be in an embodiment containing at least one of the compounds represented by the general formulas (13) to (20) in addition to the compound represented by the general formula (1).
- the compound represented by the following general formula may have any isomer structure as long as at least one of its isomer structures (for example, tautomer structure) applies to this general formula.
- the compounds represented by the general formulas (1) to (20) used in the present invention will be described in more detail.
- R 11 represents a phenyl group or an unsubstituted alkyl group having 1 to 4 carbon atoms.
- the phenyl group that can be taken as R 11 may have a substituent.
- the substituent in R 11 include a substituent selected from the substituent T described later, which includes a halogen atom, an aliphatic group, an unsaturated aliphatic group, an aryl group, an aliphatic oxy group, an acyloxy group and an aliphatic oxy.
- R 11 is preferably a methyl group, an ethyl group, a propyl group, or an unsubstituted phenyl group, more preferably a methyl group, an ethyl group, or an unsubstituted phenyl group, and most preferably a methyl group or an unsubstituted phenyl group.
- R 12 represents a phenyl group or an unsubstituted alkyl group having 1 to 4 carbon atoms. The phenyl group that can be taken as R 12 may have a substituent.
- Examples of the substituent in R 12 include a substituent selected from the substituent T described later, which includes a halogen atom, an aliphatic group, an unsaturated aliphatic group, an aryl group, an aliphatic oxy group, an acyloxy group and an aliphatic oxy.
- R 12 is preferably a methyl group, an ethyl group, a propyl group, a butyl group, or an unsubstituted phenyl group, and more preferably a t-butyl group or an unsubstituted phenyl group.
- R 13 and R 14 represent an alkyl group having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms which can be taken as R 13 and R 14 may have a substituent.
- Examples of the substituent in R 13 and R 14 include a substituent selected from the substituent T described later, and a hydroxyl group, a halogen atom, an unsaturated aliphatic group, an aryl group, an aliphatic oxy group and an acyloxy group (more preferably).
- R 13 and R 14 are preferably an alkyl group having 2 to 6 carbon atoms, preferably an unsubstituted alkyl group having 2 to 4 carbon atoms, and 2 carbon atoms having a hydroxyl group, an alkylcarbonyloxy group, or an alkylcarbonyl group as a substituent.
- Alkyl groups of ⁇ 4 are more preferred.
- R 21 and R 22 represent an alkyl group having 1 to 18 carbon atoms.
- the number of carbon atoms of the alkyl group having 1 to 18 carbon atoms that can be taken as R 21 and R 22 is preferably 1 to 16, and more preferably 1 to 14.
- the alkyl group having 1 to 18 carbon atoms which can be taken as R 21 and R 22 may have a substituent.
- the substituent in R 21 and R 22 include a group selected from the substituent T described later, and an aryloxy group (preferably a phenoxy group, more preferably a 4-cyclohexylphenoxy group) and an aryl group (phenyl group are preferable).
- carbamoyloxy group preferably phenylaminocarbonyloxy group
- halogen atom unsaturated aliphatic group
- acyloxy group preferably phenylaminocarbonyloxy group
- aliphatic oxycarbonyloxy amino group
- acylamino group aliphatic oxycarbonylamino group
- sulfamoyl preferably phenylaminocarbonyloxy group
- R 21 and R 22 may be the same or different, but R 21 and R 22 are preferably different.
- R 21 and R 22 are an unsubstituted alkyl group having 1 to 6 carbon atoms, a phenyl group, a phenoxy group (preferably a phenoxy group further having a substituent selected from the substituent T, and a cyclohexylphenoxy group), or It is preferably an alkyl group having 7 to 14 carbon atoms and having a phenylaminocarbonyloxy group as a substituent.
- R 23 represents a hydrogen atom or a methyl group.
- R 23 is preferably a methyl group.
- R 24 represents a hydrogen atom or an alkyl group.
- the number of carbon atoms of the alkyl group that can be taken as R 24 is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 5.
- the alkyl group that can be taken as R 24 may have a substituent.
- R 21 and R 24 may be coupled to each other to form a ring.
- R 24 is preferably a hydrogen atom or bonded to R 21 to form a ring, and is preferably a hydrogen atom or bonded to R 21 to form a piperidine ring (which may have a substituent). ) Is more preferable.
- X 31 represents a hydrogen atom or a bromine atom.
- R 31 represents a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms.
- R 31 is preferably a hydrogen atom, a methyl group, an ethyl group, or a propyl group, and more preferably a hydrogen atom or an isopropyl group.
- R 32 and R 33 represent an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms which can be taken as R 32 and R 33 may have a substituent.
- Examples of the substituent in R 32 and R 33 include a substituent selected from the substituent T described later, which includes a halogen atom, an unsaturated aliphatic group, an aryl group, an aliphatic oxy group, an acyloxy group, and an aliphatic oxycarbonyl.
- R 32 and R 33 an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable, and an n-propyl group and an n-butyl group are more preferable.
- X 41 represents a hydrogen atom or a chlorine atom.
- R 41 represents an unsubstituted alkoxy group having 1 to 4 carbon atoms or an amino group having 0 to 4 carbon atoms.
- the amino group having 0 to 4 carbon atoms which can be taken as R 41 may have a substituent.
- the substituent in R 41 include a substituent selected from the substituent T described later, such as a halogen atom, an aliphatic group, an unsaturated aliphatic group, an aryl group, an aliphatic oxy group, an acyloxy group hydroxyl group, and a cyano group. Etc. are preferable.
- R 41 is preferably an unsubstituted alkoxy group or an alkylamino group having 1 to 4 carbon atoms, and more preferably an ethoxy group or a dimethylamino group.
- R 42 and R 43 represent an alkyl group having 1 to 4 carbon atoms.
- the alkyl group having 1 to 4 carbon atoms which can be taken as R 42 and R 43 may have a substituent.
- Examples of the substituent in R 42 and R 43 include a substituent selected from the substituent T described later, which includes a halogen atom, an unsaturated aliphatic group, an aliphatic oxy group, an acyloxy group, an aliphatic oxycarbonyloxy, and a fat.
- Group thio groups aliphatic oxycarbonyl groups, hydroxyl groups, cyano groups and the like are preferable.
- R 43 and R 43 an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable, and an ethyl group is more preferable.
- R 51 represents a hydrogen atom, a halogen atom, or an alkoxycarbonyl group having 2 to 10 carbon atoms.
- the halogen atom that can be taken as R 51 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
- the alkoxycarbonyl group having 2 to 10 carbon atoms which can be taken as R 51 may have a substituent.
- R 51 examples include a substituent selected from the substituent T described later, such as a halogen atom, an unsaturated aliphatic group, an aryl group, an aliphatic oxy group, an acyloxy group, an aliphatic thio group, and a hydroxyl group. Is preferable.
- R 51 is preferably an alkoxycarbonyl group having 7 to 10 carbon atoms having a chlorine atom or a phenyl group as a substituent, and more preferably a chlorine atom or a benzyloxycarbonyl group.
- R 52 represents an alkyl group having 1 to 6 carbon atoms.
- the alkyl group having 1 to 6 carbon atoms which can be taken as R 52 may have a substituent.
- substituents in R 52 include a substituent selected from the substituent T described later, such as a halogen atom, an unsaturated aliphatic group, an aryl group, an aliphatic oxy group, an acyloxy group, an aliphatic thio group, and a hydroxyl group. Is preferable.
- R 52 is preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, and more preferably an n-butyl group.
- R 61 and R 62 represent an alkyl group having 1 to 4 carbon atoms.
- the alkyl group having 1 to 4 carbon atoms which can be taken as R 61 and R 62 may have a substituent.
- the substituent in R 61 and R 62 include a substituent selected from the substituent T described later, which includes a halogen atom, an unsaturated aliphatic group, an aryl group, an aliphatic oxy group, an acyloxy group, an acyl group, and a hydroxyl group. Is preferable.
- R 61 and R 62 an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is more preferable.
- R 71 represents an alkoxy group having 1 to 4 carbon atoms or an amino group having 0 to 4 carbon atoms.
- the alkoxy group having 1 to 4 carbon atoms and the amino group having 0 to 4 carbon atoms which can be taken as R 71 may have a substituent.
- the substituent in R 71 include a substituent selected from the substituent T described later, such as a halogen atom, an aliphatic group, an unsaturated aliphatic group, an aryl group, an aliphatic oxy group, an acyloxy group, a hydroxyl group and a cyano. Groups and the like are preferred.
- R 71 is preferably an unsubstituted alkoxy group having 1 to 4 carbon atoms or an amino group having 1 to 4 carbon atoms having an alkyl group as a substituent, and more preferably an ethoxy group or a dimethylamino group.
- R 72 , R 73 and R 74 represent an alkyl group having 1 to 4 carbon atoms.
- the alkyl group having 1 to 4 carbon atoms which can be taken as R 72 , R 73 and R 74 may have a substituent.
- R 72 , R 73 and R 74 examples include a substituent selected from the substituent T described later, and a halogen atom, an unsaturated aliphatic group, an aryl group, an aliphatic oxy group, an acyloxy group and a hydroxyl group. Etc. are preferable.
- R 72 , R 73 and R 74 are preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group or an ethyl group.
- X 81 represents a hydrogen atom or a chlorine atom. Chlorine atom is preferable for X 81 .
- R 81 and R 82 represent an unsubstituted alkyl group having 1 to 6 carbon atoms. As R 81 and R 82 , an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group, an ethyl group, or a propyl group is more preferable.
- R 83 represents a hydrogen atom, an unsubstituted alkyl group having 1 to 4 carbon atoms, or an unsubstituted alkoxy group having 1 to 4 carbon atoms.
- R 83 is preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and more preferably a hydrogen atom, a methyl group, or an ethoxy group.
- R 84 represents a methyl group or an ethyl group.
- R 85 represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a 5- or 6-membered heteroaryl group.
- the aryl group that can be taken as R85 is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.
- the 5- or 6-membered heteroaryl group that can be taken as R85 may have any of an oxygen atom, a nitrogen atom, and a sulfur atom as the heteroatom, and examples thereof include a frill group, a pyridyl group, and a thienyl group.
- the alkyl group having 1 to 4 carbon atoms, the aryl group, and the 5- or 6-membered heteroaryl group which can be taken as R85 may have a substituent.
- Examples of the substituent in R85 include a substituent selected from the substituent T described later, which includes a halogen atom, an aliphatic group, an unsaturated aliphatic group, an aryl group, an aliphatic oxy group, an acyloxy group and an aliphatic oxy.
- a carbonyl group, an aliphatic oxycarbonyl group, a hydroxyl group, a cyano group, a nitro group and the like are preferable.
- R 85 is preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, a phenyl group, a frill group or a pyridyl group, and more preferably a methyl group, an ethyl group, a frill group or a pyridyl group.
- R 91 represents an alkyl group having 1 to 4 carbon atoms.
- the alkyl group having 1 to 4 carbon atoms which can be taken as R 91 may have a substituent.
- the substituent in R 91 include a halogen atom, an unsaturated aliphatic group, an aryl group, an aliphatic oxy group, an acyloxy group, an aliphatic oxycarbonyloxy, an aliphatic oxycarbonyl group, and a hydroxyl group.
- R 91 is preferably an unsubstituted alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group, an ethyl group, or a propyl group.
- R 92 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
- the alkyl group having 1 to 4 carbon atoms and the alkoxy group having 1 to 4 carbon atoms which can be taken as R 92 may have a substituent.
- the substituent in R 92 include a halogen atom, an unsaturated aliphatic group, an aliphatic oxy group, an acyloxy group, an aliphatic oxycarbonyloxy, an aliphatic thio group hydroxyl group and the like.
- R 92 is preferably a hydrogen atom, an unsubstituted alkyl group having 1 to 4 carbon atoms, or an unsubstituted alkoxy group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group, or a methoxy group.
- R 93 and R 94 represent an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms which can be taken as R 93 and R 94 may have a substituent.
- R 93 and R 94 examples include a substituent selected from the substituent T described later, such as a halogen atom, an unsaturated aliphatic group, an aliphatic oxy group, an acyloxy group, an aliphatic oxycarbonyloxy, and an acyl. Groups, aliphatic oxycarbonyl groups, hydroxyl groups, cyano groups and the like are preferred.
- R 93 and R 94 an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable, an ethyl group and an isopropyl group are more preferable, and an ethyl group is further preferable.
- R 101 and R 102 represent an alkyl group having 1 to 8 carbon atoms.
- the alkyl group having 1 to 8 carbon atoms which can be taken as R 101 and R 102 may have a substituent.
- the substituent in R 101 and R 102 include a substituent selected from the substituent T described later, such as a halogen atom, an unsaturated aliphatic group, an aryl group, an aliphatic oxy group, an acyloxy group, and an aliphatic oxycarbonyl.
- R 101 and R 102 an unsubstituted alkyl group having 1 to 6 carbon atoms is preferable, and an n-hexyl group is more preferable.
- R 103 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkyl group having 1 to 3 carbon atoms which can be taken as R 103 may have a substituent.
- R 103 examples include a substituent selected from the substituent T described later, and a halogen atom, an unsaturated aliphatic group, an aliphatic oxy group, an aliphatic thio group and the like are preferable.
- R 103 is preferably an unsubstituted alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group.
- R 111 and R 112 represent an alkyl group having 1 to 4 carbon atoms.
- the alkyl group having 1 to 4 carbon atoms which can be taken as R 111 and R 112 may have a substituent.
- the substituent in R 111 and R 112 include a substituent selected from the substituent T described later, which includes a halogen atom, an unsaturated aliphatic group, an aliphatic oxy group, an acyloxy group, an acylamino group, and an aliphatic thio group.
- Acrylic group, aliphatic oxycarbonyl group, hydroxyl group, cyano group and the like are preferable.
- R 111 and R 112 an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable, and an ethyl group is more preferable.
- R 113 represents an alkyl group having 1 to 4 carbon atoms.
- the alkyl group having 1 to 4 carbon atoms which can be taken as R 113 may have a substituent. Examples of the substituent in R 113 include a substituent selected from the substituent T described later, and a halogen atom, an unsaturated aliphatic group, an aliphatic oxy group, a hydroxyl group and the like are preferable.
- R 113 preferably has an unsubstituted alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.
- R 121 and R 122 represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
- Examples of the aryl group having 6 to 10 carbon atoms that can be taken as R 121 and R 122 include a phenyl group and a naphthyl group.
- the alkyl group having 1 to 6 carbon atoms and the aryl group having 6 to 10 carbon atoms which can be taken as R 121 and R 122 may have a substituent.
- R 121 and R 122 examples include a substituent selected from the substituent T described later, such as a halogen atom, an aliphatic group (preferably an alkyl group), an unsaturated aliphatic group, an aryl group and an aliphatic group.
- a substituent selected from the substituent T described later such as a halogen atom, an aliphatic group (preferably an alkyl group), an unsaturated aliphatic group, an aryl group and an aliphatic group.
- R 121 and R 122 an unsubstituted alkyl group having 1 to 6 carbon atoms and a phenyl group having an alkyl group as a substituent are preferable, and a methyl group, an ethyl group, an isopropyl group and a methylphenyl group are more preferable.
- R 131 represents a halogen atom, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms.
- the halogen atom that can be taken as R 131 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a bromine atom is preferable.
- the aryl group contained in the aryloxy group having 6 to 10 carbon atoms which can be taken as R 131 is preferably a phenyl group or a naphthyl group.
- the alkoxy group having 1 to 8 carbon atoms and the aryloxy group having 6 to 10 carbon atoms which can be taken as R 131 may have a substituent.
- the substituent in R 131 include a substituent selected from the substituent T described later, and a hydroxyl group, a halogen atom, an aliphatic group, an unsaturated aliphatic group, an aryl group, an aliphatic oxy group, an acyloxy group, and a fat.
- Group oxycarbonyloxy, aryloxycarbonyloxy group, aliphatic thio group, acyl group, aryloxycarbonyl group, aliphatic oxycarbonyl group, cyano group and the like are preferable.
- R 131 is preferably an alkoxy group having a hydroxyl group as a substituent, a halogen atom, or an unsubstituted aryloxy group having 6 to 10 carbon atoms, and preferably an ethoxy group, a phenoxy group, or a bromine atom having a hydroxyl group as a substituent.
- R 141 and R 142 represent an aryl group having 6 to 10 carbon atoms.
- the aryl group having 6 to 10 carbon atoms which can be taken as R 141 and R 142 is preferably a phenyl group or a naphthyl group.
- the aryl group having 6 to 10 carbon atoms which can be taken as R 141 and R 142 may have a substituent.
- Examples of the substituent in R 141 and R 142 include a substituent selected from the substituent T described later, which includes a halogen atom, an aliphatic group, an unsaturated aliphatic group, an aliphatic oxy group, an acyloxy group, and an aliphatic oxy.
- R 141 and R 142 are preferably phenyl groups.
- R 151 represents an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 1 to 6 carbon atoms.
- the alkyl group having 1 to 6 carbon atoms and the alkenyl group having 1 to 6 carbon atoms which can be taken as R 151 may have a substituent.
- the substituent in R 151 include a substituent selected from the substituent T described later, which includes an unsaturated aliphatic group, an aliphatic oxy group, an acyloxy group, an aliphatic oxycarbonyloxy, an aliphatic oxycarbonyl group, and a hydroxyl group. Etc. are preferable.
- R 151 an unsubstituted alkyl group having 2 to 6 carbon atoms or an unsubstituted alkenyl group having 2 to 6 carbon atoms is preferable, and an ethyl group, an n-propyl group, an n-butyl group and an allyl group are more preferable.
- R 152 represents an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms which can be taken as R 152 may have a substituent.
- R 152 examples include a substituent selected from the substituent T described later, and a halogen atom, an aliphatic group, an unsaturated aliphatic group, an aliphatic oxy group, a hydroxyl group and the like are preferable.
- R 152 an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is more preferable.
- R 153 and R 154 represent an alkyl group having 1 to 6 carbon atoms. The alkyl group having 1 to 6 carbon atoms which can be taken as R 153 and R 154 may have a substituent.
- R 153 and R 154 examples include a substituent selected from the substituent T described later, which includes a halogen atom, an unsaturated aliphatic group, an aliphatic oxy group, an acyloxy group, an acylamino group, a hydroxyl group, and a cyano group. Etc. are preferable.
- R 153 and R 154 an unsubstituted alkyl group having 2 to 6 carbon atoms is preferable, and an n-propyl group and an n-butyl group are preferable.
- R161 represents an alkyl group having 1 to 4 carbon atoms.
- the alkyl group having 1 to 4 carbon atoms which can be taken as R161 may have a substituent.
- the substituent in R161 include a substituent selected from the substituent T described later, and a halogen atom, an unsaturated aliphatic group, an aliphatic oxy group, a hydroxyl group and the like are preferable.
- R161 an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group, an ethyl group and an isopropyl group are particularly preferable.
- R 162 and R 163 represent an alkyl group having 1 to 10 carbon atoms.
- the alkyl group having 1 to 10 carbon atoms which can be taken as R 162 and R 163 may have a substituent.
- the substituent in R 162 and R 163 include a substituent selected from the substituent T described later, such as a halogen atom, an unsaturated aliphatic group, an aryl group (preferably a phenyl group), an aliphatic oxy group, and an acyloxy group.
- alkylcarbonyloxy group acylamino group, aliphatic oxycarbonylamino group, aliphatic or arylsulfonylamino group, aliphatic thio group, aliphatic or arylsulfonyl group, acyl group, aryloxycarbonyl group, aliphatic oxy
- a carbonyl group, a hydroxyl group, a cyano group and the like are preferable.
- an unsubstituted alkyl group having 1 to 4 carbon atoms (more preferably a methyl group or an ethyl group), a methylcarbonyloxyethyl group, a benzyl group or the like is preferable.
- R 171 represents an alkyl group having 1 to 6 carbon atoms.
- the alkyl group having 1 to 6 carbon atoms which can be taken as R 171 may have a substituent.
- the substituent in R 171 include a substituent selected from the substituent T described later, which includes a halogen atom, an unsaturated aliphatic group, an aliphatic oxy group, an acyloxy group, an acyl group, an aryloxycarbonyl group and an aliphatic group. Oxycarbonyl groups and the like are preferred.
- R 171 an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable, and a t-butyl group is more preferable.
- R172 represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms.
- Examples of the aryl group having 6 to 10 carbon atoms that can be taken as R172 include a phenyl group and a naphthyl group.
- the alkyl group having 1 to 6 carbon atoms and the aryl group having 6 to 10 carbon atoms which can be taken as R172 may have a substituent.
- the substituent in R 172 include a substituent selected from the substituent T described later, such as a halogen atom, an aliphatic group (preferably an alkyl group), an aliphatic oxy group, an acyloxy group, an acylamino group and an aliphatic thio.
- R172 a phenyl group having a substituent (preferably an alkyl group) is preferable, and a methylphenyl group is more preferable.
- R173 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms which can be taken as R173 may have a substituent. Examples of the substituent in R 173 include a substituent selected from the substituent T described later, and a halogen atom, an unsaturated aliphatic group, an aliphatic oxy group, an acyloxy group and the like are preferable.
- R173 a hydrogen atom or an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is more preferable.
- R 174 and R 175 represent an alkyl group having 1 to 4 carbon atoms.
- the alkyl group having 1 to 4 carbon atoms which can be taken as R 174 and R 175 may have a substituent.
- the substituent in R 174 and R 175 include a substituent selected from the substituent T described later, which includes a halogen atom, an unsaturated aliphatic group, an aliphatic oxy group, an acyloxy group, an acyl group, and an aliphatic oxycarbonyl.
- R 174 and R 175 an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable, and an ethyl group is more preferable.
- R181 represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms.
- Examples of the aryl group having 6 to 10 carbon atoms that can be taken as R181 include a phenyl group and a naphthyl group.
- the alkyl group having 1 to 4 carbon atoms and the aryl group having 6 to 10 carbon atoms which can be taken as R181 may have a substituent.
- the substituent in R181 include a substituent selected from the substituent T described later, and a halogen atom, an aliphatic group, an aliphatic oxy group, an acyloxy group, an acyl group and the like are preferable.
- R181 a phenyl group having a substituent is preferable, and a chlorophenyl group is more preferable.
- R182 represents an alkyl group having 1 to 12 carbon atoms.
- the number of carbon atoms of the alkyl group having 1 to 12 carbon atoms which can be taken as R182 is preferably 1 to 10, more preferably 2 to 10, and even more preferably 2 to 6.
- the alkyl group having 1 to 12 carbon atoms which can be taken as R182 may have a substituent.
- Examples of the substituent in R182 include a substituent selected from the substituent T described later, an aryl group, an aliphatic oxy group, an amino group, an acylamino group, an aminocarbonylamino group, an aliphatic oxycarbonylamino group and an aryl.
- Oxycarbonylamino group, aliphatic or arylsulfonylamino group, imide group (preferably N-phthalimide group) and the like are preferable.
- an alkyl group having 3 to 12 carbon atoms is preferable, an unsubstituted alkyl group having 3 to 12 carbon atoms, or an alkyl group having 10 to 12 carbon atoms having N-phthalimide as a substituent is preferable, and an isopropyl group, Alternatively, an isopropyl group having an N-phthalimide group as a substituent is more preferable.
- R183 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms which can be taken as R183 may have a substituent.
- R183 examples include a substituent selected from the substituent T described later, and a halogen atom, an unsaturated aliphatic group, an aliphatic oxy group, an acyloxy group and the like are preferable.
- R183 is preferably an unsubstituted alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and more preferably a hydrogen atom.
- R184 and R185 represent an alkyl group having 1 to 12 carbon atoms.
- the number of carbon atoms of the alkyl group having 1 to 12 carbon atoms which can be taken as R 184 and R 185 is preferably 1 to 10, more preferably 2 to 9, and even more preferably 2 to 6.
- the alkyl group having 1 to 12 carbon atoms which can be taken as R 184 and R 185 may have a substituent.
- substituents in R 184 and R 185 include a substituent selected from the substituent T described later, and an alkoxy group and an aryloxy group (further, an aliphatic oxy group is preferably substituted, for example, alkoxy. Phenoxy group), alkylcarbonyloxy group, cyano group and the like are preferable.
- R 184 and R 185 include an unsubstituted alkyl group having 2 to 6 carbon atoms, or an alkyl group having 2 to 11 carbon atoms having an alkoxy group, an alkoxyphenoxy group, an alkylcarbonyloxy group, or a cyano group as a substituent. preferable.
- R 191 and R 192 represent an alkyl group having 1 to 6 carbon atoms.
- the alkyl group having 1 to 6 carbon atoms which can be taken as R 191 and R 192 may have a substituent.
- the substituent in R 191 and R 192 include a substituent selected from the substituent T described later, which includes a halogen atom, an unsaturated aliphatic group, an aliphatic oxy group, an acyloxy group, an acyl group, and an aliphatic oxycarbonyl. Groups, hydroxyl groups, cyano groups and the like are preferred.
- R 191 and R 192 an unsubstituted alkyl group having 3 to 6 carbon atoms is preferable, and an n-butyl group is more preferable.
- R193 represents an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. Examples of the aryl group having 6 to 10 carbon atoms that can be taken as R193 include a phenyl group and a naphthyl group.
- the alkyl group having 1 to 6 carbon atoms and the aryl group having 6 to 10 carbon atoms which can be taken as R 193 may have a substituent.
- Examples of the substituent in R 193 include a substituent selected from the substituent T described later, which include a halogen atom, an aliphatic group, an unsaturated aliphatic group, an aryl group, an aliphatic oxy group, an acyloxy group and an acylamino group.
- a substituent selected from the substituent T described later which include a halogen atom, an aliphatic group, an unsaturated aliphatic group, an aryl group, an aliphatic oxy group, an acyloxy group and an acylamino group.
- An aliphatic or arylsulfonylamino group, an aliphatic thio group, an acyl group, an aliphatic oxycarbonyl group and the like are preferable.
- R193 an unsubstituted alkyl group having 1 to 6 carbon atoms and an unsubstituted aryl group having 6 to 10 carbon atoms are preferable, and a phenyl group, an n-butyl group and a t-butyl group are more preferable.
- R194 represents an alkyl group or an amino group having 0 to 12 carbon atoms. The number of carbon atoms of the alkyl group that can be taken as R194 is preferably 1 to 12, more preferably 2 to 10, and even more preferably 3 to 8.
- the number of carbon atoms of the amino group having 0 to 12 carbon atoms which can be taken as R194 is preferably 1 to 12, more preferably 2 to 12, and even more preferably 2 to 10.
- the alkyl group which can be taken as R194 and the amino group having 0 to 12 carbon atoms may have a substituent.
- the substituent in R 194 include a substituent selected from the substituent T described later, and an alkyl group, an alkylcarbonyl group, an arylcarbonyl group and the like are preferable.
- R194 is preferably an unsubstituted alkyl group having 3 to 6 carbon atoms or an amino group having 2 to 12 carbon atoms having a substituent, preferably an n-butyl group, an isobutyl group, or an alkylcarbonyl group or an arylcarbonyl group. Amino groups having 4 to 12 carbon atoms are more preferable.
- R 201 represents an alkoxy group having 1 to 4 carbon atoms or an amino group having 0 to 6 carbon atoms.
- the alkoxy group having 1 to 4 carbon atoms and the amino group having 0 to 6 carbon atoms which can be taken as R201 may have a substituent.
- the substituent in R 201 include a substituent selected from the substituent T described later, a halogen atom, an aliphatic group (preferably an alkyl group), an unsaturated aliphatic group, an aliphatic oxy group, and an acyloxy group.
- An acyl group, an aliphatic oxycarbonyl group, a hydroxyl group, a cyano group and the like are preferable.
- R 201 is preferably an unsubstituted alkoxy group having 1 to 4 carbon atoms or a dialkylamino group having 2 to 6 carbon atoms, and more preferably a methoxy group, an ethoxy group or a dimethylamino group.
- R 202 and R 203 represent an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms which can be taken as R 202 and R 203 may have a substituent.
- R 202 and R 203 examples include a substituent selected from the substituent T described later, which includes a halogen atom, an unsaturated aliphatic group, an aliphatic oxy group, an acyloxy group, an acyl group, and an aliphatic oxycarbonyl. Groups, hydroxyl groups, cyano groups and the like are preferred.
- R 202 and R 203 an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
- substituent T examples include the following.
- the substituent possessed by the group is selected from the substituents T listed below so as to satisfy the total carbon number.
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable.
- the aliphatic group is a linear, branched or cyclic aliphatic group, and the saturated aliphatic group includes an alkyl group, a cycloalkyl group and a bicycloalkyl group, and may have a substituent. The number of these carbon atoms is preferably 1 to 30.
- Examples include methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group, benzyl group and 2-ethylhexyl group. Can be done.
- the cycloalkyl group is preferably a cycloalkyl group having 3 to 30 carbon atoms. Examples include a cyclohexyl group, a cyclopentyl group, and a 4-n-dodecylcyclohexyl group.
- bicycloalkyl group examples include a bicycloalkyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms.
- examples thereof include a bicyclo [1.2.2] heptane-2-yl group and a bicyclo [2.2.2] octane-3-yl group.
- it also includes a tricyclo structure having many ring structures.
- the unsaturated aliphatic group is a linear, branched or cyclic unsaturated aliphatic group, and includes an alkenyl group, a cycloalkenyl group, a bicycloalkenyl group, and an alkynyl group.
- alkenyl group examples include a linear, branched and cyclic alkenyl group.
- alkenyl group an alkenyl group having 2 to 30 carbon atoms is preferable. Examples thereof include a vinyl group, an allyl group, a prenyl group, a geranyl group, and an oleyl group.
- the cycloalkene group is preferably a cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group from which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms has been removed.
- Examples include 2-cyclopentene-1-yl group and 2-cyclohexene-1-yl group.
- the bicycloalkenyl group a bicycloalkenyl group having 5 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a bicycloalkene having one double bond is preferable.
- Examples thereof include a bicyclo [2.2.1] hept-2-en-1-yl group and a bicyclo [2.2.2] octo-2-en-4-yl group.
- the alkynyl group is preferably an alkynyl group having 2 to 30 carbon atoms, and examples thereof include an ethynyl group and a propargyl group.
- the aryl group is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a p-tolyl group (methylphenyl group), a naphthyl group, an m-chlorophenyl group and an o-hexadecanoylaminophenyl group.
- a phenyl group which may have a substituent is preferable.
- the heterocyclic group is a monovalent group obtained by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound, and they may be further condensed.
- the heterocyclic group thereof is preferably a 5- or 6-membered heterocyclic group, and the heteroatom having a ring structure is preferably an oxygen atom, a sulfur atom, or a nitrogen atom. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms.
- the heterocycle in the heterocyclic group includes a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a quinazoline ring, a synnoline ring, a phthalazine ring, a quinoxaline ring, a pyrrol ring, an indole ring, and a furan ring.
- the aliphatic oxy group (for example, an alkoxy group) preferably has 1 to 30 carbon atoms.
- a methoxy group, an ethoxy group, an isopropoxy group, an n-octyloxy group, a methoxyethoxy group, a hydroxyethoxy group, a 3-carboxypropoxy group and the like can be mentioned.
- the aryloxy group is preferably an aryloxy group having 6 to 30 carbon atoms. Examples of the aryloxy group include a phenoxy group, a 2-methylphenoxy group, a 4-t-butylphenoxy group, a 3-nitrophenoxy group, a 2-tetradecanoylaminophenoxy group and the like. Preferably, it is a phenyloxy group which may have a substituent.
- the acyloxy group is preferably a formyloxy group, an alkylcarbonyloxy group having 2 to 30 carbon atoms, or an arylcarbonyloxy group having 6 to 30 carbon atoms.
- Examples of the acyloxy group include a formyloxy group, an acetyloxy group, a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, a p-methoxyphenylcarbonyloxy group and the like.
- the carbamoyloxy group is preferably a carbamoyloxy group having 1 to 30 carbon atoms.
- carbamoyloxy groups include N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N, N-di-n-octylaminocarbonyloxy group, Nn-octyl. Carbamoyloxy group and the like can be mentioned.
- the aliphatic oxycarbonyloxy group (for example, an alkoxycarbonyloxy group) preferably has 2 to 30 carbon atoms and may have a substituent.
- a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, an n-octylcarbonyloxy group and the like can be mentioned.
- the aryloxycarbonyloxy group is preferably an aryloxycarbonyloxy group having 7 to 30 carbon atoms.
- Examples of the aryloxycarbonyloxy group include a phenoxycarbonyloxy group, a p-methoxyphenoxycarbonyloxy group, a pn-hexadecyloxyphenoxycarbonyloxy group and the like. It is preferably a phenoxycarbonyloxy group which may have a substituent.
- Amino groups include amino groups, aliphatic amino groups (eg, alkylamino groups), arylamino groups and heterocyclic amino groups.
- the amino group is preferably an aliphatic amino group having 1 to 30 carbon atoms (for example, an alkylamino group) and an arylamino group having 6 to 30 carbon atoms.
- amino groups include, for example, amino groups, methylamino groups, dimethylamino groups, anilino groups, N-methyl-anilino groups, diphenylamino groups, hydroxyethylamino groups, carboxyethylamino groups, sulfoethylamino groups, Examples thereof include a 3,5-dicarboxyanilino group and a 4-quinolylamino group.
- the acylamino group is preferably a formylamino group, an alkylcarbonylamino group having 1 to 30 carbon atoms, or an arylcarbonylamino group having 6 to 30 carbon atoms.
- acylamino group examples include a formylamino group, an acetylamino group, a pivaloylamino group, a lauroylamino group, a benzoylamino group, a 3,4,5-tri-n-octyloxyphenylcarbonylamino group and the like.
- the aminocarbonylamino group is preferably an aminocarbonylamino group having 1 to 30 carbon atoms.
- Examples of the aminocarbonylamino group include a carbamoylamino group, an N, N-dimethylaminocarbonylamino group, an N, N-diethylaminocarbonylamino group, a morpholinocarbonylamino group and the like.
- the term "amino" in this group has the same meaning as "amino" in the above-mentioned amino group.
- the aliphatic oxycarbonylamino group (for example, an alkoxycarbonylamino group) preferably has 2 to 30 carbon atoms and may have a substituent.
- a methoxycarbonylamino group, an ethoxycarbonylamino group, a t-butoxycarbonylamino group, an n-octadecyloxycarbonylamino group, an N-methyl-methoxycarbonylamino group and the like can be mentioned.
- the aryloxycarbonylamino group is preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms.
- aryloxycarbonylamino group examples include a phenoxycarbonylamino group, a p-chlorophenoxycarbonylamino group, an mn-octyloxyphenoxycarbonylamino group and the like.
- a phenyloxycarbonylamino group which may have a substituent is preferable.
- the sulfamoylamino group is preferably a sulfamoylamino group having 0 to 30 carbon atoms.
- the sulfamoylamino group examples include a sulfamoylamino group, an N, N-dimethylaminosulfonylamino group, an Nn-octylaminosulfonylamino group and the like.
- the aliphatic arylsulfonylamino group may have an aliphatic sulfonylamino group having 1 to 30 carbon atoms (for example, an alkylsulfonylamino group) and an arylsulfonylamino group having 6 to 30 carbon atoms (preferably a phenylsulfonyl group having a substituent). Amino group) is preferable.
- a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, a p-methylphenylsulfonylamino group and the like can be mentioned.
- the aliphatic thio group (for example, an alkyl thio group) is preferably an alkyl thio group having 1 to 30 carbon atoms.
- alkylthio group include a methylthio group, an ethylthio group, an n-hexadecylthio group and the like.
- the sulfamoyl group is preferably a sulfamoyl group having 0 to 30 carbon atoms.
- sulfamoyl groups include N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfamoyl group, N-acetylsulfamoyl group, N-benzoylsulfa.
- Moil group, N- (N'-phenylcarbamoyl) sulfamoyl) group and the like can be mentioned.
- the aliphatic or arylsulfinyl group is preferably an aliphatic sulfinyl group having 1 to 30 carbon atoms (for example, an alkylsulfinyl group) and an arylsulfinyl group having 6 to 30 carbon atoms (preferably a phenylsulfinyl group which may have a substituent).
- a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group, a p-methylphenylsulfinyl group and the like can be mentioned.
- an aliphatic sulfonyl group having 1 to 30 carbon atoms for example, an alkylsulfonyl group
- an arylsulfonyl group having 6 to 30 carbon atoms preferably a phenylsulfonyl group which may have a substituent
- methyl sulfonyl, ethyl sulfonyl, phenyl sulfonyl, p-toluene sulfonyl group and the like can be mentioned.
- the acyl group includes a formyl group, an aliphatic carbonyl group having 2 to 30 carbon atoms (for example, an alkylcarbonyl group), an arylcarbonyl group having 7 to 30 carbon atoms (preferably a phenylcarbonyl group which may have a substituent), and carbon.
- a heterocyclic carbonyl group bonded to a carbonyl group with a number of 4 to 30 carbon atoms is preferred.
- acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl group and the like can be mentioned.
- the aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 30 carbon atoms.
- Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl group and the like. It is preferably a phenyloxycarbonyl group which may have a substituent.
- the aliphatic oxycarbonyl group (for example, an alkoxycarbonyl group) preferably has 2 to 30 carbon atoms and may have a substituent.
- the carbamoyl group is preferably a carbamoyl group having 1 to 30 carbon atoms.
- Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl group and the like.
- Examples of the aryl or heterocyclic azo group include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo group and the like.
- Examples of the imide group include an N-succinimide group and an N-phthalimide group.
- hydroxyl groups, cyano groups, nitro groups, sulfo groups, and carboxyl groups can be mentioned.
- Each of these groups may further have a substituent, and examples of such a substituent include the above-mentioned substituent T.
- the compound represented by the general formula (1) can be produced by the method described in US Pat. No. 5,789,560.
- the compound represented by the general formula (2) is, for example, Disperse Yellow 201 (for example, Last Yellow 8070 (manufactured by Arimoto Chemical Industry Co., Ltd., trade name), Macrolex Yellow 6G (manufactured by Lanxess, trade name)) and the like.
- Disperse Yellow 201 for example, Last Yellow 8070 (manufactured by Arimoto Chemical Industry Co., Ltd., trade name), Macrolex Yellow 6G (manufactured by Lanxess, trade name)
- the dehydration condensation reaction between malononitrile and an aminobenzaldehyde derivative which is obtained as a commercial product or is generally performed (for example, Journal of the Society of Diers and Colorists (1977) 93 (4) pp. 126-133. It can be synthesized by the method).
- the compound represented by the general formula (3) can be obtained as a commercial product such as HSY-2186 (manufactured by Mitsubishi Chemical Corporation, trade name) or by the method described in International Publication No. 2018-91979. Can be synthesized.
- the compound represented by the general formula (4) can be obtained as a commercially available product such as HSY-2701 (manufactured by Mitsubishi Chemical Corporation, trade name), or is a commonly used pyrazolone derivative and aminobenzaldehyde derivative. It can be synthesized by a dehydration condensation reaction with (for example, the method described in Chinese Patent No. 100,546,979).
- the compound represented by the general formula (5) can be obtained as a commercial product such as a reagent manufactured by BOC Science (catalog number 69808-32-8), or a commonly used aniline derivative and pyridone. It can be synthesized by a diazo coupling reaction with a derivative (for example, the method described in Zeitscrift feel Chemie (1989) 29 (11) pp. 422-423).
- the compound represented by the general formula (6) includes Solvent Yellow 93 (for example, Last Yellow 8000 (manufactured by Arimoto Chemical Industry Co., Ltd., trade name), KP Last Yellow G (manufactured by Kiwa Chemical Industry Co., Ltd., trade name), etc.) and the like. It is obtained as a commercial product as in the above, or synthesized by a commonly used condensation reaction between a pyrazolone derivative and an orthoformic acid ester (for example, the method described in Pharmaceutical Journal (1953) Vol. 73, pp. 1063-166). can do.
- Solvent Yellow 93 for example, Last Yellow 8000 (manufactured by Arimoto Chemical Industry Co., Ltd., trade name), KP Last Yellow G (manufactured by Kiwa Chemical Industry Co., Ltd., trade name), etc.
- the compound represented by the general formula (7) is active methylene by a Vilsmeier reaction after N-alkylating 2,3,3-trimethylindorenin in the same manner as in a commonly used method for synthesizing a merocyanine dye.
- the site can be formylated and subsequently synthesized by a dehydration condensation reaction with a pyrazolone derivative.
- the compound represented by the general formula (8) can be obtained as a commercially available product such as HSB-2115, HSB-2131 and HSB-2207 (all manufactured by Mitsubishi Chemical Co., Ltd., trade names), or is generally obtained. It can be synthesized by the dehydration condensation reaction between the 4-nitrosoaniline derivative and the phenol derivative (for example, the method described in Japanese Patent No. 5,308,692).
- the compound represented by the general formula (9) is synthesized by a commonly used dehydration condensation reaction between a 4-nitrosoaniline derivative and a naphthol derivative (for example, the method described in Japanese Patent No. 5,308,692). can do.
- the compound represented by the general formula (10) includes a reagent manufactured by Alpha Chemistry (catalog number ACM75214618), Disperse Blue354 (for example, Folon Brilliant Blue SR (trade name) manufactured by Clariant), and Kayalon Polyester Brilliant Blue. Obtained as a commercial product such as S (manufactured by Nippon Kayaku Co., Ltd., trade name), or by a commonly used method (for example, the method described in Chinese Patent No. 106,675,082). Can be synthesized.
- Alpha Chemistry catalog number ACM75214618
- Disperse Blue354 for example, Folon Brilliant Blue SR (trade name) manufactured by Clariant
- Kayalon Polyester Brilliant Blue Obtained as a commercial product such as S (manufactured by Nippon Kayaku Co., Ltd., trade name), or by a commonly used method (for example, the method described in Chinese Patent No. 106,675,082). Can be synthesized.
- the compound represented by the general formula (11) is a diazo coupling reaction between an aniline derivative and an aminothiophene derivative, followed by a diazo coupling reaction with a 3-acylaminoaniline derivative (for example, Chinese Patent No. 106,928,745). It can be synthesized by the method described in the document).
- the compound represented by the general formula (12) includes Solvent Blue 36 (for example, Sumipast Blue OA (manufactured by Sumika Chemitex Co., Ltd., trade name), Plus Blue8510 (manufactured by Arimoto Chemical Industry Co., Ltd., trade name), etc.), Solvent. It can be obtained as a commercial product such as Blue 63 (for example, Last Blue 8540 (manufactured by Arimoto Chemical Industry Co., Ltd., trade name)).
- Solvent Blue 36 for example, Sumipast Blue OA (manufactured by Sumika Chemitex Co., Ltd., trade name), Plus Blue8510 (manufactured by Arimoto Chemical Industry Co., Ltd., trade name), etc.
- Solvent It can be obtained as a commercial product such as Blue 63 (for example, Last Blue 8540 (manufactured by Arimoto Chemical Industry Co., Ltd., trade name)).
- the compound represented by the general formula (13) is Dispersed Red 60 (for example, Last Red 8375 (manufactured by Arimoto Chemical Industry Co., Ltd., trade name) or Sumikaron Red E-FBL (manufactured by Sumika Chemitex Co., Ltd., trade name)). It can be obtained as a commercial product such as.
- the compound represented by the general formula (14) can be obtained as a commercial product such as Disperse Violet 26 (for example, Sumikalon Bordeaux SE BL (manufactured by Sumika Chemitex Co., Ltd., trade name)).
- the compound represented by the general formula (15) can be obtained as a commercial product such as HSR-2150 and HSR-2164 (both manufactured by Mitsubishi Chemical Corporation, trade names).
- the compound represented by the general formula (16) is a commonly used diazo coupling reaction between 5-amino-3-methylisothiazole-4-carbonitrile and a 3-acylaminoaniline derivative (for example, a special case). It can be synthesized by the method described in Japanese Patent Publication No. 2004-345270).
- the compound represented by the general formula (17) is a commonly used oxidative coupling reaction between a 5-amino-2- (N, N-dialkylamino) pyridine derivative and a pyrazorotriazole derivative (for example, a patent). It can be synthesized by the method described in No. 3,513,792).
- the compound represented by the general formula (18) is synthesized by a commonly used condensation reaction between a 4-nitrosoaniline derivative and a pyrazorotriazole derivative (for example, the method described in JP-A-2007-262165). be able to
- the compounds represented by the general formula (19) are commonly used 2- (N, N-dialkyl) -5-formylthiazole derivatives and 6-hydroxy-2-pyridone-3-carbonitrile derivatives. It can be synthesized by a condensation reaction with (for example, the method described in Japanese Patent No. 2839675).
- the compound represented by the general formula (20) is a commonly used reaction between a 4- (dicyanomethylene) -1-phenyl-4-pyrazolone derivative and an N, N-dialkylaniline derivative (for example, Days). It can be synthesized by and Pigments (1988) 9 (5), the method described on pages 393 to 399).
- the heat-sensitive transfer recording sheet of the present invention it is possible to form a process black having a high concentration, excellent color, and a tightening effect of other colors.
- the detailed mechanism is unknown, but it is considered as follows.
- the compound (magenta dye) represented by the general formula (1) has high transferability, and the absorption waveform is sharp in the low to medium density print region, so that it is vivid and the color reproduction range is wide, but the density saturation of the high density print is wide. There is a characteristic that the absorption waveform becomes broad in the region.
- a dye layer containing a magenta dye represented by the general formula (1), a dye layer containing a yellow dye represented by the general formulas (2) to (7), and general formulas (8) to By using the dye layer containing the cyan dye represented by 12), the boundaries of the yellow absorption waveform, the magenta absorption waveform, and the cyan absorption waveform are efficiently filled in the obtained process black portion, and the boundary is flat in the visible region. As it approaches absorption, it can form a good quality process black. Further, according to the thermal transfer recording sheet having a preferable form of the present invention, in addition to the above effects, it is possible to obtain an image having a high color balance at the time of fading. The reason is considered as follows.
- the magenta dye represented by the general formula (1) has high light resistance and moist heat fastness, and even when mixed with other dyes (in addition to the magenta dye represented by the general formula (1) in the ink sheet, other magenta When a dye is used in combination, or when a cyan dye or a yellow dye is mixed with a magenta dye represented by the general formula (1) in printing), fading is not accelerated catalytically.
- the dye in the dye layer of each color tone, can be used alone or in combination of two or more.
- the preferred combinations of the cyan dye, the yellow dye, and the magenta dye in the present invention will be described.
- the preferred combination of dyes can be further combined with the preferred combination of dyes of different hues.
- the cyan dye preferably contains a compound represented by the general formula (8) and at least one compound represented by any of the general formulas (9) to (12). According to this combination, in addition to the above-mentioned effects of the present invention, it is possible to enhance the color balance at the time of fading of a gray image due to light. Further, the reverse transferability can be reduced (that is, the return of the dye to the ink sheet (reverse transfer) at the time of printing can be reduced).
- the total content (I) of the compound represented by the general formula (8) and the content of the compound represented by any of the general formulas (9) to (12) (II).
- the cyan dye also preferably contains a compound represented by the general formula (8) and a compound represented by the general formula (12). According to this combination, in addition to the effect of the present invention, the color balance at the time of fading by light of a gray image is enhanced, the reverse transferability is lowered, and the residual ratio of each dye at the time of fading by light of a monochromatic image is increased. It can be enhanced, and the fading balance in a dark place with high temperature and high humidity can be enhanced.
- the yellow dye preferably contains a compound represented by the general formula (4) and at least one compound represented by any of the general formulas (2), (3), (5) to (7). ..
- the yellow dye preferably contains a compound represented by the general formula (4) and at least one compound represented by the general formula (2) or (6).
- the content (III) of the compound represented by the general formula (4) is represented by any of the general formulas (2), (3) and (5) to (7).
- the yellow dye contains a compound represented by the general formula (3) and a compound represented by the general formula (2).
- the ratio of the content (XVI) of the compound represented by the general formula (3) to the content (V) of the compound represented by the general formula (2) is a mass ratio.
- (XVI): (V) 90 to 50:10 to 50, more preferably 80 to 60:20 to 40.
- (XVI) + (V) 100.
- the magenta dye preferably contains a compound represented by the general formula (1) and at least one compound represented by any of the general formulas (13) to (20).
- the total content (VI) of the compound represented by the general formula (1) and the content of the compound represented by any of the general formulas (13) to (20) (VII).
- (VI) :( VII) 90 to 50:10 to 50 is preferable, and 80 to 60:20 to 40 is more preferable.
- (VI) + (VII) 100.
- the magenta dye also preferably contains a compound represented by the general formula (1) and a compound represented by the general formula (15).
- the ratio of the content of the compound represented by the general formula (1) (VIII) to the content of the compound represented by the general formula (15) (IX) is a mass ratio.
- (VIII): (IX) 90 to 50:10 to 50 is preferable, and 80 to 60:20 to 40 is more preferable.
- (VIII) + (IX) 100.
- the magenta dye also preferably contains a compound represented by the general formula (1), a compound represented by the general formula (15), and a compound represented by the general formula (13).
- the content (X) of the compound represented by the general formula (1), the content (XI) of the compound represented by the general formula (15), and the general formula (13) are used.
- the magenta dye also preferably contains a compound represented by the general formula (1), a compound represented by the general formula (13), and a compound represented by the general formula (14). When the above compounds are used in combination, the content of the compound represented by the general formula (1) (XIII), the content of the compound represented by the general formula (13) (XIV), and the general formula (14) are used.
- the magenta dye contains a compound represented by the general formula (1)
- the yellow dye contains at least one of the compounds represented by any of the general formulas (2) to (7)
- the cyan dye contains the general formula (8).
- the compound represented by the general formula (12) are more preferably contained.
- the magenta dye contains the compound represented by the general formula (1), and the yellow dye contains the compound represented by the general formula (4) and any of the general formulas (2), (3), (5) to (7).
- the magenta dye contains a compound represented by the general formula (1), the yellow dye contains a compound represented by the general formula (4) and a compound represented by the general formula (2) or (6), and a cyan dye. Is preferably contained in the compound represented by the general formula (8) and at least one of the compounds represented by any of the general formulas (9) to (12).
- the magenta dye contains a compound represented by the general formula (1)
- the yellow dye contains a compound represented by the general formula (3) and a compound represented by the general formula (2)
- the cyan dye contains the compound represented by the general formula (2). It is preferable to include the compound represented by 8) and at least one of the compounds represented by any of the general formulas (9) to (12).
- the magenta dye contains at least one of a compound represented by the general formula (1) and a compound represented by any of the general formulas (13) to (20), and the yellow dye is represented by the general formula (4).
- a compound and at least one of the compounds represented by any of the general formulas (2), (3), (5) to (7) are included, and the cyan dye is generally represented by the general formula (8). It preferably contains at least one of the compounds represented by any of the formulas (9) to (12).
- the dye used in the present invention can also be used in combination with a dye.
- the dye to be used in combination is not particularly limited as long as it is diffused by heat, can be incorporated into a thermal transfer recording sheet, and is transferred from a thermal transfer recording sheet to an image receiving sheet by heating, and has been conventionally used as a dye for a thermal transfer sheet.
- a dye that has been used or a known dye can be used.
- Preferred dyes to be used in combination include, for example, diarylmethane dyes, triarylmethane dyes, thiazole dyes, methine dyes such as merocyanine, indian aniline, acetophenone azomethin, pyrazoloazomethin, imidazole azomethine, imidazole azomethine, pyridone azomethin and the like.
- azomethine dyes Representative azomethine dyes, xanthene dyes, oxazine dyes, dicyanostyrene, cyanomethylene dyes represented by tricyanostyrene, thiazine dyes, azine dyes, aclysine dyes, benzeneazo dyes, pyridone azo, thiophenazo, isothiazole azo, pyrrole azo, Examples thereof include azo dyes such as pyrar azo, imidazole azo, thiadiazol azo, triazole azo, and dizuazo, spiropyran dye, indolinospiropiran dye, fluorane dye, rhodamine lactam dye, naphthoquinone dye, anthraquinone dye, quinophthalone dye, and indoaniline dye.
- azo dyes such as pyrar azo, imidazole azo, thiadiazol azo, triazole
- the dye of each hue is coated on the substrate in a state of being dispersed in a polymer compound called a binder.
- a binder for the thermal transfer recording sheet used in the present invention, various known binders can be used.
- polymer compounds for binders include acrylic resins such as polyacrylonitrile, polyacrylic acid ester, and polyacrylamide, polyvinyl acetal resins such as polyvinyl acetacetal and polyvinyl butyral, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxy cellulose, and hydroxypropyl cellulose.
- Modified cellulose resins such as ethyl hydroxyethyl cellulose, methyl cellulose, acetate cellulose, vinegar butyrate cellulose, propionate cellulose acetate, cellulose nitrate, cellulose resins such as nitrocellulose, ethyl hydroxyethyl cellulose and ethyl cellulose, polyurethane resins, polyamide resins, polyester resins, polycarbonate resins. , Phenoxy resin, phenol resin, epoxy resin, various estramers and the like. In addition to using these alone, it is also possible to mix or copolymerize them.
- a polyvinyl acetal resin is preferable, and a polyvinyl acetal resin is more preferable.
- acetal resin having an acetal portion in the resin of 80% by mass or more and an acetal acetal ratio of 90% by mass or more in the acetal portion.
- Such an acetal resin can be synthesized by the method according to Japanese Patent No. 3065111 and the documents cited in this specification, as well as Eslex KS-5 (trade name) manufactured by Sekisui Chemical Industry Co., Ltd. and Electrochemical Industry Co., Ltd. There are commercially available products such as Denka Butyral # 5000-D (trade name).
- the cross-linking agent is a compound having a property of reacting with a functional group attached to a main chain or a side chain of a polymer compound to bond the polymers to each other.
- Diisocyanate compound As aromatic polyisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, trizine diisocyanate, naphthalin diisocyanate and the like, and as aliphatic polyisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylerring diisocyanate, hydrogenated xylerin diisocyanate, Examples thereof include dicyclohexylmethane diisocyanate.
- Triisocyanate compound Trimethylol propane-modified tolylene diisocyanate, isocyanurate-bonded tolylene diisocyanate, trimethylolpropane-modified hexamethylene diisocyanate, isocyanurate-bonded hexamethylene diisocyanate, burette-bonded hexamethylene diisocyanate, trimethylol isophorone diisocyanate, isocyanurate Examples thereof include bound isophorone diisocyanate, triphenylmethane triisocyanate, and tris (isocyanatephenyl) thiophosphate. It is also preferable to use a mixture of these isocyanate compounds or a polymer having an isocyanate compound in the main chain or side chain.
- isocyanates are commercially available under trade names such as Barnock (manufactured by Dainippon Ink and Chemicals Co., Ltd.), Takenate, MT-Olestar (all manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), and Coronate (manufactured by Nippon Polyurethane Industry Co., Ltd.). It is possible.
- the amount of isocyanates used is preferably in the range of 0.2 to 2.0, preferably in the range of 0.3 to 1.5 in terms of the molar ratio (NCO / H) of the isocyanate group (-NCO) and the active hydrogen (H) of the binder. Is more preferable.
- a catalyst may be added for the purpose of promoting the cross-linking reaction between the binder and isocyanates.
- Such catalysts are described in "Latest Polyurethane Materials and Applied Technologies” (MC Publishing Co., Ltd., 2005).
- the dye layer usually contains a dye and a binder, but may contain waxes, a polymer compound having a fluorine atom-containing aliphatic group, a silicone compound, polymer particles, and inorganic particles, if necessary. can.
- a polymer compound having a fluorine atom-containing aliphatic group and a silicone compound preferably used in the present invention will be described.
- Fluorine release agent (polymer compound having a fluorine atom-containing aliphatic group)
- a preferred form is a polymer compound having a fluorine atom-containing aliphatic group in the side chain.
- the polymer compound having a fluorine atom-containing aliphatic group in the side chain is derived from the fluorine atom-containing aliphatic compound produced by the telomerization method (also called the telomer method) or the oligomerization method (also called the oligomer method). Can be done.
- the fluorine atom-containing aliphatic compound can be easily synthesized by, for example, the method described in JP-A-2002-90991.
- the fluorine atom-containing aliphatic group is an aliphatic group (straight-chain, branched or cyclic aliphatic group) having at least one fluorine atom as a substituent, and preferably has 1 to 36 carbon atoms.
- substituents examples include an alkyl group, an aryl group, a heterocyclic group, a halogen atom other than a fluorine atom, a hydroxyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an alkylamino group and an arylamino group. , Heterocyclic amino group, acylamino group, sulfonamino group, carbamoyl group, sulfamoyl group, cyano group, nitro group, acyl group, sulfonyl group, ureido group, urethane group and the like.
- the fluorine atom-containing aliphatic group is most preferably a perfluoroalkyl group.
- the polymer compound having a fluorine atom-containing aliphatic group in the side chain is preferably a polymer or copolymer of a monomer having a fluorine atom-containing aliphatic group, and such a monomer is an acrylic acid compound (for example, acrylic acids).
- acrylic acid esters, acrylic acid amides, acrylic acid esters, acrylic acid amides are preferable, acrylic acid esters are more preferable), methacrylic acid compounds (for example, methacrylic acids, methacrylic acid esters, methacrylic acid amides).
- a fluorine atom-containing aliphatic group is used as a substituent in the acyl moiety or alcohol or amide moiety (group substituting for a nitrogen atom) of a methacrylic acid ester or a methacrylic acid amide, more preferably a methacrylic acid ester.
- a polymer compound obtained by a monomer having a fluorine atom-containing aliphatic group as a substituent in the monomer or the acrylonitrile compound is preferable.
- the polymer compound having a fluorine atom-containing aliphatic group in the side chain is a copolymer with a monomer having a fluorine atom-containing aliphatic group, and the monomers to be combined are acrylates, methacrylates, acrylonitriles, and acrylamide. Classes, methacrylicamides, olefins, styrenes and the like, among which acrylates, methacrylates, acrylonitriles, acrylamides and methacrylicamides are preferable, and acrylates and methacrylates are more preferable.
- the copolymer is preferable, and it may be a binary copolymer, a ternary copolymer, or more.
- a copolymer of a monomer having a fluorine atom-containing aliphatic group and (poly (oxyalkylene)) acrylate and / or (poly (oxyalkylene)) methacrylate is preferable, and even those irregularly distributed are blocked. It may be copolymerized.
- the poly (oxyalkylene) group include poly (oxyethylene) group, poly (oxypropylene) group, poly (oxybutylene) group, and poly (oxyethylene, oxypropylene, and oxyethylene). It may be a unit having alkylenes having different chain lengths in the same polymer chain such as block conjugate) or poly (block conjugate of oxyethylene and oxypropylene).
- the copolymer of the monomer having a fluorine atom-containing aliphatic group and the (poly (oxyalkylene)) acrylate (or methacrylate) is not only a binary copolymer but also two or more different fluorine atom-containing aliphatic groups. It may be a ternary or more copolymer obtained by simultaneously copolymerizing a monomer having a
- the mass average molecular weight of the polymer compound having a fluorine atom-containing aliphatic group in the side chain is preferably 5,000 to 100,000, more preferably 8,000 to 50,000, and even more preferably 10. It is 000 to 40,000.
- poly (oxyalkylene)) acrylate (or methacrylate) copolymer acrylate (or methacrylate) having a perfluorohexyl group, (poly (oxyethylene)) acrylate (or methacrylate) and (poly (oxypropylene)).
- the polymer compound having these fluorine atom-containing aliphatic groups in the side chain is commercially available under a general name such as "perfluoroalkyl-containing oligomer", and for example, the following products can be used.
- the polymer compound having a fluorine atom-containing aliphatic group in the side chain is preferably nonionic (one having no dissociated group in water, for example, a sulfo group or a carboxyl group), and has a certain water solubility. It is more preferable to have.
- the constant water solubility means that the polymer compound has a solubility of 1% or more in pure water at 25 ° C. Specifically, it is a polymer compound having a hydroxyl group and an oxyalkylene group as described above.
- Compounds exhibiting solubility in water such as Megafuck F-479, Megafuck F-480SF, Megafuck F-484, and Megafuck F-486 (all of which are trade names), are preferable.
- the polymer compound having a fluorine atom-containing aliphatic group in the side chain may be contained in any of the dye layers of yellow, magenta, cyan and, if necessary, black, and even if it is contained in one dye layer, a plurality of dyes may be contained. It may be contained in the layer. It is preferably contained in each of the yellow, magenta, and cyan dye layers. Further, the amount of the polymer compound having a fluorine atom-containing aliphatic group in the side chain can be determined according to the type and amount of the dye and the binder, and is preferably 0 with respect to the total solid content (mass) of the dye layer. It is 0.01% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, and further preferably 0.2% by mass to 5% by mass.
- Silicone mold release agent (silicone compound) Next, a silicone compound suitably used for the thermal transfer recording sheet of the present invention will be described. In the thermal transfer recording sheet of the present invention, it is also preferable to use a silicone compound in combination.
- the silicone compound in the present invention is a compound having a polysiloxane structure having SiO as a repeating unit in the main chain or side chain in the molecule.
- a typical example is a silicone oil in which a hydrogen atom, an alkyl group or an aryl group is bonded on a Si atom of a polymer main chain having SiO as a repeating unit.
- polysiloxane refers to a structure having a hydrogen atom, an alkyl group, and an aryl group on a Si atom with SiO as a repeating unit, like the above-mentioned silicone oil.
- the silicone compound preferably used in the present invention is a silicone graft polymer or a silicone block polymer.
- the silicone graft polymer is a polymer having a structure in which a large number of side chains having a polysiloxane structure are branched in a branch shape from one main chain constituting the polymer.
- the silicone block polymer is a polymer having a structure in which a polysiloxane structure is embedded in a main chain constituting the polymer.
- the main chain in the silicone graft polymer may be a polymer of a single monomer or a copolymer of a plurality of types of monomers. Further, it may have a block polymer structure in which a plurality of polymer segments are bonded. Further, the side chain may have only a polysiloxane structure or may be mixed with other structures. Further, the polysiloxane portion of the side chain may be composed of one kind of polysiloxane portion or may be composed of a plurality of different types of polysiloxane portions.
- the average content of the polysiloxane portion in the polymer is preferably in the range of 5% by mass or more and 70% by mass or less, and more preferably 10% by mass or more and 50% by mass or less.
- the portion of the polymer chain may be a polymer of a single monomer or a copolymer of a plurality of types of monomers.
- the part of the polymer chain may consist of a plurality of different types of polymer chains.
- the polysiloxane portion may also be composed of a plurality of different types of polysiloxane portions as in the case of the polymer chain. Further, both the polymer chain and the polysiloxane portion may have side chains to form a so-called graft polymer structure.
- the average content of the polysiloxane portion in the polymer is preferably in the range of 5% by mass or more and 70% by mass or less, and more preferably 10% by mass or more and 50% by mass or less.
- Such polymers can be synthesized by various methods. For example, a method of directly reacting a polysiloxane portion having a functional group that reacts with the above functional group after forming a polymer chain having an appropriate functional group as a main chain, or a method of reacting with a cross-linking agent such as diisocyanate. Etc. are known. Moreover, such a polymer is also commercially available. For example, Dialomer SP712 (trade name), manufactured by Dainichiseika Kogyo Co., Ltd., and the like can be mentioned.
- a more preferable structure of such a polymer is that the portion of the polymer chain has a structure similar to that of the binder used.
- the polymer chain of the silicone compound has a polyvinyl acetal acetal structure.
- the base material of the thermal transfer recording sheet of the present invention and the protective layer transfer sheet described later is not particularly limited, and any conventionally known material can be used as long as it has the required heat resistance and strength. can. Examples include polyamides, polyimides and polyester films.
- the thickness of the base material can be appropriately changed depending on the material so that its strength, heat resistance and the like are appropriate, but is preferably 1 to 100 ⁇ m. It is more preferably 2 to 50 ⁇ m, and even more preferably 3 to 10 ⁇ m.
- a dye barrier layer for preventing the dye from diffusing toward the substrate can be provided between the dye layer and the substrate.
- a normal one can be used, for example, a polyvinyl alcohol resin, a polyvinyl acetal resin having a low degree of acetalization (acetal portion is 50% or less with respect to the entire resin), and the like.
- the surface of the base material may be subjected to an easy-adhesion treatment for the purpose of improving the wettability and adhesiveness of the coating liquid.
- an easy-adhesion treatment for the purpose of improving the wettability and adhesiveness of the coating liquid.
- resin surface modifications such as corona discharge treatment, flame treatment, ozone treatment, ultraviolet treatment, radiation treatment, roughening treatment, chemical treatment, vacuum plasma treatment, atmospheric pressure plasma treatment, primer treatment, grafting treatment, etc. Quality technology can be exemplified.
- an easy-adhesive layer can be formed on the substrate by coating.
- the resin used for the easy-adhesion layer includes polyester resin, polyacrylic acid ester resin, polyvinyl acetate resin, vinyl resin such as polyvinyl chloride resin and polyvinyl alcohol resin, polyvinyl acetal resin such as polyvinyl acetacetal and polyvinyl butyral, and poly.
- examples thereof include ether resin, polyurethane resin, styrene acrylate resin, polyacrylamide resin, polyamide resin, polystyrene resin, polyethylene resin, polypropylene resin and the like.
- the easy-adhesive layer may be formed by applying a coating liquid containing the above resin to an unstretched film when the film used for the base material is melt-extruded and then stretching the film.
- two or more types of the above processing can be used in combination.
- transferable protective layer laminate that can be used for the thermal transfer recording sheet of the present invention.
- the heat-sensitive transfer recording sheet is provided with the transferable protective layer laminate in a surface-sequential manner with each of the dye layers.
- a transferable protective layer laminate may be provided on the substrate and prepared as a protective layer transfer sheet separately from the thermal transfer recording sheet.
- the transferable protective layer laminate is for forming a protective layer made of a transparent resin on a heat-transferred image by thermal transfer to cover and protect the image, and is used for scratch resistance, light resistance, weather resistance, and chemical resistance. The purpose is to improve durability such as sex.
- the transferable protective layer laminate can be formed on the substrate in the order of a release layer, a transferable protective layer, and an adhesive layer from the substrate side. It is also possible to form the transferable protective layer with a plurality of layers. When the transferable protective layer also has the functions of other layers, it is possible to omit the release layer and the adhesive layer. When a release layer is used, it is also possible to use a base material provided with an easy-adhesive layer.
- the resin forming the transferable protective layer a resin having excellent scratch resistance, chemical resistance, transparency, and hardness is preferable, and polyester resin, acrylic resin, polystyrene resin, polyurethane resin, acrylic urethane resin, and each of these resins are used.
- a silicone-modified resin, an ultraviolet blocking resin, a mixture of these resins, an ionizing radiation curable resin, an ultraviolet curable resin and the like can be used.
- polyester resin and acrylic resin are preferable. It is also possible to carry out cross-linking with the various cross-linking agents described above.
- the back surface layer on the other surface (back surface) of the surface of the base material coated with the dye layer that is, on the side in contact with the thermal head or the like.
- the protective layer transfer sheet it is preferable to provide the back surface layer on the other surface (back surface) of the surface of the base material coated with the transferable protective layer, that is, on the side in contact with the thermal head or the like.
- the back layer is provided so that the heat-sensitive transfer recording sheet can withstand the heat energy from the thermal head, prevents heat fusion, and enables smooth running. In recent years, as the speed of printers has increased, the thermal energy of thermal heads has increased, so the need for them has increased.
- the back layer is formed by applying a binder to which a lubricant, a mold release agent, a surfactant, an inorganic particle, an organic particle, a pigment or the like is added. Further, an intermediate layer may be provided between the back surface layer and the base material, and a layer made of inorganic fine particles and a water-soluble resin or a hydrophilic resin that can be emulsified is disclosed.
- a known resin having high heat resistance can be used as the binder.
- cellulose resins such as ethyl cellulose, hydroxycellulose, hydroxypropyl cellulose, methyl cellulose, acetate cellulose, vinegar butyrate cellulose, propionate cellulose acetate, nitrocellulose, polyvinyl alcohol, polyvinyl acetate, polyvinyl butyral, polyvinyl acetal, polyvinyl acetatetal resin.
- Vinyl chloride-vinyl acetate copolymer vinyl resin such as polyvinylpyrrolidone, acrylic resin such as polymethylmethacrylate, ethylpolyacrylate, polyacrylamide, acrylonitrile-styrene copolymer, polyamide resin, polyimide resin, polyamideimide resin , Polyvinyltoluene resin, Kumaron inden resin, polyester resin, polyurethane resin, polyether resin, polybutadiene resin, polycarbonate resin, chlorinated polyolefin resin, fluororesin, epoxy resin, phenol resin, silicone resin, silicone-modified or fluorine-modified urethane, etc. Can be mentioned alone or as a mixture of natural or synthetic resins.
- a technique of irradiating an ultraviolet ray or an electron beam to crosslink the resin is known. It is also possible to crosslink by heating using a crosslinking agent. At this time, a catalyst may be added.
- a crosslinking agent polyisocyanate and the like are known, and for this purpose, a resin having a functional group having a hydroxyl group is suitable.
- a back layer is formed by adding a filler such as an alkali metal salt or an alkaline earth salt of a phosphoric acid ester and calcium carbonate to a reaction product of polyvinyl butyral and an isocyanate compound. It is disclosed to do.
- JP-A-6-99671 a polymer compound forming a heat-resistant slipping layer is reacted with a silicone compound having an amino group and an isocyanate compound having two or more isocyanate groups in one molecule. It is disclosed that you will get.
- the back layer may contain additives such as lubricants, plasticizers, stabilizers, fillers, and fillers for removing head deposits.
- the lubricant includes fluorides such as calcium fluoride, barium fluoride and graphite fluoride, sulfides such as molybdenum disulfide, tungsten disulfide and iron sulfide, oxides such as lead oxide, alumina and molybdenum oxide, graphite and mica.
- Boron nitride solid lubricant consisting of inorganic compounds such as clays (talc, acidic whiteness, etc.), organic resins such as fluorine resin and silicone resin, silicone oils, metal surfactants such as stearic acid metal salts, polyethylene wax, paraffin Examples thereof include various waxes such as waxes, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and surfactants such as fluorine-containing surfactants.
- Phosphoric acid ester surfactants such as alkyl phosphoric acid monoesters and zinc salts of alkyl phosphoric acid diesters are also used, but they have acid roots, and when the amount of heat from the thermal head becomes large, the phosphoric acid ester decomposes and further the back layer. There is a problem that the pH of the ester is lowered and the corrosion and wear of the thermal head becomes severe.
- a method using a neutralized phosphate ester surfactant, a method using a neutralizing agent such as magnesium hydroxide, and the like are known.
- other additives include higher fatty acid alcohols, organopolysiloxanes, organic carboxylic acids and their derivatives, fine particles of inorganic compounds such as talc and silica, and the like.
- the back layer is a conventionally known method such as gravure coating, roll coating, blade coating, wire bar, etc., in which a coating liquid obtained by dissolving or dispersing a material in which an additive is added to a binder as exemplified above is dissolved or dispersed in a solvent. It is formed by applying with.
- the film thickness is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 5 ⁇ m.
- the thermal transfer image receiving sheet preferably has at least one receiving layer containing a thermoplastic receiving polymer that receives the dye on the substrate.
- the receiving layer can contain an ultraviolet absorber, a mold release agent, a lubricant, an antioxidant, a preservative, a surfactant, and other additives.
- An intermediate layer such as a heat insulating layer (porous layer), a gloss control layer, a white background adjusting layer, a charge adjusting layer, an adhesive layer, and a primer layer may be formed between the base material and the receiving layer.
- the receiving layer and these intermediate layers are preferably formed by simultaneous layer coating, and a plurality of intermediate layers can be provided as needed.
- a curl adjustment layer, a writing layer, and a charge adjustment layer may be formed on the back surface side of the base material.
- a general method such as a roll coat, a bar coat, a gravure coat, and a gravure reverse coat can be used.
- Latex In the present invention, it is preferable to use a dye-stainable polymer latex for the receiving layer as the thermal transfer image receiving sheet. Further, the polymer latex may be used alone or in combination of a plurality of polymer latexes.
- the polymer latex is generally a thermoplastic resin dispersed as fine particles in a water-soluble dispersion medium. Examples of the thermoplastic resin used for the polymer latex of the present invention include polycarbonate, polyester, polyacrylate, vinyl chloride copolymer, polyurethane, styrene-acrylonitrile copolymer, polycaprolactone and the like. Of these, polycarbonate, polyester and vinyl chloride copolymers are preferable, and polyester and vinyl chloride copolymers are particularly preferable.
- Polyester is obtained by condensation of a dicarboxylic acid derivative and a diol compound, may contain an aromatic ring or a saturated carbonized ring, or may have a water-soluble group for imparting dispersibility.
- vinyl chloride copolymer examples include vinyl chloride and vinyl acetate copolymer, vinyl chloride and acrylic rate copolymer, vinyl chloride and methacrylate copolymer, vinyl chloride and vinyl acetate and acrylate copolymer, and vinyl chloride. And a copolymer of acrylate and ethylene. As described above, a binary copolymer or a copolymer of ternary or more may be used, and the monomers may be irregularly distributed or may be block-copolymerized. Auxiliary monomer components such as vinyl alcohol derivative, maleic acid derivative, and vinyl ether derivative may be added to this copolymer.
- the vinyl chloride component is preferably contained in an amount of 50% by mass or more in the copolymer, and the auxiliary monomer component such as a maleic acid derivative or a vinyl ether derivative is preferably contained in an amount of 10% by mass or less.
- the polymer latex may be used alone or as a mixture.
- the polymer latex may have a uniform structure or a core / shell type, and at this time, the glass transition temperature of the resin forming the core and the shell may be different.
- the glass transition temperature (Tg) of such a polymer latex is preferably 20 ° C. or higher and 90 ° C. or lower, and more preferably 25 ° C. or higher and 80 ° C. or lower.
- acrylate latex examples include Nippon Zeon Corporation, NipolLX814 (Tg25 ° C.), NipolLX857X2 (Tg43 ° C.), and the like (all trade names).
- Commercially available polyester latex includes Toyobo Co., Ltd.'s Vironal MD-1100 (Tg40 ° C), Vironal MD-1400 (Tg20 ° C), Vironal MD-1480 (Tg20 ° C), MD-1985 (Tg20 ° C), etc. (Both are product names).
- vinyl chloride copolymers include Viniblanc 276 (Tg33 ° C) manufactured by Nisshin Kagaku Kogyo Co., Ltd., Viniblanc 609 (Tg48 ° C), Sumi Elite 1320 (Tg30 ° C) manufactured by Sumika Chemtex Co., Ltd., and Sumi. Elite 1210 (Tg 20 ° C.) and the like (both are trade names) can be mentioned.
- the amount of the polymer latex added is preferably 50 to 98% by mass, more preferably 70 to 95% by mass, based on the solid content of the polymer latex in the receiving layer.
- the average particle size of the polymer latex is preferably 1 to 50,000 nm, more preferably 5 to 1000 nm.
- the heat insulating layer contains a hollow polymer.
- the hollow polymer in the present invention is a polymer particle having voids inside the particles, and is preferably an aqueous dispersion.
- aqueous dispersion For example, 1) water or the like inside a partition wall formed of polystyrene, acrylic resin, styrene-acrylic resin or the like.
- a resin consisting of vinylidene, polyacrylonitrile, polyacrylic acid, polyacrylic acid ester, or a mixture or polymer thereof, and after coating, the low boiling point liquid inside the particles expands due to heating to expand the inside.
- a resin consisting of vinylidene, polyacrylonitrile, polyacrylic acid, polyacrylic acid ester, or a mixture or polymer thereof, and after coating, the low boiling point liquid inside the particles expands due to heating to expand the inside.
- examples thereof include a hollow foaming microballoon, 3) a microballoon obtained by preheating and foaming 2) above to form a hollow polymer.
- the non-foaming type hollow polymer particles described in 1) above are preferable, and two or more kinds can be mixed and used as needed. Specific examples include Low Pake HP-1055 manufactured by Roam and Hearth, SX866 (B) manufactured by JSR, and Nipol MH5055 manufactured by Zeon Corporation (all trade names).
- the average particle size of these hollow polymers is preferably 0.1 to 5.0 ⁇ m, more preferably 0.2 to 3.0 ⁇ m, and particularly preferably 0.4 to 1.4 ⁇ m.
- the hollow polymer preferably has a porosity of 20 to 70%, more preferably 30 to 60%.
- the size of the hollow polymer particles is calculated by measuring the equivalent circle-equivalent diameter of the outer diameter of the hollow polymer particles using a transmission electron microscope.
- the average particle size is obtained by observing at least 300 hollow polymer particles using a transmission electron microscope, calculating the equivalent circle diameter of the outer shape, and averaging them.
- the porosity of the hollow polymer is obtained from the ratio of the volume of the void portion to the particle volume.
- the glass transition temperature (Tg) is preferably 70 ° C. or higher and 200 ° C. or lower, and more preferably 90 ° C. or higher and 180 ° C. or lower.
- hollow polymer lattex is particularly preferable.
- the receiving layer and / or the heat insulating layer can contain a water-soluble polymer.
- the water-soluble polymer has a solubility of 0.05 g or more, more preferably 0.1 g or more, still more preferably 0.5 g or more with respect to 100 g of water at 20 ° C.
- water-soluble polymers that can be used in the present invention, caraginans, pectin, dextrin, gelatin, casein, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, polyvinylpyrrolidone copolymer, polyvinyl alcohol, polyethylene glycol, polypropylene glycol. , Water-soluble polyester and the like. Of these, gelatin and polyvinyl alcohol are preferable.
- gelatin having a molecular weight of 10,000 to 1,000,000 can be used.
- the gelatin used in the present invention may contain anions such as Cl ⁇ and SO 4 2- , or may contain cations such as Fe 2+ , Ca 2+ , Mg 2+ , Sn 2+ and Zn 2+ . ..
- Gelatin is preferably added by dissolving it in water.
- known cross-linking agents such as an aldehyde-type cross-linking agent, an N-methylol-type cross-linking agent, a vinyl sulfone-type cross-linking agent, and a chlorotriazine-type cross-linking agent can be added to gelatin.
- vinyl sulfone-type cross-linking agents and chlorotriazine-type cross-linking agents are preferable, and specific examples thereof include bisvinylsulfonylmethyl ether, N, N'-ethylene-bis (vinylsulfonylacetamide) ethane, and 4,6-dichloro. -2-Hydroxy-1,3,5-triazine or a sodium salt thereof can be mentioned.
- polyvinyl alcohol various polyvinyl alcohols such as completely saponified products, partially saponified products, and modified polyvinyl alcohols can be used.
- these polyvinyl alcohols those described in "Poval” (published by Polymer Publishing Association) co-authored by Koichi Nagano et al. Are used.
- the polyvinyl alcohol can be adjusted in viscosity or stabilized by a small amount of solvent or inorganic salts added to the aqueous solution.
- the content of boric acid can improve the coated surface quality, which is preferable.
- the amount of boric acid added is preferably 0.01 to 40% by mass with respect to polyvinyl alcohol.
- polyvinyl alcohol examples include PVA-105, PVA-110, PVA-117, and PVA-117H as fully saponified products, and PVA-203, PVA-205, PVA-210, and PVA-220 as partially saponified products.
- modified polyvinyl alcohol examples include C-118, HL-12E, KL-118, and MP-203 (trade names, all manufactured by Kuraray Co., Ltd.).
- the receiving layer of the thermal transfer image receiving sheet can contain the above-mentioned polymer compound having a fluorine atom-containing aliphatic group in the side chain.
- it may contain the same polymer compound as the polymer compound having a fluorine atom-containing aliphatic group in the side chain contained in the heat-sensitive transfer recording sheet, or may contain a different polymer compound in the same category. Is also a preferred embodiment in the present invention.
- solid waxes such as polyethylene wax and amide wax known as mold release agents, silicone oil, phosphoric acid ester compounds, fluorine-containing surfactants, and silicone surfactants may be contained.
- the content of the polymer compound having a fluorine atom-containing aliphatic group in the side chain is 0.01% by mass to 20% by mass, preferably 0.1% by mass, based on the total solid content (mass) of the receiving layer. It is about 10% by mass, more preferably 1% by mass to 5% by mass.
- the receiving layer of the heat-sensitive transfer image receiving sheet and the dye layer of the heat-sensitive transfer recording sheet are superposed so as to be in contact with each other, and the thermal energy corresponding to the image signal from the thermal head is obtained. It is preferable to form an image by imparting. Specific image formation can be performed in the same manner as that described in, for example, Japanese Patent Application Laid-Open No. 2005-88545.
- the print time is preferably less than 15 seconds, more preferably 3 to 12 seconds, still more preferably 3 to 7 seconds, from the viewpoint of shortening the time until the printed matter is provided to the consumer.
- the line speed at the time of printing is preferably 0.73 msec / line or less, and more preferably 0.65 msec / line or less.
- the maximum temperature reached by the thermal head at the time of printing is preferably 180 ° C. or higher and 450 ° C. or lower, and more preferably 200 ° C. or higher and 450 ° C. or lower. Further, 350 ° C. or higher and 450 ° C. or lower is preferable.
- the present invention can be used in printers, copiers, etc. that utilize a thermal transfer recording method.
- the heat energy applying means at the time of thermal transfer any conventionally known applying means can be used, and for example, a recording device such as a thermal printer (for example, Hitachi, Ltd. (trade name), video printer VY-100) or the like can be used.
- a recording device such as a thermal printer (for example, Hitachi, Ltd. (trade name), video printer VY-100) or the like can be used.
- the intended purpose can be sufficiently achieved by applying thermal energy of about 5 to 100 mJ / mm 2 .
- the above-mentioned thermal transfer image receiving sheet can be applied to various applications such as a sheet-fed or roll-shaped thermal transfer image receiving sheet capable of thermal transfer recording, cards, a sheet for creating a transmissive original, etc. by appropriately selecting a base material. You can also do it.
- magenta dye layer coating liquid ⁇ Preparation example of magenta dye layer coating liquid>
- Exemplified compound (1-1) 5.0 parts by mass, polyvinyl acetal resin (KS-3 (trade name), manufactured by Sekisui Chemical Co., Ltd.) 5.0 parts by mass, matting agent (Frosen UF (trade name), manufactured by Sumitomo Seiko Co., Ltd.) ) 0.1 part by mass, 45 parts by mass of methyl ethyl ketone and 45 parts by mass of toluene were mixed to prepare a magenta dye layer coating liquid (M1).
- KS-3 polyvinyl acetal resin
- matting agent Rosen UF (trade name), manufactured by Sumitomo Seiko Co., Ltd.)
- cyan dye layer coating liquid ⁇ Preparation example of cyan dye layer coating liquid>
- Exemplified compound (8-1) 5.0 parts by mass, polyvinyl acetal resin (KS-3 (trade name), manufactured by Sekisui Chemical Co., Ltd.) 5.0 parts by mass, matting agent (Frosen UF (trade name), manufactured by Sumitomo Seiko Co., Ltd.) ) 0.1 part by mass, 45 parts by mass of methyl ethyl ketone and 45 parts by mass of toluene were mixed to prepare a cyan dye layer coating liquid (C1).
- KS-3 polyvinyl acetal resin
- matting agent Rosen UF (trade name), manufactured by Sumitomo Seiko Co., Ltd.)
- Acrylic polyol resin (Acridic A-801 (trade name), manufactured by Dainippon Ink and Chemicals Co., Ltd.) 26.0 parts by mass, zinc stearate (SZ-2000 (trade name), manufactured by Sakai Chemical Industry Co., Ltd.) 0.43 mass Part, Phosphoric acid ester (Prysurf A217 (trade name), manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 1.27 parts by mass, 50% isocyanate compound solution (Bernock D-800 (trade name), manufactured by Dainippon Ink and Chemicals Co., Ltd.) 8.0 parts by mass and 64 parts by mass of methyl ethyl ketone / toluene (mass ratio 2/1) were mixed to prepare a back layer coating liquid.
- Acrylic polyol resin (Acridic A-801 (trade name), manufactured by Dainippon Ink and Chemicals Co., Ltd.) 26.0 parts by mass, zinc stearate (SZ-2000 (trade name), manufactured
- a release layer coating liquid was prepared by mixing 5.0 parts by mass of a modified cellulose resin (L-30 (trade name), manufactured by Daicel Chemical Industries, Ltd.) and 95.0 parts by mass of methyl ethyl ketone.
- Acrylic resin (Dianal BR-77 (trade name), manufactured by Mitsubishi Rayon Co., Ltd.) 25 parts by mass, UV absorber 1 (2,4,6-tris (4-butoxy-2-hydroxyphenyl) -1,3,5- Triazine, Catalog No. 3135-19-1, 2 parts by mass, UV absorber 2 (2- (2-hydroxy-5-methylphenyl) benzotriazole, Catalog No. 2440-22-4, Tokyo Kasei Co., Ltd.) 1 part by mass, UV absorber 3 (2- (5-t-butyl-2-hydroxyphenyl) benzotriazole, Catalog No.
- UV absorber 4 (2-t-butyl-6- (5-chloro-2H-benzotriazole-2-yl) -4-methylphenol, catalog number 3896-11-5, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 1 part by mass
- 0.4 parts by mass of polymethylmethacrylate fine particles Teuftic FH-S005 (trade name), manufactured by Nippon Exlan Industries, Ltd.
- 46 parts by mass of methyl ethyl ketone 46 parts by mass of methyl ethyl ketone, and 24 parts by mass of toluene were mixed to prepare an adhesive layer coating liquid.
- Example 1 Preparation of a heat-sensitive transfer recording sheet A polyester film having a thickness of 4.5 ⁇ m (Lumirror 5A-F595 (trade name), manufactured by Toray Industries, Inc.) having an easy-adhesion treatment on one side is used as a base material, and this polyester film is used.
- the above-mentioned back layer coating liquid was applied to the surface of the non-easy-adhesive surface so that the amount of solid content applied after drying was 1 g / m 2 . After drying, it was heat-treated at 50 ° C. and cured.
- the magenta dye layer coating liquid (M1), the yellow dye layer coating liquid (Y1), the cyan dye layer coating liquid (C1), and A heat-sensitive transfer recording sheet was prepared in which the transferable protective layer laminates were applied in a surface-sequential manner (so that the regions of each hue were adjacent to each other on the easy-adhesion-treated surface).
- the solid content coating amount of each dye layer was adjusted to 0.8 g / m 2 .
- the release layer coating liquid is applied, dried, the protective layer coating liquid is applied on the protective layer coating liquid, and after further drying, the adhesive layer is applied on the release layer coating liquid. It was carried out by applying a working solution.
- Examples 2 to 90 and Comparative Examples 1 to 13 Magenta dye (M dye), yellow dye (Y dye), cyan dye (C1) in the preparation of magenta dye layer coating liquid (M1), yellow dye layer coating liquid (Y1), and cyan dye layer coating liquid (C1).
- the heat-sensitive transfer recording sheets of Examples 2 to 90 in the same manner as in Example 1 except that the combination of (C dye) was changed as shown in Table 1-1 and Table 1-2 (collectively referred to as Table 1).
- the heat-sensitive transfer recording sheets of Comparative Examples 1 to 13 were prepared.
- the amount of dye in each dye layer coating liquid is the same as that of M1, Y1 and C1 (5.0 parts by mass), and when multiple types of dyes are used in a certain dye layer coating liquid, a plurality of types are used.
- the total amount of dyes was 5.0 parts by mass, and the amount ratios of the plurality of dyes were adjusted as shown in Table 1 and used.
- the heat-sensitive transfer recording sheets of Examples 1 to 90 of the present invention and the heat-sensitive transfer recording sheets of Comparative Examples 1 to 13 are heat-sensitive transfer printers (Fujifilm Thermal Photoprinter ASK-300 (trade name), manufactured by FUJIFILM Corporation). An image print was output on printing paper (Fujifilm Quality Thermal Photo Paper (trade name), manufactured by FUJIFILM Corporation), and the following evaluation test was conducted.
- Tables 2-1 to 2-4 are collectively referred to as Table 2.
- Evaluation test 1 Process black density evaluation Necessary for color measurement using color chart data (S7, S8, S9, and S10) of high-definition color digital standard image CMYK / SCID (JIS standard X9201: 2001) as an output image. Taking into account the size, all 928 color charts were printed so that one color chart would be 10 mm square. Using an automatic scanning table (i1iO (trade name), manufactured by X-Rite), the obtained color charts are measured for L *, a *, and b * values in the CIELab color system at a viewing angle of 2 °. did.
- CMYK / SCID JIS standard X9201: 2001
- a color chart group having a * value and a b * value of -3 or more and less than 3 is extracted from all the color chart groups, and the color chart group is included.
- the L * value of the smallest L * value (highest density black) was evaluated according to the following evaluation criteria. The results are shown in Table 2. In this evaluation, the smaller the value of the lightness L *, the higher the density as black. As black, when the brightness is 22 or more, it is grayish and blurry black, but when the brightness is around 20, it becomes a black that can be practically tolerated, and when the brightness is smaller than 18, it is a high density that gives a sense of luxury and profoundness. It becomes black. In addition, high density black is important for printing characters and barcodes more clearly. --Evaluation criteria-- A: less than 18 B: 18 or more and less than 22 C: 22 or more
- Evaluation test 2 Evaluation of other color tightening effect Evaluation was performed using the evaluation image pattern 1 shown in FIG.
- K indicates a process black portion (RGB values: R0, G0, B0)
- Y indicates a yellow portion (RGB values: R255, G255, B0)
- M indicates a magenta portion (RGB values: R0, G0, B0).
- C indicates a cyan portion (RGB values R0, G255, B255)
- W indicates a white portion (RGB values R255, G255, B255).
- the process black portion (K) has a size of 90 mm ⁇ 90 mm, and the yellow portion (Y), the magenta portion (M), the cyan portion (C), and the white portion (W) are respectively. It has a size of 25 mm ⁇ 25 mm.
- the yellow portion (Y), the magenta portion (M), the cyan portion (C), and the white portion (W) are formed in the process black portion at intervals of 10 mm in two upper and lower stages.
- the process black portion has the highest reached density (highest density black), and the yellow, magenta, and cyan portions have the reflection density (ISO density status T, viewing angle 2 °). Was printed so as to be 1.0.
- the white part is the part where the dye is not transferred (the color part of the photographic paper).
- the obtained print of the image pattern 1 for evaluation was visually evaluated according to the following evaluation criteria. The number of panels was 10, and the evaluation criteria shown by the most panels were used as the evaluation values.
- the single solid image having the same density used for the evaluation is an image obtained by printing only an image having the same RGB value as the yellow part, the magenta part, or the cyan part with the same reflection density as the above. Furthermore, the unprinted photographic paper was used as a single solid white image. The results are shown in Table 2. --Evaluation criteria--- A: It looks very tight (the color part (yellow part, magenta part, cyan part, and white part) looks darker than the solid image with the same density alone, and the outline is clear). B: Looks tight (the color part looks the same as the solid image with the same density, but the outline is clear)
- C It looks blurry (the color part looks lighter than the solid image with the same density, or the outline looks blurry).
- Evaluation test 3 Color reproduction volume evaluation L * value, a * value, in the CIELab color system printed using the above-mentioned evaluation test 1 and measured using an automatic scanning table (i1iO (trade name), manufactured by X-Rite). And b * values were plotted three-dimensionally to calculate the color reproduction volume of each heat-sensitive transfer recording sheet. With respect to the obtained color reproduction volume, a relative value was obtained with the color reproduction volume of Comparative Example 4 as a reference (100%), and the evaluation was made according to the following evaluation criteria. The results are shown in Table 2. The higher the color reproduction volume, the more various colors can be expressed, including highly saturated colors.
- the color reproduction volume not only enables design that can realize faithful color reproduction in photographic prints, but also makes it possible to reproduce vivid primary colors that could not be reproduced in conventional prints for digital images that often use primary colors. It also shows that it is possible to reproduce similar colors.
- Evaluation criteria-- S 110% or more A: 105% or more and less than 110% B: 100% or more and less than 105% C: less than 100%
- Evaluation test 4 Light resistance evaluation 1 / Monochromatic fading balance The balance of fading property due to light in the monochromatic region of each dye was evaluated as follows. Images of yellow, magenta, and cyan of 30 mm square were printed separately so that the reflection densities of yellow, magenta, and cyan (ISO density status T, viewing angle 2 °) were 1.0. The obtained print was subjected to a light resistance test (sample temperature 25 ° C., irradiation amount 100 kilolux, 366 nm or less cutoff filter used, irradiation time) using a xenon weather meter (XL-75L (trade name), manufactured by Suga Test Instruments Co., Ltd.). 72 hours) was carried out.
- XL-75L xenon weather meter
- the reflection concentrations of yellow, magenta, and cyan after the test were measured, and the residual ratio with respect to the reflection density before the light resistance test was calculated for each.
- the difference between the maximum and the minimum was calculated and evaluated according to the following evaluation criteria.
- the evaluation criteria are as follows. The results are shown in Table 2.
- the small difference in the residual rate means that the photobleaching speeds of the dyes in the single color portions of the yellow, magenta, and cyan prints of the printed image are close to each other, and the fading balance is excellent. It is preferable that the color fading balance is excellent because the color fades evenly without color bias.
- Evaluation test 5 Light resistance evaluation 2 / Gray fading balance The balance of fading property due to light in the color mixing region of each dye was evaluated as follows. A 30 mm square gray image was printed with a yellow, magenta, and cyan heat-sensitive transfer recording sheet, and the reflection densities of yellow, magenta, and cyan (ISO density status T, viewing angle 2 °) were 1.0. A printed image (gray) was created by sequentially stacking and printing so as to be.
- a light resistance test (sample temperature 25 ° C., irradiation amount 100 kilolux, 366 nm or less cutoff filter used, irradiation) was performed on this printed image using a xenon weather meter (XL-75L (trade name), manufactured by Suga Test Instruments Co., Ltd.). Time 72 hours) was carried out.
- the reflection densities of yellow, magenta, and cyan in the gray image after the test were measured, and the residual ratio with respect to the reflection density before each light resistance test was calculated.
- the difference between the maximum and the minimum was calculated and evaluated according to the following evaluation criteria. The results are shown in Table 2.
- the fact that the difference in the residual rate is small indicates that the color fading balance due to light in the gray portion (color mixed portion) of the printed image is good.
- the dyes of each hue may have a significantly different degree of fading due to light due to the interaction within the color mixing region.
- the fading balance of the mixed color portion in the printed image is very important in the photographic print. If the gray fading balance is poor, for example, in a print of a person's face, black hair changes to brown hair, and the skin color changes to reddish (hot skin color) or bluish (skin color that makes you feel like blood), which is not preferable. If the gray fading balance is excellent, the above problem is solved and it is preferable as the fading of the print. --Evaluation criteria-- A: Less than 5% B: 5% or more and less than 10% C: 10% or more
- Evaluation test 6 Evaluation over time at high temperature and high humidity in a dark place The balance of fading property at high temperature when each dye was mixed was evaluated as follows.
- the gray image created in the same manner as in the evaluation test 5 was placed in a constant temperature and humidity machine (model number: ARS-0220-J, manufactured by ESPEC) under high temperature and high humidity aging conditions in a dark place (temperature 65 ° C., relative humidity 70%). RH, 90 days in time).
- the reflection densities of yellow, magenta, and cyan in the gray image after the treatment were measured, respectively, and the residual ratio with respect to the reflection density before the treatment was calculated.
- the difference between the maximum and the minimum was calculated and evaluated according to the following evaluation criteria. The results are shown in Table 2. The smaller the difference in the residual rate, the better the gray fading balance due to the high temperature and high humidity of the printed image.
- Evaluation test 7 Reverse transferability Each dye is sequentially printed on the image forming area of photographic paper so that solid images (50 mm square) of magenta, yellow, and cyan dyes overlap in this order to produce a black print image. Obtained.
- the magenta dye in the dye contained in each dye layer is extracted from the yellow dye layer and the cyan dye layer of the heat-sensitive transfer recording sheet after use using methyl ethyl ketone / toluene (weight ratio 1/1). Quantified using high speed chromatography. The ratio (mass%) of the magenta dye to the total dye content in each dye layer was determined, and the largest value was evaluated according to the following evaluation criteria. The results are shown in Table 2.
- the thermal transfer recording sheets of Examples 1 to 90 can form a high-concentration process black and tighten other colors. Since it also has an effect, it can be seen that a good black can be formed.
- each thermal transfer recording sheet of the present invention has a wider color reproduction volume and can express various colors.
- the color reproducibility tends to be improved by using the cyan dye as at least one of a compound represented by the general formula (8) and a compound represented by any of the general formulas (9) to (12). ..
- each thermal transfer recording sheet of the present invention Comparing each thermal transfer recording sheet of the present invention with each thermal transfer recording sheet of the comparative example, in a preferable form of each thermal transfer recording sheet of the present invention, the fading balance is good even when exposed to light or high temperature and high humidity conditions. , It can be seen that the color balance of the image lasts a long time.
- the cyan dye as at least one of a compound represented by the general formula (8) and a compound represented by any of the general formulas (9) to (12), each dye due to light in the color mixing portion can be used.
- the balance of fading can be further enhanced, and if the compound represented by the general formula (8) and the compound represented by the general formula (12) are used, the balance of fading of each dye due to light and high temperature and humidity can be further enhanced.
- each thermal transfer recording sheet of the present invention Comparing each thermal transfer recording sheet of the present invention with each thermal transfer recording sheet of the comparative example, it can be seen that there is little reverse transfer in the preferred form of each thermal transfer recording sheet of the present invention.
- the cyan dye as at least one of a compound represented by the general formula (8) and a compound represented by any of the general formulas (9) to (12), reverse transcription can be efficiently reduced. Can be done.
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Abstract
Description
従来、感熱転写記録シートの色素及びその組み合わせの改良は様々な試みがなされている。例えば特許文献1ではイソチアゾリルアゾチアゾール色素を用いた感熱転写記録シートが提案されている。また特許文献2ではイソチアゾリルアゾチアゾール色素を含むマゼンタ染料層とアリーリデンピラゾロン色素を含むイエロー染料層を有する感熱転写記録シートが提案されている。この感熱転写記録シートによれば、肌色の再現性を高めることができることが記載されている。
上記方式による印刷は、近年では写真プリント以外にも、従業員証や学生証のような身分証明書(IDカード)にも用いられるようになってきた。この身分証明書においては、文字情報やバーコードの印刷部分に用いられるブラックの品質(特に色味)は非常に重要である。そのためブラックは、ブラック染料のみを用いて印刷されたり、熱溶融法転写方式によって別プロセスとして印刷されたりしている。しかし、印刷の速度向上やコストの点で、シアン染料、イエロー染料、マゼンタ染料の3色を順次転写させて形成するプロセスブラックで上記用途に十分な高品質のブラックを表現できることが望まれているが、その色味については改善の余地があった。
さらに、上記方式による印刷対象の拡大に伴い、これまであまりなかったプリント配色(例えば黒地背景のカラーでの文字情報印刷など)が多く使用されるようになってきた。このような配色においては黒地の濃さ(ブラックの高濃度化)による視覚効果によってカラーが際立つため(他色の引き締め効果)、ブラックの高品質化が求められ続けている。
特許文献1は、イソチアゾリルアゾチアゾール色素を含有する感熱転写記録シートについて記載しているものの、他の色相の染料との組合せについては具体的な開示がない。
特許文献2に記載の感熱転写記録シートには、形成されるプロセスブラックによる他色の引き締め効果等の点で改善の余地があった。
本発明は、高濃度かつ色味に優れ、他色の引き締め効果にも優れたプロセスブラックの形成が可能な感熱転写記録シートを提供することを課題とする。
〔1〕
基材と、基材上に色材層とを有する感熱転写記録シートであって、
色材層は、イエロー染料を含有するイエロー染料層、マゼンタ染料を含有するマゼンタ染料層、及びシアン染料を含有するシアン染料層を有し、
マゼンタ染料は、下記一般式(1)で表される化合物を含み、
イエロー染料は、下記一般式(2)~(7)のいずれかで表される化合物の少なくとも1種を含み、
シアン染料は、下記一般式(8)~(12)のいずれかで表される化合物の少なくとも1種を含む、
感熱転写記録シート。
シアン染料が、一般式(8)で表される化合物と、一般式(9)~(12)のいずれかで表される化合物の少なくとも1種とを含む、〔1〕に記載の感熱転写記録シート。
〔3〕
シアン染料中、一般式(8)で表される化合物の含有量(I)と、一般式(9)~(12)のいずれかで表される化合物の含有量の合計(II)との比が、質量比で、(I):(II)=90~50:10~50である、〔1〕又は〔2〕に記載の感熱転写記録シート。
〔4〕
シアン染料が、一般式(8)で表される化合物と一般式(12)で表される化合物とを含む、〔1〕~〔3〕のいずれか1つに記載の感熱転写記録シート。
〔5〕
イエロー染料が、一般式(4)で表される化合物と、一般式(2)、(3)、(5)、(6)及び(7)のいずれかで表される化合物の少なくとも1種とを含む、〔1〕~〔4〕のいずれか1つに記載の感熱転写記録シート。
〔6〕
イエロー染料が、一般式(4)で表される化合物と、一般式(2)及び(6)のいずれかで表される化合物の少なくとも1種とを含む、〔1〕~〔5〕のいずれか1つに記載の感熱転写記録シート。
〔7〕
イエロー染料が、一般式(3)で表される化合物と、一般式(2)で表される化合物とを含む、〔1〕~〔4〕のいずれか1つに記載の感熱転写記録シート。
マゼンタ染料が、一般式(1)で表される化合物と、下記一般式(13)~(20)のいずれかで表される化合物の少なくとも1種とを含む、〔1〕~〔7〕のいずれか1つに記載の感熱転写記録シート。
マゼンタ染料が、一般式(1)で表される化合物と、一般式(15)で表される化合物とを含む、〔1〕~〔8〕のいずれか1つに記載の感熱転写記録シート。
〔10〕
マゼンタ染料が、一般式(1)で表される化合物と、一般式(15)で表される化合物と、一般式(13)で表される化合物とを含む、〔1〕~〔9〕のいずれか1つに記載の感熱転写記録シート。
〔11〕
マゼンタ染料が、一般式(1)で表される化合物と、一般式(13)で表される化合物と、一般式(14)で表される化合物とを含む、〔1〕~〔9〕のいずれか1つに記載の感熱転写記録シート。
本明細書において化合物の表示(例えば、化合物と末尾に付して呼ぶとき)については、この化合物そのもののほか、その塩、そのイオンを含む意味に用いる。また、所望の効果を奏する範囲で、置換基を導入するなど構造の一部を変化させた誘導体を含む意味である。
本明細書において置換基が解離性の水素原子(水素原子が塩基の作用により解離する基)を有する場合、この置換基にはイオンないし塩の形態が含まれる。
本明細書において置換又は無置換を明記していない置換基、連結基等(以下、置換基等という。)については、その基に適宜の置換基を有していてもよい意味である。よって、本明細書において、単に、「~基」(例えば「アルキル基」)と記載されている場合であっても、この「~基」(例えば「アルキル基」)は、置換基を有しない態様(例えば「無置換アルキル基」)に加えて、更に置換基を有する態様(例えば「置換アルキル基」)も包含する。これは置換又は無置換を明記していない化合物についても同義である。好ましい置換基としては、後記する置換基Tが挙げられる。
本明細書において単に「置換基」という場合、後記する置換基Tから選ばれる置換基が好ましく適用される。
本明細書において、特定の符号で示された置換基等が複数あるとき、又は複数の置換基等を同時若しくは択一的に規定するときには、それぞれの置換基等は互いに同一でも異なっていてもよいことを意味する。また、特に断らない場合であっても、複数の置換基等が隣接するときにはそれらが互いに連結したり縮環したりして環を形成していてもよい意味である。
本発明において、アルキル基というときは、直鎖、分岐、もしくは環状のアルキル基を表す。アルキル基を含む基(アルコキシ基、アルコキシカルボニル基等)中のアルキル基についても同様である。
本発明において、ある基の炭素数を規定する場合、この炭素数は、本発明ないし本明細書において特段の断りのない限りは、基全体の炭素数を意味する。つまり、この基がさらに置換基を有する形態である場合、この置換基を含めた全体の炭素数を意味する。
本発明において、炭素数0のアミノ基とは一般的な無置換アミノ基(NH2基)を表す。アミノ基の炭素数が1以上であるとき、その炭素数は置換基を含めたアミノ基全体の炭素数を意味する。例えば、後述する例示化合物(7-1)は、一般式(7)におけるR71として炭素数2のアミノ基(ジメチルアミノ基)を有している。
最初に、本発明の感熱転写記録シートについて詳細に説明する。
本発明の感熱転写記録シートは、基材と、基材上に色材層とを有する感熱転写記録シートであり、色材層は、イエロー染料を含有するイエロー染料層、マゼンタ染料を含有するマゼンタ染料層、及びシアン染料を含有するシアン染料層を有する。
本発明の感熱転写記録シートは、基材上に色材層を有し、色材層は、イエロー染料層、マゼンタ染料層、及びシアン染料層を有する。本発明の感熱転写記録シートは、これらの染料層に加えて、ブラック染料層を有していてもよい。これらの染料層は、同一の基材上に面順次に塗り分けられているのが好ましい。一例として、イエロー、マゼンタ及びシアンの各色相の染料層が同一の基材の長軸方向に、感熱転写受像シートの記録面の面積に対応して面順次に塗り分けられている場合を挙げることができる。基材を長尺にして、上記各染料層を面順次に繰り返し塗り分けてもよい。この3層に加えて、ブラックの色相の染料層と転写性保護層のどちらか、あるいは双方が塗り分けられるのも好ましい態様である。
この様な態様を取る場合、各色の開始点をプリンターに伝達する目的で、感熱転写記録シート上に目印を付与することも好ましい態様である。このように面順次で塗り分けることによって、染料の転写による画像の形成、さらには画像上への保護層の積層を一つの感熱転写記録シートで行なうことが可能となる。
しかしながら、本発明は上記のような染料層の設け方に限定されるものではない。昇華型熱転写インク層(染料層)と熱溶融転写インク層を併設することも可能であり、また、イエロー、マゼンタ、シアン及びブラック以外の色相の染料層を設ける等の変更をすることも可能である。また、形態としては長尺であっても良いし、枚葉の熱転写シートであっても良い。
染料層の塗布は、ロールコート、バーコート、グラビアコート、グラビアリバースコート等の一般的な方法で行われる。また染料層の塗布量は、0.1~2.0g/m2(固形分換算、以下本発明における塗布量は特に断りのない限り、固形分換算の数値である。)が好ましく、更に好ましくは0.2~1.2g/m2である。染料層の膜厚は0.1~2.0μmであることが好ましく、更に好ましくは0.2~1.2μmである。
以下、各染料について説明する。
マゼンタ染料は、下記一般式(1)で表される化合物を含み、イエロー染料は、下記一般式(2)~(7)のいずれかで表される化合物の少なくとも1種を含み、シアン染料は、下記一般式(8)~(12)のいずれかで表される化合物の少なくとも1種を含む。
さらに、マゼンタ染料は、一般式(1)で表される化合物に加えて、一般式(13)~(20)で表される化合物の少なくとも1種を含む態様とすることもできる。
本発明において、下記一般式で表される化合物は、その異性体構造(例えば、互変異性体構造)の少なくとも1つがこの一般式に当てはまる限り、どのような異性体構造をとるものでもよい。
以下に、本発明で使用する一般式(1)~(20)で表される化合物についてさらに詳細に説明する。
R12はフェニル基、又は炭素数1~4の無置換アルキル基を示す。R12としてとりうるフェニル基は、置換基を有していてもよい。R12における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、脂肪族基、不飽和脂肪族基、アリール基、脂肪族オキシ基、アシルオキシ基、脂肪族オキシカルボニルオキシ基、アミノ基、アシルアミノ基、アミノカルボニルアミノ基、脂肪族もしくはアリールスルホニルアミノ基、脂肪族チオ基、スルファモイル基、脂肪族もしくはアリールスルホニル基、アシル基、脂肪族オキシカルボニル基、カルバモイル基、水酸基、シアノ基、ニトロ基等が好ましい。R12は、メチル基、エチル基、プロピル基、ブチル基、又は無置換フェニル基が好ましく、t-ブチル基、又は無置換フェニル基がより好ましい。
R13及びR14は炭素数1~8のアルキル基を示す。R13及びR14としてとりうる炭素数1~8のアルキル基は、置換基を有していてもよい。R13及びR14における置換基としては、後述する置換基Tから選択される置換基が挙げられ、水酸基、ハロゲン原子、不飽和脂肪族基、アリール基、脂肪族オキシ基、アシルオキシ基(より好ましくは、アルキルカルボニルオキシ基)、アリールオキシカルボニルオキシ基、アミノ基、アシルアミノ基、脂肪族オキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、脂肪族もしくはアリールスルホニルアミノ基、脂肪族チオ基、脂肪族もしくはアリールスルホニル基、アシル基、アリールオキシカルボニル基、脂肪族オキシカルボニル基、カルバモイル基、シアノ基等が好ましい。R13及びR14は、炭素数2~6のアルキル基が好ましく、炭素数2~4の無置換アルキル基、及び、水酸基、アルキルカルボニルオキシ基、又はアルキルカルボニル基を置換基として有する炭素数2~4のアルキル基がより好ましい。
R23は水素原子、又はメチル基を示す。R23は、メチル基であることが好ましい。
R24は水素原子、又はアルキル基を示す。R24としてとりうるアルキル基の炭素数は、1~8が好ましく、1~6がより好ましく、1~5がさらに好ましい。R24としてとりうるアルキル基は、置換基を有していてもよい。R24における置換基としては、不飽和脂肪族基、アリール基、脂肪族オキシ基、アシルオキシ基、脂肪族オキシカルボニルオキシ、アミノ基、アシルアミノ基、アミノカルボニルアミノ基、脂肪族オキシカルボニルアミノ基、スルファモイルアミノ基、脂肪族もしくはアリールスルホニルアミノ基、脂肪族チオ基、スルファモイル基、脂肪族もしくはアリールスルホニル基、アシル基、脂肪族オキシカルボニル基、カルバモイル基、水酸基等が挙げられる。
R21とR24は互いに結合して環を形成してもよい。
R24は、水素原子であるか、R21と結合して環を形成していることが好ましく、水素原子であるか、R21と結合してピペリジン環(置換基を有していてもよい)を形成していることがより好ましい。
R31は水素原子、又は炭素数1~4の無置換アルキル基を示す。R31は、水素原子、メチル基、エチル基、又はプロピル基が好ましく、水素原子又はイソプロピル基であることがより好ましい。
R32及びR33は炭素数1~6のアルキル基を示す。R32及びR33としてとりうる炭素数1~6のアルキル基は、置換基を有していてもよい。R32及びR33における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、不飽和脂肪族基、アリール基、脂肪族オキシ基、アシルオキシ基、脂肪族オキシカルボニルオキシ、アシルアミノ基、アミノカルボニルアミノ基、脂肪族オキシカルボニルアミノ基、脂肪族もしくはアリールスルホニルアミノ基、脂肪族チオ基、スルファモイル基、脂肪族もしくはアリールスルフィニル基、脂肪族もしくはアリールスルホニル基、アシル基、脂肪族オキシカルボニル基、水酸基、シアノ基等が好ましい。R32及びR33は、炭素数1~4の無置換アルキル基が好ましく、n-プロピル基、n-ブチル基がより好ましい。
R41は炭素数1~4の無置換アルコキシ基、又は炭素数0~4のアミノ基を示す。R41としてとりうる炭素数0~4のアミノ基は、置換基を有していてもよい。R41における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、脂肪族基、不飽和脂肪族基、アリール基、脂肪族オキシ基、アシルオキシ基水酸基、シアノ基等が好ましい。R41は、炭素数1~4の無置換アルコキシ基、又はアルキルアミノ基が好ましく、エトキシ基、又はジメチルアミノ基がより好ましい。
R42及びR43は炭素数1~4のアルキル基を示す。R42及びR43としてとりうる炭素数1~4のアルキル基は、置換基を有していてもよい。R42及びR43における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、不飽和脂肪族基、脂肪族オキシ基、アシルオキシ基、脂肪族オキシカルボニルオキシ、脂肪族チオ基、脂肪族オキシカルボニル基、水酸基、シアノ基等が好ましい。R43及びR43は、炭素数1~4の無置換アルキル基が好ましく、エチル基がより好ましい。
R52は炭素数1~6のアルキル基を示す。R52としてとりうる炭素数1~6のアルキル基は、置換基を有してもよい。R52における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、不飽和脂肪族基、アリール基、脂肪族オキシ基、アシルオキシ基、脂肪族チオ基、水酸基等が好ましい。R52は、炭素数1~4の無置換アルキル基が好ましく、n-ブチル基がより好ましい。
R61及びR62としてとりうる炭素数1~4のアルキル基は、置換基を有していてもよい。R61及びR62における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、不飽和脂肪族基、アリール基、脂肪族オキシ基、アシルオキシ基、アシル基、水酸基が好ましい。R61及びR62は、炭素数1~4の無置換アルキル基が好ましく、メチル基がより好ましい。
R71としてとりうる炭素数1~4のアルコキシ基及び炭素数0~4のアミノ基は、置換基を有していてもよい。R71における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、脂肪族基、不飽和脂肪族基、アリール基、脂肪族オキシ基、アシルオキシ基、水酸基、シアノ基等が好ましい。R71は、炭素数1~4の無置換アルコキシ基、又はアルキル基を置換基として有する炭素数1~4のアミノ基が好ましく、エトキシ基、又はジメチルアミノ基がより好ましい。
R72、R73及びR74は炭素数1~4のアルキル基を示す。R72、R73及びR74としてとりうる炭素数1~4のアルキル基は、置換基を有していてもよい。R72、R73及びR74における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、不飽和脂肪族基、アリール基、脂肪族オキシ基、アシルオキシ基、水酸基等が好ましい。R72、R73及びR74は、炭素数1~4の無置換アルキル基が好ましく、メチル基、又はエチル基がより好ましい。
R81及びR82は炭素数1~6の無置換アルキル基を示す。R81及びR82は、炭素数1~4の無置換アルキル基が好ましく、メチル基、エチル基、又はプロピル基がより好ましい。
R83は水素原子、炭素数1~4の無置換アルキル基、又は炭素数1~4の無置換アルコキシ基を示す。R83は、水素原子、メチル基、エチル基、メトキシ基、又はエトキシ基が好ましく、水素原子、メチル基、エトキシ基がより好ましい。
R84はメチル基、又はエチル基を示す。
R85は炭素数1~4のアルキル基、アリール基、又は5員もしくは6員のヘテロアリール基を示す。R85としてとりうるアリール基は、炭素数6~30のアリール基が好ましく、フェニル基、ナフチル基等が挙げられる。R85としてとりうる5もしくは6員のヘテロアリール基は、ヘテロ原子として、酸素原子、窒素原子、及び硫黄原子のいずれを有するものでもよく、フリル基、ピリジル基、チエニル基等が挙げられる。R85としてとりうる炭素数1~4のアルキル基、アリール基、及び5もしくは6員のヘテロアリール基は、置換基を有していてもよい。R85における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、脂肪族基、不飽和脂肪族基、アリール基、脂肪族オキシ基、アシルオキシ基、脂肪族オキシカルボニルオキシ、アリールオキシカルボニルオキシ基、アミノ基、アシルアミノ基、アミノカルボニルアミノ基、脂肪族オキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、脂肪族チオ基、脂肪族もしくはアリールスルホニル基、アシル基、アリールオキシカルボニル基、脂肪族オキシカルボニル基、水酸基、シアノ基、ニトロ基等が好ましい。R85は、炭素数1~4の無置換アルキル基、フェニル基、フリル基又はピリジル基が好ましく、メチル基、エチル基、フリル基、又はピリジル基がより好ましい。
R92は水素原子、炭素数1~4のアルキル基、又は炭素数1~4のアルコキシ基を示す。R92としてとりうる炭素数1~4のアルキル基及び炭素数1~4のアルコキシ基は、置換基を有していてもよい。R92における置換基としては、ハロゲン原子、不飽和脂肪族基、脂肪族オキシ基、アシルオキシ基、脂肪族オキシカルボニルオキシ、脂肪族チオ基水酸基等が挙げられる。R92は、水素原子、炭素数1~4の無置換アルキル基、又は炭素数1~4の無置換アルコキシ基が好ましく、水素原子、メチル基、又はメトキシ基がより好ましい。
R93及びR94は炭素数1~6のアルキル基を示す。R93及びR94としてとりうる炭素数1~6のアルキル基は、置換基を有していてもよい。R93及びR94における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、不飽和脂肪族基、脂肪族オキシ基、アシルオキシ基、脂肪族オキシカルボニルオキシ、アシル基、脂肪族オキシカルボニル基、水酸基、シアノ基等が好ましい。R93及びR94は、炭素数1~4の無置換アルキル基が好ましく、エチル基、イソプロピル基がより好ましく、エチル基がさらに好ましい。
R103は水素原子、又は炭素数1~3のアルキル基を示す。R103として取りうる炭素数1~3のアルキル基は、置換基を有していてもよい。R103における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、不飽和脂肪族基、脂肪族オキシ基、脂肪族チオ基等が好ましい。R103は、炭素数1~3の無置換アルキル基が好ましく、メチル基がより好ましい。
R113は炭素数1~4のアルキル基を示す。R113としてとりうる炭素数1~4のアルキル基は、置換基を有していてもよい。R113における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、不飽和脂肪族基、脂肪族オキシ基、水酸基等が好ましい。R113は、炭素数1~4の無置換アルキル基が好ましく、メチル基がより好ましい。
R121及びR122としてとりうる炭素数6~10のアリール基としては、フェニル基、ナフチル基が挙げられる。R121及びR122としてとりうる炭素数1~6のアルキル基及び炭素数6~10のアリール基は、置換基を有していてもよい。R121及びR122における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、脂肪族基(アルキル基が好ましい)、不飽和脂肪族基、アリール基、脂肪族オキシ基、アシルオキシ基、脂肪族オキシカルボニルオキシ、アリールオキシカルボニルオキシ基、アシルアミノ基、脂肪族オキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、脂肪族もしくはアリールスルホニルアミノ基、脂肪族チオ基、脂肪族もしくはアリールスルホニル基、アシル基、アリールオキシカルボニル基、脂肪族オキシカルボニル基、水酸基、シアノ基等が好ましい。R121及びR122としては、炭素数1~6の無置換アルキル基、及びアルキル基を置換基として有するフェニル基が好ましく、メチル基、エチル基、イソプロピル基、及びメチルフェニル基がより好ましい。
R131としてとりうるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、及びヨウ素原子が挙げられ、臭素原子が好ましい。
R131としてとりうる炭素数6~10のアリールオキシ基が有するアリール基は、フェニル基、ナフチル基が好ましい。
R131としてとりうる炭素数1~8のアルコキシ基及び炭素数6~10のアリールオキシ基は、置換基を有していてもよい。R131における置換基としては、後述する置換基Tから選択される置換基が挙げられ、水酸基、ハロゲン原子、脂肪族基、不飽和脂肪族基、アリール基、脂肪族オキシ基、アシルオキシ基、脂肪族オキシカルボニルオキシ、アリールオキシカルボニルオキシ基、脂肪族チオ基、アシル基、アリールオキシカルボニル基、脂肪族オキシカルボニル基、シアノ基等が好ましい。
R131は、水酸基を置換基として有するアルコキシ基、ハロゲン原子、又は炭素数6~10の無置換アリールオキシ基が好ましく、水酸基を置換基として有するエトキシ基、フェノキシ基、又は臭素原子が好ましい。
R141及びR142としてとりうる炭素数6~10のアリール基は、フェニル基、ナフチル基が好ましい。R141及びR142としてとりうる炭素数6~10のアリール基は、置換基を有していてもよい。R141及びR142における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、脂肪族基、不飽和脂肪族基、脂肪族オキシ基、アシルオキシ基、脂肪族オキシカルボニルオキシ、アシルアミノ基、アミノカルボニルアミノ基、脂肪族オキシカルボニルアミノ基、脂肪族チオ基、アシル基、脂肪族オキシカルボニル基、水酸基、シアノ基等が好ましい。R141及びR142は、フェニル基が好ましい。
R152は炭素数1~4のアルキル基を示す。R152としてとりうる炭素数1~4のアルキル基は、置換基を有していてもよい。R152における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、脂肪族基、不飽和脂肪族基、脂肪族オキシ基、水酸基等が好ましい。R152としては、炭素数1~4の無置換アルキル基が好ましく、メチル基がより好ましい。
R153及びR154は炭素数1~6のアルキル基を示す。R153及びR154としてとりうる炭素数1~6のアルキル基は、置換基を有していてもよい。R153及びR154における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、不飽和脂肪族基、脂肪族オキシ基、アシルオキシ基、アシルアミノ基、水酸基、シアノ基等が好ましい。R153及びR154としては、炭素数2~6の無置換アルキル基が好ましく、n-プロピル基、n-ブチル基が好ましい。
R162及びR163は炭素数1~10のアルキル基を示す。R162及びR163としてとりうる炭素数1~10のアルキル基は、置換基を有していてもよい。R162及びR163における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、不飽和脂肪族基、アリール基(フェニル基が好ましい)脂肪族オキシ基、アシルオキシ基(アルキルカルボニルオキシ基が好ましい)、アシルアミノ基、脂肪族オキシカルボニルアミノ基、脂肪族もしくはアリールスルホニルアミノ基、脂肪族チオ基、脂肪族もしくはアリールスルホニル基、アシル基、アリールオキシカルボニル基、脂肪族オキシカルボニル基、水酸基、シアノ基等が好ましい。R162及びR163としては、炭素数1~4の無置換アルキル基(より好ましくは、メチル基、エチル基)、メチルカルボニルオキシエチル基、ベンジル基等が好ましい。
R172は炭素数1~6のアルキル基、又は炭素数6~10のアリール基を示す。R172としてとりうる炭素数6~10のアリール基としては、フェニル基、ナフチル基が挙げられる。R172としてとりうる炭素数1~6のアルキル基及び炭素数6~10のアリール基は、置換基を有していてもよい。R172における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、脂肪族基(アルキル基が好ましい)、脂肪族オキシ基、アシルオキシ基、アシルアミノ基、脂肪族チオ基、アシル基、脂肪族オキシカルボニル基等が好ましい。R172としては、置換基(好ましくはアルキル基)を有するフェニル基が好ましく、メチルフェニル基がより好ましい。
R173は水素原子、又は炭素数1~4のアルキル基を示す。R173としてとりうる炭素数1~4のアルキル基は、置換基を有していてもよい。R173における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、不飽和脂肪族基、脂肪族オキシ基、アシルオキシ基等が好ましい。R173としては、水素原子、又は炭素数1~4の無置換アルキル基が好ましく、メチル基がより好ましい。
R174及びR175は炭素数1~4のアルキル基を示す。R174及びR175としてとりうる炭素数1~4のアルキル基は、置換基を有していてもよい。R174及びR175における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、不飽和脂肪族基、脂肪族オキシ基、アシルオキシ基、アシル基、脂肪族オキシカルボニル基、水酸基、シアノ基等が好ましい。R174及びR175としては、炭素数1~4の無置換アルキル基が好ましく、エチル基がより好ましい。
R181としてとりうる炭素数6~10のアリール基としては、フェニル基、ナフチル基が挙げられる。R181としてとりうる炭素数1~4のアルキル基及び炭素数6~10のアリール基は、置換基を有していてもよい。R181における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、脂肪族基、脂肪族オキシ基、アシルオキシ基、アシル基等が好ましい。R181としては、置換基を有するフェニル基が好ましく、クロロフェニル基がより好ましい。
R182は炭素数1~12のアルキル基を示す。R182としてとりうる炭素数1~12のアルキル基の炭素数は、1~10が好ましく、2~10がより好ましく、2~6がさらに好ましい。R182としてとりうる炭素数1~12のアルキル基は、置換基を有していてもよい。R182における置換基としては、後述する置換基Tから選択される置換基が挙げられ、アリール基、脂肪族オキシ基、アミノ基、アシルアミノ基、アミノカルボニルアミノ基、脂肪族オキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、脂肪族もしくはアリールスルホニルアミノ基、イミド基(N-フタルイミド基が好ましい)等が好ましい。R182としては、炭素数3~12のアルキル基が好ましく、炭素数3~12の無置換アルキル基、又はN-フタルイミドを置換基として有する炭素数10~12のアルキル基が好ましく、イソプロピル基、又はN-フタルイミド基を置換基として有するイソプロピル基がより好ましい。
R183は水素原子、又は炭素数1~4のアルキル基を示す。R183としてとりうる炭素数1~4のアルキル基は、置換基を有していてもよい。R183における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、不飽和脂肪族基、脂肪族オキシ基、アシルオキシ基等が好ましい。R183は、炭素数1~4の無置換アルキル基、又は水素原子が好ましく、水素原子がより好ましい。
R184及びR185は炭素数1~12のアルキル基を示す。R184及びR185としてとりうる炭素数1~12のアルキル基の炭素数は、1~10が好ましく、2~9がより好ましく、2~6がさらに好ましい。R184及びR185としてとりうる炭素数1~12のアルキル基は、置換基を有していてもよい。R184及びR185における置換基としては、後述する置換基Tから選択される置換基が挙げられ、アルコキシ基、アリールオキシ基(さらに脂肪族オキシ基が置換していることが好ましく、例えば、アルコキシフェノキシ基)、アルキルカルボニルオキシ基、シアノ基等が好ましい。R184及びR185としては、炭素数2~6の無置換アルキル基、又はアルコキシ基、アルコキシフェノキシ基、アルキルカルボニルオキシ基、もしくはシアノ基を置換基として有する、炭素数2~11のアルキル基が好ましい。
R191及びR192としてとりうる炭素数1~6のアルキル基は、置換基を有していてもよい。R191及びR192における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、不飽和脂肪族基、脂肪族オキシ基、アシルオキシ基、アシル基、脂肪族オキシカルボニル基、水酸基、シアノ基等が好ましい。R191及びR192としては、炭素数3~6の無置換アルキル基が好ましく、n-ブチル基がより好ましい。
R193は炭素数1~6のアルキル基、又は炭素数6~10のアリール基を示す。R193としてとりうる炭素数6~10のアリール基としては、フェニル基、ナフチル基が挙げられる。R193としてとりうる炭素数1~6のアルキル基及び炭素数6~10のアリール基は、置換基を有していてもよい。R193における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、脂肪族基、不飽和脂肪族基、アリール基、脂肪族オキシ基、アシルオキシ基、アシルアミノ基、脂肪族もしくはアリールスルホニルアミノ基、脂肪族チオ基、アシル基、脂肪族オキシカルボニル基等が好ましい。R193としては、炭素数1~6の無置換アルキル基、炭素数6~10の無置換アリール基が好ましく、フェニル基、n-ブチル基、t-ブチル基がより好ましい。
R194はアルキル基、又は炭素数0~12のアミノ基を示す。R194としてとりうるアルキル基の炭素数は、1~12が好ましく、2~10がより好ましく、3~8がさらに好ましい。R194としてとりうる炭素数0~12のアミノ基の炭素数は、1~12が好ましく、2~12がより好ましく、2~10がさらに好ましい。R194としてとりうるアルキル基及び炭素数0~12のアミノ基は、置換基を有していてもよい。R194における置換基としては、後述する置換基Tから選択される置換基が挙げられ、アルキル基、アルキルカルボニル基、アリールカルボニル基等が好ましい。R194は、炭素数3~6の無置換アルキル基、又は置換基を有する炭素数2~12のアミノ基が好ましく、n-ブチル基、イソブチル基、又はアルキルカルボニル基もしくはアリールカルボニル基を置換基として有する炭素数4~12のアミノ基がより好ましい。
R201としてとりうる炭素数1~4のアルコキシ基及び炭素数0~6のアミノ基は、置換基を有していてもよい。R201における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、脂肪族基(アルキル基が好ましい)、不飽和脂肪族基、脂肪族オキシ基、アシルオキシ基、アシル基、脂肪族オキシカルボニル基、水酸基、シアノ基等が好ましい。R201は、炭素数1~4の無置換アルコキシ基、又は炭素数2~6のジアルキルアミノ基が好ましく、メトキシ基、エトキシ基、又はジメチルアミノ基がより好ましい。
R202及びR203は炭素数1~4のアルキル基を示す。R202及びR203としてとりうる炭素数1~4のアルキル基は、置換基を有していてもよい。R202及びR203における置換基としては、後述する置換基Tから選択される置換基が挙げられ、ハロゲン原子、不飽和脂肪族基、脂肪族オキシ基、アシルオキシ基、アシル基、脂肪族オキシカルボニル基、水酸基、シアノ基等が好ましい。R202及びR203は、炭素数1~4の無置換アルキル基が好ましく、メチル基、又はエチル基がより好ましい。
ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、及びヨウ素原子が挙げられる。中でも塩素原子、臭素原子が好ましく、特に塩素原子が好ましい。
脂肪族基は、直鎖、分枝または環状の脂肪族基であり、飽和脂肪族基には、アルキル基、シクロアルキル基、ビシクロアルキル基が含まれ、置換基を有してもよい。これらの炭素数は1~30が好ましい。例としてはメチル基、エチル基、n-プロピル基、イソプロピル基、t-ブチル基、n-オクチル基、エイコシル基、2-クロロエチル基、2-シアノエチル基、ベンジル基及び2-エチルヘキシル基を挙げることができる。シクロアルキル基は、炭素数3~30のシクロアルキル基が好ましい。例としては、シクロヘキシル基、シクロペンチル基、4-n-ドデシルシクロヘキシル基を挙げることができる。ビシクロアルキル基としては、炭素数5~30のビシクロアルキル基、つまり、炭素数5~30のビシクロアルカンから水素原子を一個取り去った一価の基を挙げることができる。例として、ビシクロ[1.2.2]ヘプタン-2-イル基、ビシクロ[2.2.2]オクタン-3-イル基を挙げることができる。さらに環構造が多いトリシクロ構造なども包含するものである。
ヘテロ環基は、芳香族もしくは非芳香族のヘテロ環化合物から一個の水素原子を取り除いた一価の基であり、それらはさらに縮環していてもよい。これらのヘテロ環基としては、好ましくは5または6員のヘテロ環基であり、また環構成のヘテロ原子としては、酸素原子、硫黄原子、窒素原子が好ましい。さらに好ましくは、炭素数3~30の5もしくは6員の芳香族のヘテロ環基である。ヘテロ環基におけるヘテロ環としては、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、キナゾリン環、シンノリン環、フタラジン環、キノキサリン環、ピロール環、インドール環、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピラゾール環、イミダゾール環、ベンズイミダゾール環、トリアゾール環、オキサゾール環、ベンズオキサゾール環、チアゾール環、ベンゾチアゾール環、イソチアゾール環、ベンズイソチアゾール環、チアジアゾール環、イソオキサゾール環、ベンズイソオキサゾール環、ピロリジン環、ピペリジン環、ピペラジン環、イミダゾリジン環、チアゾリン環が挙げられる。
脂肪族オキシ基(例えばアルコキシ基)は、炭素数は1~30が好ましい。例えば、メトキシ基、エトキシ基、イソプロポキシ基、n-オクチルオキシ基、メトキシエトキシ基、ヒドロキシエトキシ基及び3-カルボキシプロポキシ基などを挙げることができる。
アリールオキシ基は、炭素数6~30のアリールオキシ基が好ましい。アリールオキシ基の例として、フェノキシ基、2-メチルフェノキシ基、4-t-ブチルフェノキシ基、3-ニトロフェノキシ基、2-テトラデカノイルアミノフェノキシ基などを挙げることができる。好ましくは、置換基を有してもよいフェニルオキシ基である。
カルバモイルオキシ基は、炭素数1~30のカルバモイルオキシ基が好ましい。カルバモイルオキシ基の例には、N,N-ジメチルカルバモイルオキシ基、N,N-ジエチルカルバモイルオキシ基、モルホリノカルボニルオキシ基、N,N-ジ-n-オクチルアミノカルボニルオキシ基、N-n-オクチルカルバモイルオキシ基などを挙げることができる。
脂肪族オキシカルボニルオキシ基(例えばアルコキシカルボニルオキシ基)は、炭素数2~30が好ましく、置換基を有していてもよい。例えば、メトキシカルボニルオキシ基、エトキシカルボニルオキシ基、t-ブトキシカルボニルオキシ基、n-オクチルカルボニルオキシ基などを挙げることができる。
アリールオキシカルボニルオキシ基は、炭素数7~30のアリールオキシカルボニルオキシ基が好ましい。アリールオキシカルボニルオキシ基の例には、フェノキシカルボニルオキシ基、p-メトキシフェノキシカルボニルオキシ基、p-n-ヘキサデシルオキシフェノキシカルボニルオキシ基などを挙げることができる。好ましくは置換基を有してもよいフェノキシカルボニルオキシ基である。
アシルアミノ基は、ホルミルアミノ基、炭素数1~30のアルキルカルボニルアミノ基、炭素数6~30のアリールカルボニルアミノ基が好ましい。アシルアミノ基の例には、ホルミルアミノ基、アセチルアミノ基、ピバロイルアミノ基、ラウロイルアミノ基、ベンゾイルアミノ基、3,4,5-トリ-n-オクチルオキシフェニルカルボニルアミノ基などを挙げることができる。
アミノカルボニルアミノ基は、炭素数1~30のアミノカルボニルアミノ基が好ましい。アミノカルボニルアミノ基の例には、カルバモイルアミノ基、N,N-ジメチルアミノカルボニルアミノ基、N,N-ジエチルアミノカルボニルアミノ基、モルホリノカルボニルアミノ基などを挙げることができる。なお、この基における「アミノ」の用語は、前述のアミノ基における「アミノ」と同じ意味である。
アリールオキシカルボニルアミノ基は、炭素数7~30のアリールオキシカルボニルアミノ基が好ましい。アリールオキシカルボニルアミノ基の例には、フェノキシカルボニルアミノ基、p-クロロフェノキシカルボニルアミノ基、m-n-オクチルオキシフェノキシカルボニルアミノ基などを挙げることができる。置換基を有してもよいフェニルオキシカルボニルアミノ基が好ましい。
スルファモイルアミノ基は、炭素数0~30のスルファモイルアミノ基が好ましい。スルファモイルアミノ基の例には、スルファモイルアミノ基、N,N-ジメチルアミノスルホニルアミノ基、N-n-オクチルアミノスルホニルアミノ基などを挙げることができる。
脂肪族アリールスルホニルアミノ基は、炭素数1~30の脂肪族スルホニルアミノ基(例えばアルキルスルホニルアミノ基)、炭素数6~30のアリールスルホニルアミノ基(好ましくは置換基を有してもよいフェニルスルホニルアミノ基)が好ましい。例えば、メチルスルホニルアミノ基、ブチルスルホニルアミノ基、フェニルスルホニルアミノ基、2,3,5-トリクロロフェニルスルホニルアミノ基、p-メチルフェニルスルホニルアミノ基などを挙げることができる。
スルファモイル基は、炭素数0~30のスルファモイル基が好ましい。スルファモイル基の例には、N-エチルスルファモイル基、N-(3-ドデシルオキシプロピル)スルファモイル基、N,N-ジメチルスルファモイル基、N-アセチルスルファモイル基、N-ベンゾイルスルファモイル基、N-(N’-フェニルカルバモイル)スルファモイル)基などを挙げることができる。
脂肪族もしくはアリールスルフィニル基は、炭素数1~30の脂肪族スルフィニル基(例えばアルキルスルフィニル基)、6~30のアリールスルフィニル基(好ましくは置換基を有してもよいフェニルスルフィニル基)が好ましい。例えば、メチルスルフィニル基、エチルスルフィニル基、フェニルスルフィニル基、p-メチルフェニルスルフィニル基などを挙げることができる。
脂肪族もしくはアリールスルホニル基は、炭素数1~30の脂肪族スルホニル基(例えばアルキルスルホニル基)、6~30のアリールスルホニル基(好ましくは置換基を有してもよいフェニルスルホニル基)が好ましい。例えば、メチルスルホニル、エチルスルホニル、フェニルスルホニル、p-トルエンスルホニル基などを挙げることができる。
アリールオキシカルボニル基は、炭素数7~30のアリールオキシカルボニル基が好ましい。アリールオキシカルボニル基の例には、フェノキシカルボニル、o-クロロフェノキシカルボニル、m-ニトロフェノキシカルボニル、p-t-ブチルフェノキシカルボニル基などを挙げることができる。好ましくは置換基を有してもよいフェニルオキシカルボニル基である。
脂肪族オキシカルボニル基(例えばアルコキシカルボニル基)は、炭素数2~30が好ましく、置換基を有してもよい。例えば、メトキシカルボニル、エトキシカルボニル、t-ブトキシカルボニル、n-オクタデシルオキシカルボニル基などを挙げることができる。
カルバモイル基は、炭素数1~30のカルバモイル基が好ましい。カルバモイル基の例には、カルバモイル、N-メチルカルバモイル、N,N-ジメチルカルバモイル、N,N-ジ-n-オクチルカルバモイル、N-(メチルスルホニル)カルバモイル基などを挙げることができる。
アリールもしくはヘテロ環アゾ基として、例えば、フェニルアゾ、4-メトキシフェニルアゾ、4-ピバロイルアミノフェニルアゾ、2-ヒドロキシ-4-プロパノイルフェニルアゾ基などを挙げることができる。
イミド基として、例えば、N-スクシンイミド基、N-フタルイミド基などを挙げることができる。
これらに加え、水酸基、シアノ基、ニトロ基、スルホ基、カルボキシル基が挙げられる。
これらの各基はさらに置換基を有してもよく、このような置換基としては、上述の置換基Tが挙げられる。
一般式(1)で表される化合物(マゼンタ染料)は転写性が高く、低~中濃度プリント領域では吸収波形がシャープなため鮮やかであり色再現域が広くなるが、高濃度プリントの濃度飽和領域では吸収波形がブロード化する特徴がある。プロセスブラック形成において、一般式(1)で表されるマゼンタ染料を含む染料層と、一般式(2)~(7)で表されるイエロー染料を含む染料層と、一般式(8)~(12)で表されるシアン染料を含む染料層を用いることにより、得られたプロセスブラック部分ではイエローの吸収波形、マゼンタ吸収波形、及びシアン吸収波形の境界が効率的に埋まり、可視領域で平坦な吸収に近づくため、良質なプロセスブラックを形成できる。
また、本発明の好ましい形態の感熱転写記録シートによれば、上記効果に加えて、退色時の色バランスの高い画像を得ることもできる。その理由は以下のように考えられる。
一般式(1)で表されるマゼンタ染料は耐光性や湿熱堅牢性が高く、他の染料と混合しても(インクシートにおいて一般式(1)で表されるマゼンタ染料に加えて他のマゼンタ染料を併用する場合、及びプリントにおいてシアン染料やイエロー染料と、一般式(1)で表されるマゼンタ染料が混合される場合の両方を指す)、触媒的に退色を加速することがない。
以下に、本発明における、シアン染料、イエロー染料、マゼンタ染料の好ましい組み合わせの態様をそれぞれ記載する。各染料の好ましい組み合わせの態様は別の色相の染料の好ましい組み合わせの態様とさらに組み合わせることができる。
シアン染料は、一般式(8)で表される化合物と一般式(12)で表される化合物とを含むことも好ましい。この組み合わせによれば、本発明の効果に加えて、グレー画像の光による退色時の色バランスを高めること、逆転写性を低下させること、単色画像の光による退色時の各染料の残存率を高めること、暗所高温高湿環境下での退色バランスを高めること等ができる。
イエロー染料が、一般式(3)で表される化合物と一般式(2)で表される化合物とを含むことも好ましい。上記化合物を組み合わせて用いる場合、一般式(3)で表される化合物の含有量(XVI)と、一般式(2)で表される化合物の含有量(V)との比は、質量比で、(XVI):(V)=90~50:10~50が好ましく、80~60:20~40がより好ましい。(XVI)+(V)=100である。
これらの組み合わせによれば、本発明の上記効果に加えて、色再現性を高めることができる。
マゼンタ染料は、一般式(1)で表される化合物と一般式(15)で表される化合物とを含むことも好ましい。上記化合物を組み合わせて用いる場合、一般式(1)で表される化合物の含有量(VIII)と一般式(15)で表される化合物の含有量(IX)との比は、質量比で、(VIII):(IX)=90~50:10~50が好ましく、80~60:20~40がより好ましい。(VIII)+(IX)=100である。
マゼンタ染料は、一般式(1)で表される化合物と、一般式(15)で表される化合物と、一般式(13)で表される化合物とを含むことも好ましい。上記化合物を組み合わせて用いる場合、一般式(1)で表される化合物の含有量(X)と、一般式(15)で表される化合物の含有量(XI)と、一般式(13)で表される化合物の含有量(XII)との比は、質量比で、(X):(XI):(XII)=90~50:5~25:5~25が好ましく、80~60:10~20:10~20がより好ましい。(X)+(XI)+(XII)=100である。
マゼンタ染料は、一般式(1)で表される化合物と、一般式(13)で表される化合物と、一般式(14)で表される化合物とを含むことも好ましい。上記化合物を組み合わせて用いる場合、一般式(1)で表される化合物の含有量(XIII)と、一般式(13)で表される化合物の含有量(XIV)と、一般式(14)で表される化合物の含有量(XV)との比、質量比で、(XIII):(XIV):(XV)=90~50:5~25:5~25が好ましく、80~60:10~20:10~20がより好ましい。(XIII)+(XIV)+(XV)=100である。
これらの組み合わせによれば、本発明の上記効果に加えて、色再現性を高めることができる。
マゼンタ染料が一般式(1)で表される化合物を含み、イエロー染料が一般式(2)~(7)のいずれかで表される化合物の少なくとも1種を含み、シアン染料が一般式(8)で表される化合物と一般式(9)~(12)のいずれかで表される化合物の少なくとも1種とを含むことが好ましい。
マゼンタ染料が一般式(1)で表される化合物を含み、イエロー染料が一般式(2)~(7)のいずれかで表される化合物の少なくとも1種を含み、シアン染料が一般式(8)で表される化合物と一般式(12)で表される化合物とを含むことがより好ましい。
マゼンタ染料が一般式(1)で表される化合物を含み、イエロー染料が一般式(4)で表される化合物と一般式(2)、(3)、(5)~(7)のいずれかで表される化合物の少なくとも1種とを含み、シアン染料が一般式(8)で表される化合物と一般式(9)~(12)のいずれかで表される化合物の少なくとも1種とを含むことが好ましい。
マゼンタ染料が一般式(1)で表される化合物を含み、イエロー染料が一般式(4)で表される化合物と一般式(2)又は(6)で表される化合物とを含み、シアン染料が一般式(8)で表される化合物と一般式(9)~(12)のいずれかで表される化合物の少なくとも1種とを含むことが好ましい。
マゼンタ染料が一般式(1)で表される化合物を含み、イエロー染料が一般式(3)で表される化合物と一般式(2)で表される化合物とを含み、シアン染料が一般式(8)で表される化合物と一般式(9)~(12)のいずれかで表される化合物の少なくとも1種とを含むことが好ましい。
マゼンタ染料が一般式(1)で表される化合物と一般式(13)~(20)のいずれかで表される化合物の少なくとも1種を含み、イエロー染料が一般式(4)で表される化合物と一般式(2)、(3)、(5)~(7)のいずれかで表される化合物の少なくとも1種とを含み、シアン染料が一般式(8)で表される化合物と一般式(9)~(12)のいずれかで表される化合物の少なくとも1種とを含むことが好ましい。
本発明に用いられる色素は、その他に色素を併用することも可能である。併用する色素としては熱により拡散し、感熱転写記録シートに組み込み可能かつ、加熱により感熱転写記録シートから受像シートに転写するものであれば特に限定されず、熱転写シート用の色素として従来から用いられてきている色素、あるいは公知の色素を用いることができる。
併用するのに好ましい色素としては、例えば、ジアリールメタン色素、トリアリールメタン色素、チアゾール色素、メロシアニン等のメチン色素、インドアニリン、アセトフェノンアゾメチン、ピラゾロアゾメチン、イミダゾルアゾメチン、イミダゾアゾメチン、ピリドンアゾメチン等に代表されるアゾメチン色素、キサンテン色素、オキサジン色素、ジシアノスチレン、トリシアノスチレン等に代表されるシアノメチレン色素、チアジン色素、アジン色素、アクリジン色素、ベンゼンアゾ色素、ピリドンアゾ、チオフェンアゾ、イソチアゾールアゾ、ピロールアゾ、ピラールアゾ、イミダゾールアゾ、チアジアゾールアゾ、トリアゾールアゾ、ジズアゾ等のアゾ色素、スピロピラン色素、インドリノスピロピラン色素、フルオラン色素、ローダミンラクタム色素、ナフトキノン色素、アントラキノン色素、キノフタロン色素、インドアニリン色素等が挙げられる。
本発明の感熱転写記録シートにおいて、各色相の染料はそれぞれバインダーと呼ばれる高分子化合物に分散された状態で基材上に塗布されていることが好ましい。本発明に用いる感熱転写記録シート用のバインダーとしては、各種公知のものが使用できる。
本発明におけるバインダーとしては、ポリビニルアセタール樹脂が好ましく、より好ましくはポリビニルアセトアセタール樹脂である。さらに好ましくは、樹脂中のアセタール部が80質量%以上かつこのアセタール部分においてアセトアセタール比が90質量%以上のポリビニルアセトアセタール樹脂である。このようなアセタール樹脂は特許第3065111号公報やこの明細書中に引用された文献による方法で合成できる他、積水化学工業株式会社製 エスレックスKS-5(商品名)、電気化学工業株式会社製 デンカブチラール#5000-D(商品名)など、商業的に入手可能な製品がある。
本発明の感熱転写記録シートにおいて、バインダーを各種架橋剤によって架橋することも好ましい態様である。
架橋剤とは、高分子化合物の主鎖や側鎖についた官能基と反応し、高分子同士を結合する性質を持つ化合物である。架橋剤は対象となる高分子化合物の種類に応じて適したものが選ばれる。代表的な例としては、ポリビニルアセタール樹脂など活性水素を有する水酸基を有した高分子化合物に対しては、分子中に複数のイソシアネート基(-N=C=O)を有するイソシアネート類が架橋剤として好ましく用いられる。以下にイソシアネート類の具体例を挙げる。
(1)ジイソシアネート化合物
芳香族ポリイソシアネートとして、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、トリジンジイソシアネート、ナフタリンジイソシアネートなどが、また脂肪族ポリイソシアネートとして、ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、キシレリンジイソシアネート、水添キシレリンジイソシアネート、ジシクロヘキシルメタンジイソシアネートなどを挙げることができる。
(2)トリイソシアネート化合物
トリメチロールプロパン変性トリレンジイソシアネート、イソシアヌレート結合トリレンジイソシアネート、トリメチロールプロパン変性ヘキサメチレンジイソシアネート、イソシアヌレート結合ヘキサメチレンジイソシアネート、ビューレット結合ヘキサメチレンジイソシアネート、トリメチロールイソホロンジイソシアネート、イソシアヌレート結合イソホロンジイソシアネート、トリフェニルメタントリイソシアネート、トリス(イソシアネートフェニル)チオフォスフェートなどを挙げることができる。
また、これらイソシアネート化合物の混合物やイソシアネート化合物を主鎖や側鎖に有するポリマーの使用も好ましい。
本発明において、染料層は、通常染料とバインダーを含有するが、必要に応じて、ワックス類、フッ素原子含有脂肪族基を有する高分子化合物、シリコーン化合物、ポリマー粒子、無機粒子を含有することができる。以下、本発明の好適に用いられるフッ素原子含有脂肪族基を有する高分子化合物とシリコーン化合物について説明する。
本発明に用いられるフッ素原子含有脂肪族基を有する高分子化合物において、好ましい形態は、フッ素原子含有脂肪族基を側鎖に有する高分子化合物である。フッ素原子含有脂肪族基を側鎖に有する高分子化合物は、テロメリゼーション法(テロマー法ともいわれる)もしくはオリゴメリゼーション法(オリゴマー法ともいわれる)により製造されたフッ素原子含有脂肪族化合物から導くことができる。フッ素原子含有脂肪族化合物は、例えば、特開2002-90991号公報に記載された方法等によって容易に合成することができる。
本発明においてフッ素原子含有脂肪族基として最も好ましくは、パーフルオロアルキル基である。
本発明においては共重合体が好ましく、2元共重合体でも3元共重合体でもそれ以上であってもかまわない。
大日本インキ化学工業株式会社製:メガファックF-470、メガファックF-471、メガファックF-472SF、メガファックF-474、メガファックF-475、メガファックF-477、メガファックF-478、メガファックF-479、メガファックF-480SF、メガファックF-472、メガファックF-483、メガファックF-484、メガファックF-486、メガファックF-487、メガファックF-489、メガファックF-172D、メガファックF-178K、メガファックF-178RM(いずれも商品名)、住友スリーエム株式会社製:ノベック(商標名) FC-4430、FC-4432(いずれも商品名)。
具体的には、水酸基、上記のようなオキシアルキレン基を有する高分子化合物であり、例えば、大日本インキ化学工業株式会社製 メガファックF-470、メガファックF-472SF、メガファックF-477、メガファックF-479、メガファックF-480SF、メガファックF-484、メガファックF-486(いずれも商品名)のように水への溶解性を示す化合物が好ましい。
また、フッ素原子含有脂肪族基を側鎖に有する高分子化合物添加量は染料とバインダーの種類や量に応じて決めることができ、染料層の全固形分(質量)に対して、好ましくは0.01質量%~20質量%であり、より好ましくは、0.1質量%~10質量%であり、さらに好ましくは0.2質量%~5質量%である。
次に、本発明の感熱転写記録シートに好適に用いられるシリコーン化合物について説明する。
本発明の感熱転写記録シートにおいては、シリコーン化合物を併用することも好ましい。本発明におけるシリコーン化合物とは、分子中の主鎖や側鎖にSiOを繰り返し単位とするポリシロキサン構造を有する化合物である。代表的なものにSiOを繰り返し単位とするポリマー主鎖のSi原子上に水素原子、アルキル基やアリール基が結合したシリコーンオイルがある。以下、本明細書において、ポリシロキサンとは、上記シリコーンオイルのように、SiOを繰り返し単位としてSi原子上に水素原子、アルキル基、アリール基を有する構造を示す。
本発明で好ましく用いられるシリコーン化合物は、シリコーングラフトポリマー、シリコーンブロックポリマーである。シリコーングラフトポリマーとは、ポリマーを構成する1本の主鎖からポリシロキサン構造を有する多数の側鎖が枝状に分かれた構造を有するポリマーである。シリコーンブロックポリマーとは、ポリマーを構成する主鎖の中にポリシロキサン構造が埋め込まれた構造を有するポリマーである。
シリコーンブロックポリマーにおいて、ポリマー鎖の部分は、単一のモノマーが重合したものであっても良いし、複数の種類のモノマーが共重合したものでも良い。ポリマー鎖の部分は、複数の異なる種類のポリマー鎖からなっても良い。ポリシロキサン部もポリマー鎖と同様に複数の異なる種類のポリシロキサン部からなっても良い。また、ポリマー鎖、ポリシロキサン部ともに側鎖を有して、いわゆるグラフトポリマー構造にしても良い。ポリマー中のポリシロキサン部の平均含量は5質量%以上70質量%以下の範囲が好ましく、10質量%以上50質量%以下がより好ましい。
また、この様なポリマーは市販もされている。例えば、ダイアロマーSP712(商品名)、大日精化工業株式会社製などが挙げられる。
本発明の感熱転写記録シート及び、後述する保護層転写シートの基材は特に限定されず、必要とされる耐熱性と強度を有するものであれば、従来公知のいずれのものでも使用することができる。
例としては、ポリアミド、ポリイミド、ポリエステルフィルムが挙げられる。
基材の厚さは、その強度及び耐熱性等が適切になるように材料に応じて適宜変更することができるが、好ましくは1~100μmである。より好ましくは2~50μmのものであり、さらに好ましくは3~10μmのものが用いられる。
本発明の感熱転写記録シートは、染料層と基材との間に染料の基材方向への拡散を防止するための染料バリア層を設けることができる。
染料バリア層としては通常のものが使用でき、例えば、ポリビニルアルコール樹脂やアセタール化度の低いポリビニルアセタール樹脂(樹脂全体に対してアセタール部分が50%以下)等である。
基材の表面に対しては、塗布液の濡れ性及び接着性の向上を目的として、易接着処理を行なってもよい。処理方法として、コロナ放電処理、火炎処理、オゾン処理、紫外線処理、放射線処理、粗面化処理、化学薬品処理、真空プラズマ処理、大気圧プラズマ処理、プライマー処理、グラフト化処理等公知の樹脂表面改質技術を例示することができる。
また、基材上に塗布によって易接着層を形成することもできる。易接着層に用いられる樹脂としては、ポリエステル樹脂、ポリアクリル酸エステル樹脂、ポリ酢酸ビニル樹脂、ポリ塩化ビニル樹脂やポリビニルアルコール樹脂等のビニル樹脂、ポリビニルアセトアセタールやポリビニルブチラール等のポリビニルアセタール樹脂、ポリエーテル樹脂、ポリウレタン樹脂、スチレンアクリレート樹脂、ポリアクリルアミド樹脂、ポリアミド樹脂、ポリスチレン樹脂、ポリエチレン樹脂、ポリプロピレン樹脂等を例示することができる。
易接着層の形成は、基材に用いられるフィルムを溶融押出し形成する時に、上記樹脂を含む塗布液を未延伸フィルムに塗布し、その後に延伸処理して行なうことも可能である。
また、上記の処理は、二種類以上を併用することもできる。
次に、本発明の感熱転写記録シートに用いることができる転写性保護層積層体について説明する。
本発明において、感熱転写記録シートに転写性保護層積層体を上記各染料層と面順次に設けるのが好ましい。転写性保護層積層体を基材上に設けて保護層転写シートとして感熱転写記録シートとは別に調製してもよい。転写性保護層積層体は、熱転写された画像の上に透明樹脂からなる保護層を熱転写で形成し、画像を覆い保護するためのものであり、耐擦過性、耐光性、耐候性、耐薬品性等の耐久性向上を目的とする。転写された染料が感熱転写受像シート表面に曝されたままでは、耐擦過性、耐光性、耐候性、耐薬品性等の画像耐久性が不十分な場合に有効である。
転写性保護層積層体は、基材上に、基材側から離型層、転写性保護層、接着剤層の順に形成することができる。転写性保護層を複数の層で形成することも可能である。転写性保護層が他の層の機能を兼ね備えている場合には、離型層、接着剤層を省くことも可能である。離型層を用いる場合は、基材として易接着層の設けられたものを用いることも可能である。
本発明の感熱転写記録シートは、染料層を塗設した基材の面の他方の面(裏面)、すなわちサーマルヘッド等に接する側に背面層を設けることが好ましい。また、保護層転写シートの場合にも、転写性保護層を塗設した基材の面の他方の面(裏面)、すなわちサーマルヘッド等に接する側に背面層を設けることが好ましい。
感熱転写記録シートの基材の裏面とサーマルヘッド等の加熱デバイスとが直接接触した状態で加熱されると、熱融着が起こりやすい。また、両者の間の摩擦が大きく、感熱転写記録シートを印画時に滑らかに搬送することが難しい。
背面層は、感熱転写記録シートがサーマルヘッドからの熱エネルギーに耐え得るように設けられるものであって、熱融着を防止し、滑らかな走行を可能にする。近年、プリンターの高速化に伴いサーマルヘッドの熱エネルギーが増加しているため、必要性は大きくなっている。
背面層は、バインダーに滑剤、離型剤、界面活性剤、無機粒子、有機粒子、顔料等を添加したものを塗布することによって形成される。また、背面層と基材との間に中間層を設けてもよく、無機微粒子と水溶性樹脂またはエマルジョン化可能な親水性樹脂からなる層が開示されている。
背面層の耐熱性を高めるため、紫外線又は電子ビームを照射して樹脂を架橋する技術が知られている。また、架橋剤を用い、加熱により架橋させることも可能である。この際、触媒が添加されることもある。架橋剤としては、ポリイソシアネート等が知られており、このためには、水酸基を有する官能基を有する樹脂が適している。特開昭62-259889号公報には、ポリビニルブチラールとイソシアネート化合物との反応生成物にリン酸エステルのアルカリ金属塩又はアルカリ土類塩及び炭酸カルシウム等の充填剤を添加することにより背面層を形成することが開示されている。また、特開平6-99671号公報には、耐熱滑性層を形成する高分子化合物を、アミノ基を有するシリコーン化合物と1分子中に2個以上のイソシアネート基を有するイソシアネート化合物を反応させることにより得ることが開示されている。
滑剤としては、フッ化カルシウム、フッ化バリウム、フッ化黒鉛等のフッ化物、二硫化モリブデン、二硫化タングステン、硫化鉄等の硫化物、酸化鉛、アルミナ、酸化モリブデン等の酸化物、グラファイト、雲母、窒化ホウ素、粘土類(滑石、酸性白度等)等の無機化合物からなる固体滑剤、フッ素樹脂、シリコーン樹脂等の有機樹脂、シリコーンオイル、ステアリン酸金属塩等の金属セッケン類、ポリエチレンワックス、パラフィンワックス等の各種ワックス類、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、ノニオン界面活性剤、フッ素含有界面活性剤等の界面活性剤を挙げることができる。
アルキルリン酸モノエステル、アルキルリン酸ジエステルの亜鉛塩等の燐酸エステル界面活性剤も用いられるが、酸根を有しており、サーマルヘッドからの熱量が大になると燐酸エステルが分解し、更に背面層のpHが低下してサーマルヘッドの腐食摩耗が激しくなるという問題点がある。これに対しては、中和したリン酸エステル界面活性剤を用いる方法、水酸化マグネシウム等の中和剤を用いる方法等が知られている。
その他の添加剤としては高級脂肪酸アルコール、オルガノポリシロキサン、有機カルボン酸及びその誘導体、タルク、シリカ等の無機化合物の微粒子等を挙げることができる。
次に本発明の感熱転写記録シートとともに、画像形成において好適に用いることができる感熱転写受像シートについて説明する。
この感熱転写受像シートは、染料を受容する熱可塑性の受容ポリマーを含有する少なくとも1層の受容層を基材上に有することが好ましい。受容層には、紫外線吸収剤、離型剤、滑剤、酸化防止剤、防腐剤、界面活性剤、その他の添加物を含有させることができる。基材と受容層との間に、例えば断熱層(多孔質層)、光沢制御層、白地調整層、帯電調節層、接着層、プライマー層等の中間層が形成されていてもよい。基材と受容層との間に少なくとも1層の断熱層を有することが好ましい。
受容層及びこれらの中間層は同時重層塗布により形成されることが好ましく、中間層は、必要に応じて複数設けることができる。
基材の裏面側にはカール調整層、筆記層、帯電調整層が形成されていてもよい。基材裏面各層を塗布するためには、ロールコート、バーコート、グラビアコート、グラビアリバースコート等の一般的な方法を用いることができる。
本発明において、感熱転写受像シートは、受容層に色素染着可能なポリマーラテックスを使用することが好ましい。またポリマーラテックスとしては単独でも複数のポリマーラテックスを混合使用してもよい。
ポリマーラテックスとは一般に熱可塑性樹脂が微粒子として水溶性の分散媒中に分散されたものである。本発明のポリマーラテックスに用いられる熱可塑性樹脂の例としては、ポリカーボネート、ポリエステル、ポリアクリレート、塩化ビニル共重合体、ポリウレタン、スチレン-アクリロニトリル共重合体、ポリカプロラクトン等が挙げられる。
このうちポリカーボネート、ポリエステル、塩化ビニル共重合体が好ましく、ポリエステル、塩化ビニル共重合体が特に好ましい。
この共重合体にはビニルアルコール誘導体やマレイン酸誘導体、ビニルエーテル誘導体等の補助的なモノマー成分を添加してもよい。共重合体において塩化ビニル成分は50質量%以上含有されていることが好ましく、またマレイン酸誘導体、ビニルエーテル誘導体等の補助的なモノマー成分は10質量%以下であることが好ましい。
ポリマーラテックスは単独でも混合物として使用してもよい。ポリマーラテックスは、均一構造であってもコア/シェル型であってもよく、このときコアとシェルをそれぞれ形成する樹脂のガラス転移温度が異なっても良い。
商業的に入手可能なポリエステルラテックスとしては、東洋紡株式会社製 バイロナールMD-1100(Tg40℃)、バイロナールMD-1400(Tg20℃)、バイロナールMD-1480(Tg20℃)、MD-1985(Tg20℃)等(いずれも商品名)が挙げられる。
商業的に入手可能な塩化ビニル共重合体としては、日信化学工業株式会社製 ビニブラン276(Tg33℃)、ビニブラン609(Tg48℃)、住化ケムテックス株式会社製スミエリート1320(Tg30℃)、スミエリート1210(Tg20℃)等(いずれも商品名)が挙げられる。
本発明において、断熱層には中空ポリマーを含有することが好ましい。
本発明における中空ポリマーとは粒子内部に空隙を有するポリマー粒子であり、好ましくは水分散物であり、例えば、1)ポリスチレン、アクリル樹脂、スチレン-アクリル樹脂等により形成された隔壁内部に水等の分散媒が入っており、塗布乾燥後、粒子内の水が粒子外に蒸発して粒子内部が中空となる非発泡型の中空ポリマー粒子、2)ブタン、ペンタン等の低沸点液体を、ポリ塩化ビニリデン、ポリアクリロニトリル、ポリアクリル酸、ポリアクリル酸エステルのいずれか又はそれらの混合物もしくは重合物よりなる樹脂で覆っており、塗工後、加熱により粒子内部の低沸点液体が膨張することにより内部が中空となる発泡型マイクロバルーン、3)上記の2)をあらかじめ加熱発泡させて中空ポリマーとしたマイクロバルーンなどが挙げられる。
これらの中でも、上記1)の非発泡型の中空ポリマー粒子が好ましく、必要に応じて2種以上混合して使用することができる。具体例としてはロームアンドハース社製 ローペイク HP-1055、JSR社製 SX866(B)、日本ゼオン社製 Nipol MH5055(いずれも商品名)などが挙げられる。
また、中空ポリマーは、空隙率が20~70%のものが好ましく、30~60%のものがより好ましい。
本発明に用いることができる感熱転写受像シートにおいて、受容層及び/または断熱層は水溶性ポリマーを含有させることができる。ここで水溶性ポリマーとは、20℃において水100gに対し0.05g以上の溶解度を有し、より好ましくは0.1g以上、さらに好ましくは0.5g以上の溶解度を有する。
またゼラチンには、アルデヒド型架橋剤、N-メチロール型架橋剤、ビニルスルホン型架橋剤、クロロトリアジン型架橋剤等の公知の架橋剤を添加することができる。このうちビニルスルホン型架橋剤、クロロトリアジン型架橋剤が好ましく、具体的例としては、ビスビニルスルホニルメチルエーテル、N,N’-エチレン-ビス(ビニルスルホニルアセタミド)エタン、4,6-ジクロロ-2-ヒドロキシ-1,3,5-トリアジンまたはそのナトリウム塩を挙げることができる。
本発明において感熱転写受像シートの受容層には、前述のフッ素原子含有脂肪族基を側鎖に有する高分子化合物を含有させることができる。この場合、感熱転写記録シートが含有するフッ素原子含有脂肪族基を側鎖に有する高分子化合物と同一の高分子化合物を含有しても同じ範疇の異なる高分子化合物を含有してもよく、いずれも本発明において好ましい態様である。また、離型剤として公知のポリエチレンワックス、アミドワックス等の固形ワックス類、シリコーンオイル、リン酸エステル化合物、フッ素含有界面活性剤、シリコーン界面活性剤を含有してもよい。
本発明の感熱転写記録シートを用いた画像形成方法では、感熱転写受像シートの受容層と感熱転写記録シートの染料層とが接するように重ね合わせて、サーマルヘッドからの画像信号に応じた熱エネルギーを付与することにより画像を形成することが好ましい。
具体的な画像形成は、例えば特開2005-88545号公報などに記載された方法と同様にして行うことができる。本発明では、消費者にプリント物を提供するまでの時間を短縮するという観点から、プリント時間は15秒未満が好ましく、3~12秒がより好ましく、さらに好ましくは、3~7秒である。
例示化合物(1-1)5.0質量部、ポリビニルアセタール樹脂(KS-3(商品名)、積水化学社製)5.0質量部、マット剤(フローセンUF(商品名)、住友精工社製)0.1質量部、メチルエチルケトン45質量部、トルエン45質量部を混合して、マゼンタ染料層塗工液(M1)を調製した。
例示化合物(2-1)5.0質量部、ポリビニルアセタール樹脂(KS-3(商品名)、積水化学社製)5.0質量部、マット剤(フローセンUF(商品名)、住友精工社製)0.1質量部、メチルエチルケトン45質量部、トルエン45質量部を混合して、イエロー染料層塗工液(Y1)を調製した。
例示化合物(8-1)5.0質量部、ポリビニルアセタール樹脂(KS-3(商品名)、積水化学社製)5.0質量部、マット剤(フローセンUF(商品名)、住友精工社製)0.1質量部、メチルエチルケトン45質量部、トルエン45質量部を混合して、シアン染料層塗工液(C1)を調製した。
アクリルポリオール樹脂(アクリディックA-801(商品名)、大日本インキ化学工業社製)26.0質量部、ステアリン酸亜鉛(SZ-2000(商品名)、堺化学工業社製)0.43質量部、リン酸エステル(プライサーフA217(商品名)、第一工業製薬社製)1.27質量部、イソシアネート化合物50%溶液(バーノックD-800(商品名)、大日本インキ化学工業社製)8.0質量部、及びメチルエチルケトン/トルエン(質量比2/1)64質量部を混合して背面層塗工液を調製した。
変性セルロース樹脂(L-30(商品名)、ダイセル化学工業社製)5.0質量部、メチルエチルケトン95.0質量部を混合し、離型層塗工液を調製した。
アクリル樹脂溶液(固形分40%、UNO-1(商品名)、岐阜セラミック(有)製)90質量部、メタノール5質量部、2-プロパノール5質量部を混合し、保護層塗工液を調製した。
アクリル樹脂(ダイアナールBR-77(商品名)、三菱レイヨン社製)25質量部、紫外線吸収剤1(2,4,6-トリス(4-ブトキシ-2-ヒドロキシフェニル)-1,3,5-トリアジン、カタログ番号3135-19-1、東京化成社製)2質量部、紫外線吸収剤2(2-(2-ヒドロキシ-5-メチルフェニル)ベンゾトリアゾール、カタログ番号2440-22-4、東京化成社製)1質量部、紫外線吸収剤3(2-(5-t-ブチル-2-ヒドロキシフェニル)ベンゾトリアゾール、カタログ番号3147-76-0、東京化成工業(株))1質量部、紫外線吸収剤4(2-t-ブチル-6-(5-クロロ-2H-ベンゾトリアゾール-2-イル)-4-メチルフェノール、カタログ番号3896-11-5、富士フイルム和光純薬社製)1質量部、ポリメタクリル酸メチル微粒子(タフチックFH-S005(商品名)、日本エクスラン工業社製)0.4質量部、メチルエチルケトン46質量部、トルエン24質量部を混合し、接着層塗工液を調製した。
基材として片面に易接着処理がされている厚さ4.5μmのポリエステルフィルム(ルミラー5A-F595(商品名)、東レ社製)を用い、このポリエステルフィルムの易接着処理がされていない面に、乾燥後の固形分塗布量が1g/m2となるように前述の背面層塗工液を塗布した。乾燥後、50℃で熱処理を行い硬化させた。
このようにして作製したポリエステルフィルムの、易接着処理されている面に、マゼンタ染料層塗工液(M1)、イエロー染料層塗工液(Y1)、シアン染料層塗工液(C1)、及び転写性保護層積層体を面順次となるように(各色相の領域が易接着処理面上において隣り合うように)塗布した感熱転写記録シートを作製した。各染料層の固形分塗布量は、0.8g/m2となるように調節した。なお、転写性保護層積層体の塗工は、離型層塗工液を塗布し、乾燥した後に、その上に保護層塗工液を塗布し、さらに乾燥した後に、その上に接着層塗工液を塗布することで実施した。
マゼンタ染料層塗工液(M1)、イエロー染料層塗工液(Y1)、シアン染料層塗工液(C1)の調製において、マゼンタ染料(M染料)、イエロー染料(Y染料)、シアン染料(C染料)の組み合わせを表1-1及び表1-2(併せて表1という)に示すように変更した以外は、実施例1と同様にして、実施例2~90の感熱転写記録シート、及び比較例1~13の感熱転写記録シートを調製した。各染料層塗工液中の染料の量はM1、Y1、C1と同量(5.0質量部)とし、ある染料層塗工液において、複数種の染料を用いる場合には、複数種の染料の合計量を5.0質量部とし、複数種の染料の量比を表1に示すように調整して用いた。
上記の本発明の実施例1~90の感熱転写記録シート及び比較例1~13の感熱転写記録シートについて、感熱転写プリンター(フジフイルムサーマルフォトプリンターASK-300(商品名)、富士フイルム社製)を用いて、印画紙(フジフイルムクオリティサーマルフォトペーパー(商品名)、富士フイルム社製)に画像プリントを出力して、以下の評価試験を行った。以下の説明において、表2-1~表2-4を併せて表2という。
出力画像として高精細カラーディジタル標準画像CMYK/SCID(JIS規格X9201:2001)のカラーチャートデータ(S7、S8、S9、及びS10)を用いて色の計測に必要なサイズを加味して1つの色票を10mm四方となるように全928色票をプリントした。得られた色票群を自動スキャニングテーブル(i1iO(商品名)、エックスライト社製)を用いて、視野角2°でCIELab表色系におけるL*値、a*値、及びb*値を計測した。無彩色(白~灰~黒)を選定するため、全色票群からa*値及びb*値のいずれについても-3以上3未満である色票群を抜き出し、その色票群の中で最も小さなL*値(最も高濃度の黒)であったもののL*値を以下の評価基準で評価した。結果を表2に示す。なお、本評価において明度L*は値が小さいものほど、黒色として濃度が高いことを示している。黒として、明度が22以上ある場合は灰色がかったぼやけた黒であるが、明度が20前後で実用上耐えうる黒となり、明度が18よりも小さな場合、高級感や重厚感を与える高濃度の黒となる。加えて高濃度の黒は、文字やバーコードをよりくっきりとプリントするためにも重要である。
--評価基準--
A:18未満
B:18以上22未満
C:22以上
図1に示した評価用画像パターン1を用いて評価した。図1において、Kはプロセスブラック部分(RGB値として、R0、G0、B0)を示し、Yはイエロー部分(RGB値として、R255、G255、B0)を示し、Mはマゼンタ部分(RGB値として、R255、G0、B255)を示し、Cはシアン部分(RGB値として、R0、G255、B255)を示し、Wはホワイト部分(RGB値として、R255、G255、B255)を示す。図1に示すように、プロセスブラック部分(K)は90mm×90mmの大きさであり、イエロー部分(Y)、マゼンタ部分(M)、シアン部分(C)、及びホワイト部分(W)は、それぞれ25mm×25mmの大きさである。イエロー部分(Y)、マゼンタ部分(M)、シアン部分(C)、及びホワイト部分(W)は、プロセスブラック部分内に、上下二段に10mmの間隔をあけて離間して形成されている。
図1に示した評価用画像パターン1を、プロセスブラック部分は最高到達濃度(最も高濃度の黒)で、イエロー、マゼンタ、及びシアンの部分は反射濃度(ISO濃度ステータスT、視野角2°)が1.0となるようにプリントした。ホワイト部分は、染料が転写されていない部分(印画紙の色の部分)である。得られた評価用画像パターン1のプリントについて、目視にて以下の評価基準で評価した。パネルは10人とし、最も多くのパネルが示した評価基準を評価値とした。評価に用いた、同濃度単独ベタ画像は、上記イエロー部分、マゼンタ部分、又はシアン部分と同じRGB値の画像のみを上記と同じ反射濃度でプリントしたものである。さらに、プリントされていない印画紙をホワイトの単独ベタ画像とした。結果を表2に示す。
--評価基準--
A:とても引き締まって見える
(カラー部分(イエロー部分、マゼンタ部分、シアン部分、及びホワイト部分)が同濃度単独ベタ画像より色濃く見え、輪郭がくっきりとしている)
B:引き締まって見える
(カラー部分が同濃度単独ベタ画像と同じ色濃さに見えるが輪郭はくっきりしている)
C:ぼやけて見える
(カラー部分が同濃度単独ベタ画像より色淡く見える、又は輪郭がぼやけて見える)
前述の評価試験1でプリントし、自動スキャニングテーブル(i1iO(商品名)、エックスライト社製)を用いて計測したCIELab表色系におけるL*値、a*値、及びb*値を3次元プロットして、各感熱転写記録シートの色再現体積を算出した。得られた色再現体積について、比較例4の色再現体積を基準(100%)とした相対値を求め、以下の評価基準で評価した。結果を表2に示す。色再現体積が高いほど、彩度の高い色を含めてさまざまな色を表現できることを意味する。色再現体積は、写真プリントにおいて、忠実な色再現を実現可能な設計ができるようになるだけでなく、原色を利用することの多いデジタル画像で、従来プリントで再現できなかったような鮮やかな原色についても近しい色みを再現できることを示している。
--評価基準--
S:110%以上
A:105%以上110%未満
B:100%以上105%未満
C:100%未満
各染料の単色領域での光による退色性のバランスを以下のようにして評価した。
30mm四方のイエロー、マゼンタ、シアンの画像を別々に、イエロー、マゼンタ、及びシアンのそれぞれの反射濃度(ISO濃度ステータスT、視野角2°)が1.0となるようにプリントした。得られたプリントについて、キセノンウェザーメーター(XL-75L(商品名)、スガ試験機社製)を用いて耐光性試験(サンプル温度25℃、照射量100キロルクス、366nm以下カットオフフィルタ使用、照射時間72時間)を実施した。試験後のイエロー、マゼンタ、及びシアンの反射濃度を測定して、それぞれについて耐光性試験前の反射濃度に対する残存率を算出した。算出したイエロー、マゼンタ、及びシアンの残存率の内、最大のものと最小のものとの差(残存率の差)を算出して、下記評価基準により評価した。評価基準は以下の通りである。結果を表2に示す。
この残存率の差が小さいことは、プリント画像のイエロー、マゼンタ、及びシアンのプリントの単色部分での各染料の光退色の速度が近いことを意味しており、退色バランスに優れる。退色のバランスに優れると色偏りなく均一に色褪せていくため好ましい。一方で、退色バランスに劣るとプリント画像が特定の色が偏って退色してしまうため、好ましくない。
--評価基準--
A:5%未満
B:5%以上10%未満
C:10%以上
各染料の混色領域での光による退色性のバランスを以下のようにして評価した。
30mm四方のグレーの画像を、イエロー、マゼンタ、及びシアンの感熱転写記録シートを用いて、イエロー、マゼンタ、及びシアンのそれぞれの反射濃度(ISO濃度ステータスT、視野角2°)が1.0となるように順次重ねてプリントしてプリント画像(グレー)を作成した。このプリント画像に対して、キセノンウェザーメーター(XL-75L(商品名)、スガ試験機社製)を用いて耐光性試験(サンプル温度25℃、照射量100キロルクス、366nm以下カットオフフィルタ使用、照射時間72時間)を実施した。試験後のグレー画像中のイエロー、マゼンタ、シアンの反射濃度を測定して、それぞれの耐光性試験前の反射濃度に対する残存率を算出した。算出したイエロー、マゼンタ、シアンの残存率の内、最大のものと最小のものとの差を算出し、下記評価基準により評価した。結果を表2に示す。
この残存率の差がより小さいことは、プリント画像のグレー部分(混色部分)での光による退色バランスがよいことを示している。各色相の染料は、混色領域内での相互作用により、各色相の染料の光による退色の度合いが大きく異なる場合がある。プリント画像における混色部分の退色バランスは、写真プリントにおいては非常に重要である。グレー退色バランスが悪いと、例えば人物の顔のプリントにおいて、黒髪が茶髪へ変化したり、肌色が赤み(熱っぽい肌色)や青み(血の気が引いたような肌色)に変化したりして好ましくない。グレー退色バランスに優れると上記が解決されプリントの退色として好ましい。
--評価基準--
A:5%未満
B:5%以上10%未満
C:10%以上
各染料の混合時の、高温としたときの退色性のバランスを以下のようにして評価した。
評価試験5と同様にして作成したグレー画像を、恒温恒湿機(型番:ARS-0220-J、エスペック社製)中において、暗所高温高湿経時条件下(温度65℃、相対湿度70%RH、経時90日)で処理した。処理後のグレー画像中のイエロー、マゼンタ、及びシアンの反射濃度をそれぞれ測定して、処理前の反射濃度に対する残存率をそれぞれ算出した。算出したイエロー、マゼンタ、及びシアンの残存率の内、最大のものと最小のものとの差を算出し、下記評価基準により評価した。結果を表2に示す。
この残存率の差が、より小さい方がプリント画像の高温高湿によるグレー退色バランスがよいことを示している。
--評価基準--
A:10%未満
B:10%以上20%未満
C:20%以上
マゼンタ、イエロー及びシアンの各染料のベタ画像(50mm四方)がこの順番に重なるように、印画紙の画像形成領域に、各染料を順次にプリントして黒色プリント画像を得た。使用後の感熱転写記録シートのイエロー染料層及びシアン染料層から、メチルエチルケトン/トルエン(重量比1/1)を用いて染料をそれぞれ抽出して、各染料層に含まれる染料中のマゼンタ染料を、高速クロマトグラフィを用いて定量した。各染料層中の全染料の含有量に占めるマゼンタ染料の割合(質量%)を求め、最も大きな数値を下記評価基準により評価した。結果を表2に示す。
このようにすることで、プリント中に、イエロー染料層、及びシアン染料層へ、印画紙の画像形性領域から、マゼンタ染料がどれだけ移行(逆転写)したかを調べることができる。印画紙からの他の染料層への染料の逆転写を抑制することで、プリント画像の色再現を確実に行うことができる。
--評価基準--
A:2%未満
B:2%以上5%未満
C:5%以上
評価試験1~7における評価結果(S、A、B、C)をもとに、これらの評価結果を下記の基準で得点化して、合計得点により総合評価を行った。合計得点が高いほど、好ましい。結果を表2に示す。
S:2点
A:1点
B:0点
C:-1点
本発明の各感熱転写記録シートと比較例の各感熱転写記録シートを比較すると、本発明の各感熱転写記録シートの好ましい形態では、逆転写が少ないことがわかる。特に、シアン染料を一般式(8)で表される化合物と一般式(9)~(12)のいずれかで表される化合物の少なくとも1種とすることにより、逆転写を効率よく低減することができる。
Y:イエロー部分
M:マゼンタ部分
C:シアン部分
W:ホワイト部分
Claims (11)
- 基材と、前記基材上に色材層とを有する感熱転写記録シートであって、
前記色材層は、イエロー染料を含有するイエロー染料層、マゼンタ染料を含有するマゼンタ染料層、及びシアン染料を含有するシアン染料層を有し、
前記マゼンタ染料は、下記一般式(1)で表される化合物を含み、
前記イエロー染料は、下記一般式(2)~(7)のいずれかで表される化合物の少なくとも1種を含み、
前記シアン染料は、下記一般式(8)~(12)のいずれかで表される化合物の少なくとも1種を含む、
感熱転写記録シート。
- 前記シアン染料が、前記一般式(8)で表される化合物と、前記一般式(9)~(12)のいずれかで表される化合物の少なくとも1種とを含む、請求項1に記載の感熱転写記録シート。
- 前記シアン染料中、前記一般式(8)で表される化合物の含有量(I)と、前記一般式(9)~(12)のいずれかで表される化合物の含有量の合計(II)との比が、質量比で、(I):(II)=90~50:10~50である、請求項1又は2に記載の感熱転写記録シート。
- 前記シアン染料が、前記一般式(8)で表される化合物と前記一般式(12)で表される化合物とを含む、請求項1~3のいずれか1項に記載の感熱転写記録シート。
- 前記イエロー染料が、前記一般式(4)で表される化合物と、前記一般式(2)、(3)、(5)、(6)及び(7)のいずれかで表される化合物の少なくとも1種とを含む、請求項1~4のいずれか1項に記載の感熱転写記録シート。
- 前記イエロー染料が、前記一般式(4)で表される化合物と、前記一般式(2)及び(6)のいずれかで表される化合物の少なくとも1種とを含む、請求項1~5のいずれか1項に記載の感熱転写記録シート。
- 前記イエロー染料が、前記一般式(3)で表される化合物と、前記一般式(2)で表される化合物とを含む、請求項1~4のいずれか1項に記載の感熱転写記録シート。
- 前記マゼンタ染料が、前記一般式(1)で表される化合物と、下記一般式(13)~(20)のいずれかで表される化合物の少なくとも1種とを含む、請求項1~7のいずれか1項に記載の感熱転写記録シート。
- 前記マゼンタ染料が、前記一般式(1)で表される化合物と、前記一般式(15)で表される化合物とを含む、請求項1~8のいずれか1項に記載の感熱転写記録シート。
- 前記マゼンタ染料が、前記一般式(1)で表される化合物と、前記一般式(15)で表される化合物と、前記一般式(13)で表される化合物とを含む、請求項1~9のいずれか1項に記載の感熱転写記録シート。
- 前記マゼンタ染料が、前記一般式(1)で表される化合物と、前記一般式(13)で表される化合物と、前記一般式(14)で表される化合物とを含む、請求項1~9のいずれか1項に記載の感熱転写記録シート。
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