JPH05150433A - Heat developable photosensitive material - Google Patents
Heat developable photosensitive materialInfo
- Publication number
- JPH05150433A JPH05150433A JP3316794A JP31679491A JPH05150433A JP H05150433 A JPH05150433 A JP H05150433A JP 3316794 A JP3316794 A JP 3316794A JP 31679491 A JP31679491 A JP 31679491A JP H05150433 A JPH05150433 A JP H05150433A
- Authority
- JP
- Japan
- Prior art keywords
- group
- dye
- image
- polymer
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- -1 silver halide Chemical class 0.000 claims abstract description 30
- 229910052709 silver Inorganic materials 0.000 claims abstract description 26
- 239000004332 silver Substances 0.000 claims abstract description 26
- 238000011161 development Methods 0.000 claims abstract description 17
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 43
- 239000000126 substance Substances 0.000 claims description 32
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 49
- 230000003068 static effect Effects 0.000 abstract description 7
- 230000002542 deteriorative effect Effects 0.000 abstract description 3
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- 238000012546 transfer Methods 0.000 description 16
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- IBWXIFXUDGADCV-UHFFFAOYSA-N 2h-benzotriazole;silver Chemical compound [Ag].C1=CC=C2NN=NC2=C1 IBWXIFXUDGADCV-UHFFFAOYSA-N 0.000 description 6
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- 238000010528 free radical solution polymerization reaction Methods 0.000 description 6
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- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 4
- 239000012964 benzotriazole Substances 0.000 description 4
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- 239000011241 protective layer Substances 0.000 description 4
- 150000003378 silver Chemical class 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 3
- 230000002745 absorbent Effects 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
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- 239000010931 gold Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
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- 238000001556 precipitation Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- UHBGYFCCKRAEHA-UHFFFAOYSA-N P-toluamide Chemical compound CC1=CC=C(C(N)=O)C=C1 UHBGYFCCKRAEHA-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910001864 baryta Inorganic materials 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000007857 hydrazones Chemical class 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
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- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
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- 230000003287 optical effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- XOIYZMDJFLKIEI-UHFFFAOYSA-N (hydroxysulfonimidoyl)oxybenzene Chemical compound NS(=O)(=O)OC1=CC=CC=C1 XOIYZMDJFLKIEI-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- MQCPOLNSJCWPGT-UHFFFAOYSA-N 2,2'-Bisphenol F Chemical class OC1=CC=CC=C1CC1=CC=CC=C1O MQCPOLNSJCWPGT-UHFFFAOYSA-N 0.000 description 1
- PWKRPBRTFVFUGQ-UHFFFAOYSA-N 2-(2-aminopropan-2-yldiazenyl)propan-2-amine;hydrochloride Chemical compound Cl.CC(C)(N)N=NC(C)(C)N PWKRPBRTFVFUGQ-UHFFFAOYSA-N 0.000 description 1
- YHCGGLXPGFJNCO-UHFFFAOYSA-N 2-(2H-benzotriazol-4-yl)phenol Chemical compound OC1=CC=CC=C1C1=CC=CC2=C1N=NN2 YHCGGLXPGFJNCO-UHFFFAOYSA-N 0.000 description 1
- NPGSYTSLEGDFCZ-UHFFFAOYSA-N 2-(4-carbamoylphenoxy)ethyl propanoate Chemical compound CCC(=O)OCCOC1=CC=C(C(N)=O)C=C1 NPGSYTSLEGDFCZ-UHFFFAOYSA-N 0.000 description 1
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- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 1
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- CHVCUJXELFQGCF-UHFFFAOYSA-N 6-methyl-[1,2,4]triazolo[1,5-a]pyrimidine Chemical compound C1=C(C)C=NC2=NC=NN21 CHVCUJXELFQGCF-UHFFFAOYSA-N 0.000 description 1
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
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- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- 101100336468 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) gem-1 gene Proteins 0.000 description 1
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- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
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- 125000000687 hydroquinonyl group Chemical class C1(O)=C(C=C(O)C=C1)* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical class OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical group [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- HAAYBYDROVFKPU-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.N.[Ag+].[O-][N+]([O-])=O HAAYBYDROVFKPU-UHFFFAOYSA-N 0.000 description 1
- NHQVTOYJPBRYNG-UHFFFAOYSA-M sodium;2,4,7-tri(propan-2-yl)naphthalene-1-sulfonate Chemical compound [Na+].CC(C)C1=CC(C(C)C)=C(S([O-])(=O)=O)C2=CC(C(C)C)=CC=C21 NHQVTOYJPBRYNG-UHFFFAOYSA-M 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229940036565 thiouracil antithyroid preparations Drugs 0.000 description 1
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Thermal Transfer Or Thermal Recording In General (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、熱現像感光材料に関
し、詳しくは転写画像の耐光性と表面光沢性の改良され
た熱現像感光材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photothermographic material, and more particularly to a photothermographic material having improved light resistance and surface gloss of a transferred image.
【０００２】[0002]
【発明の背景】現像工程を加熱下で行なう熱現像処理は
公知でありカラー画像を得る場合、色素画像を感光材料
から受像層に転写するいわゆる転写型の熱現像感光材料
も良く知られている。BACKGROUND OF THE INVENTION A heat development treatment in which a development step is carried out under heating is known, and a so-called transfer type photothermographic material which transfers a dye image from a light-sensitive material to an image receiving layer is well known when a color image is obtained. ..
【０００３】受像層に転写した色素画像の画像安定性、
特に耐光性を向上させるために、紫外線吸収剤を受像層
に使用することは良く知られている。Image stability of the dye image transferred to the image receiving layer,
In particular, it is well known to use an ultraviolet absorber in the image receiving layer in order to improve the light resistance.
【０００４】特開昭59-158289号には、2-ヒドロキシフ
ェニルベンゾトリアゾール系の紫外線吸収剤を熱現像使
用色素受像材料および、感熱転写用色素受像材料に使用
することが記載されている。しかしながら、ここに記載
された紫外線吸収剤（以下ＵＶ剤と言う）を上記色素受
像材料に用いた場合、確かに耐光性の改良効果が認めら
れるものの、加熱下で色素を転写させるために、添加し
たＵＶ剤のかなりの量が、受像材料から、熱現像感光材
料または、感熱転写記録体に逆転写する事が判明した。
その結果、充分な紫外線カット効果が得られなくなるこ
とが分かった。更に、上記ＵＶ剤では、特に疎水性のバ
インダー中に添加された場合、色素画像の転写後、プリ
ントを保存中に受像層表面に上記ＵＶ剤が析出し、表面
光沢を低下させることが判明した。特に、プリントの保
存中の温度が高温状態と低温状態を繰り返した場合にそ
うした受像層表面への析出が起こり易くなることが分か
った。JP-A-59-158289 describes the use of a 2-hydroxyphenylbenzotriazole type ultraviolet absorber as a dye image receiving material for heat development and a dye image receiving material for thermal transfer. However, when the ultraviolet absorber described here (hereinafter referred to as UV agent) is used in the dye image-receiving material, although the effect of improving the light resistance is certainly recognized, it is added in order to transfer the dye under heating. It was found that a considerable amount of the UV agent was transferred from the image-receiving material to the photothermographic material or the thermal transfer recording material in a reverse transfer manner.
As a result, it was found that a sufficient UV blocking effect cannot be obtained. Furthermore, it has been found that the above UV agent, particularly when added to a hydrophobic binder, causes the UV gloss to be deposited on the surface of the image receiving layer during storage of the print after transfer of the dye image, thereby lowering the surface gloss. .. In particular, it has been found that such precipitation on the surface of the image receiving layer is likely to occur when the temperature during storage of the print is repeatedly high and low.
【０００５】かかる欠点を改良するために、本出願人は
先に色素受像材料にポリマー紫外線吸収剤を使用するこ
とを提供している（特開昭62-260152号）。To remedy such drawbacks, the applicant has previously provided the use of polymeric UV absorbers in dye image receiving materials (JP-A-62-260152).
【０００６】これにより、転写後の受像層面の光沢が長
期の保存によっても相当改善されることが分かったが、
しかしながら、熱現像感光材料から加熱下で色素転写を
行った場合には必ずしも充分ではないことが判明した。As a result, it was found that the gloss of the image-receiving layer surface after transfer was considerably improved even after long-term storage.
However, it has been found that it is not always sufficient when dye transfer is performed from a photothermographic material under heating.
【０００７】即ち、通常、熱現像感光材料にＵＶ剤を添
加するのは周知のことであり、ＵＶ剤は、通常、露光時
の紫外線を吸収して適正な分光感度分布を作るため、あ
るいは、熱現像感光材料の製造時に塗布時や切断時に高
速で搬送される際に生じる静電気の放電によるスタチッ
クカブリの軽減等の目的で使用される。しかし、色素画
像が受像層に転写される際に、熱現像感光材料に添加し
たＵＶ剤も受像層に同時に一部転写していることが判明
した。That is, it is generally known that a UV agent is added to a photothermographic material, and the UV agent usually absorbs ultraviolet rays at the time of exposure to form an appropriate spectral sensitivity distribution, or It is used for the purpose of reducing static fog caused by discharge of static electricity that occurs during high speed conveyance during coating or cutting during the production of a photothermographic material. However, it was found that when the dye image was transferred to the image receiving layer, the UV agent added to the photothermographic material was also partially transferred to the image receiving layer at the same time.
【０００８】そして、この熱現像感光材料に添加したＵ
Ｖ剤の受像層に転写により、プリントを長期間保存した
場合には上記と同様に、プリント表面にその一部が析出
することが判明した。U added to the photothermographic material
When the print was stored for a long time, it was found that a part of the V agent was deposited on the surface of the print by transfer to the image receiving layer of the V agent.
【０００９】[0009]
【発明の目的】本発明の目的は、色素受像層表面の光沢
性を長期間劣化させることなく、熱現像感光材料を製造
する際のスタチックカブリを防止した熱現像感光材料を
提供することにある。OBJECT OF THE INVENTION It is an object of the present invention to provide a photothermographic material capable of preventing static fog during production of the photothermographic material without deteriorating the glossiness of the surface of the dye image-receiving layer for a long period of time. is there.
【００１０】[0010]
【発明の構成】上記本発明の目的は、支持体上に、バイ
ンダー、感光性ハロゲン化銀、熱現像処理により拡散性
色素を放出または形成する色素供与物質、及び下記一般
式〔１〕で表される繰り返し単位を有するポリマー紫外
線吸収剤を含有することを特徴とする熱現像感光材料に
よって達成される。The above object of the present invention is to provide a support, a binder, a photosensitive silver halide, a dye-providing substance which releases or forms a diffusible dye by heat development, and a compound represented by the following general formula [1]. The photothermographic material is characterized by containing a polymer ultraviolet absorber having a repeating unit of
【００１１】[0011]
【化２】 [Chemical 2]
【００１２】式中、Ｒ1，Ｒ2およびＲ3はそれぞれ同じ
であっても異なっていても良く、水素原子または炭素原
子数１〜４のアルキル基を表す。In the formula, R 1 , R 2 and R 3 may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
【００１３】Ｌは-CONH-、-COO-またはフェニレン基を
表す。L represents -CONH-, -COO- or phenylene group.
【００１４】Ａは炭素原子数１〜20のアルキレン基また
は炭素原子数６〜20のアリーレン基を表し、Ｂは-NR4CO
2-、-COO-、-OCO-、-CONR4-、-SO2NR4-、-NR4SO2-、-SO
2-、または-O-基を表す。A represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, and B represents -NR 4 CO
2 -, - COO -, - OCO -, - CONR 4 -, - SO 2 NR 4 -, - NR 4 SO 2 -, - SO
Represents 2- or -O-group.
【００１５】Ｒ4は水素原子または炭素原子数１〜20の
アルキル基又は炭素原子数６〜20のアリール基を表す。R 4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.
【００１６】ｍとｎはそれぞれ独立に０または１を表
す。M and n each independently represent 0 or 1.
【００１７】Ｑは紫外線吸収剤残基を表す。Q represents an ultraviolet absorber residue.
【００１８】以下、本発明の構成を詳細に説明する。The structure of the present invention will be described in detail below.
【００１９】一般式〔１〕で表される繰り返し単位にお
いて、Ｒ1，Ｒ2およびＲ3は水素原子または炭素原子１
〜４のアルキル基であるが、好ましくは水素原子または
メチル基である。特に好ましくはＲ1とＲ3が共に水素原
子であり、Ｒ2が水素原子またはメチル基である。In the repeating unit represented by the general formula [1], R 1 , R 2 and R 3 are hydrogen atom or carbon atom 1
Alkyl groups of 4 to 4, but preferably a hydrogen atom or a methyl group. Particularly preferably, R 1 and R 3 are both hydrogen atoms, and R 2 is a hydrogen atom or a methyl group.
【００２０】一般式〔１〕において、Ｑで表される紫外
線吸収剤残基は好ましくは下記一般式〔２〕、〔３〕ま
たは〔４〕で表される。In the general formula [1], the ultraviolet absorbent residue represented by Q is preferably represented by the following general formula [2], [3] or [4].
【００２１】[0021]
【化３】 [Chemical 3]
【００２２】〔Ｒ8およびＲ9はハロゲン原子、アルキル
基、アルコキシ基、アシル基、アシルオキシ基又はヒド
ロキシ基を表す。[R 8 and R 9 represent a halogen atom, an alkyl group, an alkoxy group, an acyl group, an acyloxy group or a hydroxy group.
【００２３】ｐは０〜４の整数、ｑは０〜３の整数を表
す。P represents an integer of 0 to 4, and q represents an integer of 0 to 3.
【００２４】ｐ及びｑが２以上のとき各々にＲ9とＲ8は
それぞれ互いに異っていてもよい。〕When p and q are 2 or more, R 9 and R 8 may be different from each other. ]
【００２５】[0025]
【化４】 [Chemical 4]
【００２６】〔式中Ｒ10はヒドロキシル基又はOR12又は
OCOR13基を表す。[Wherein R 10 is a hydroxyl group or OR 12 or
Represents OCOR 13 group.
【００２７】Ｒ11は、ハロゲン原子、アルキル基、アシ
ル基、アシルオキシ基、ヒドロキシル基又はアミノ基を
表す。Ｒ12，Ｒ13はアルキル基、又はアリール基を表
す。R 11 represents a halogen atom, an alkyl group, an acyl group, an acyloxy group, a hydroxyl group or an amino group. R 12 and R 13 represent an alkyl group or an aryl group.
【００２８】ｒは０又は１を表し、ｓは０〜２の整数を
表す。R represents 0 or 1, and s represents an integer of 0-2.
【００２９】ｓ＝２のときＲ11は異なっていてもよ
い。〕特に、一般式〔２〕または〔３〕で表されるベン
ゾトリアゾール系紫外線吸収剤残基が特に好ましい。When s = 2, R 11 may be different. In particular, the benzotriazole-based UV absorber residue represented by the general formula [2] or [3] is particularly preferable.
【００３０】以下、本発明で用いられる一般式〔１〕で
表される繰り返し単位の具体的な例を示す。Specific examples of the repeating unit represented by the general formula [1] used in the present invention are shown below.
【００３１】[0031]
【化５】 [Chemical 5]
【００３２】[0032]
【化６】 [Chemical 6]
【００３３】[0033]
【化７】 [Chemical 7]
【００３４】[0034]
【化８】 [Chemical 8]
【００３５】[0035]
【化９】 [Chemical 9]
【００３６】上記以外にも特開昭53-1078935号第４〜６
頁、同58-185677号第３頁、同61-42652号及び同62-2601
52号第４〜６頁に記載のモノマーから誘導される繰り返
し単位も有用である。In addition to the above, JP-A-53-1078935, Nos. 4 to 6
Pp. 58-185677 page 3, pp. 61-42652 and 62-2601.
Repeating units derived from the monomers described in No. 52, pages 4-6 are also useful.
【００３７】本発明の上記一般式〔１〕で表される繰り
返し単位を有するポリマー紫外線吸収剤（以下本発明の
ＵＶ剤と言う）は一般式〔１〕で表される繰り返し単位
とは別の繰り返し単位を１以上有している共重合であっ
ても良く、そのような別の繰り返し単位を構成するモノ
マーとしては、例えばアクリル酸エステル類、メタアク
リル酸エステル類、ビニルエステル類、アクリルアミド
類、メタアクリルアミド類、ビニルエーテル類、オレフ
ィン類、スチレン類、アクリル酸類、メタクリル酸類、
イタコン酸類、マレイン酸類等がある。具体的には、特
開昭62-260152号７〜９頁に記載された単量体が挙げら
れる。中でも、アクリル酸エステル類（例えばブチルア
クリレート、エチルアクリレート等）、メタアクリル酸
エステル類（ブチルメタアクリレート、オクチルメタア
クリレート等）、スチレン類が好ましい。The polymer ultraviolet absorber having a repeating unit represented by the above general formula [1] of the present invention (hereinafter referred to as UV agent of the present invention) is different from the repeating unit represented by the general formula [1]. It may be a copolymer having one or more repeating units, and examples of the monomer constituting such another repeating unit include acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, Methacrylamides, vinyl ethers, olefins, styrenes, acrylic acids, methacrylic acids,
There are itaconic acids, maleic acids and the like. Specific examples thereof include the monomers described in JP-A-62-260152, pages 7-9. Among them, acrylic acid esters (for example, butyl acrylate, ethyl acrylate, etc.), methacrylic acid esters (butyl methacrylate, octyl methacrylate, etc.), and styrenes are preferable.
【００３８】以下本発明のポリマーＵＶ剤の具体的な例
を挙げる。Specific examples of the polymer UV agent of the present invention will be given below.
【００３９】但し以下のポリマーの記載において、一般
式〔１〕で表される繰り返し単位と共に共重合される成
分のモノマーは以下のものを表す。However, in the following description of the polymer, the monomer of the component copolymerized with the repeating unit represented by the general formula [1] is as follows.
【００４０】ＳＴ：スチレン ＢＡ：n-ブチルアクリレート ＭＢＡ：n-ブチルメタクリレート ＭＭＡ：メチルメタクリレート ＮＢＡＡ：N-ブチルアクリルアミド ＭＡ：メチルアクリレート ＥＭＡ：エチルメタクリレート 以下に共重合ポリマーの具体例を挙げる。ST: Styrene BA: n-Butyl Acrylate MBA: n-Butyl Methacrylate MMA: Methyl Methacrylate NBAA: N-Butyl Acrylamide MA: Methyl Acrylate EMA: Ethyl Methacrylate The following are specific examples of the copolymer.
【００４１】Ｐ−１ (Ｍ-１)50-(ＢＡ)50 Ｐ−２ (Ｍ-１)50-(ＭＢＡ)50 Ｐ−３ (Ｍ-１)70-(ＭＡ)30 Ｐ−４ (Ｍ-１)40-(ＮＢＡＡ)60 Ｐ−５ (Ｍ-１)60-(ＥＭＡ)40 Ｐ−６ (Ｍ-１)50-(ＢＡ)45-(ＳＴ)5 Ｐ−７ (Ｍ-１)70-(ＭＭＡ)30 Ｐ−８ (Ｍ-５)60-(ＢＡ)40 Ｐ−９ (Ｍ-５)40-(ＭＡ)60 Ｐ−10 (Ｍ-５)60-(ＢＡ)30-(ＭＭＡ)10 Ｐ−11 (Ｍ-８)50-(ＢＡ)50 Ｐ−12 (Ｍ-８)70-(ＭＢＡ)30 Ｐ−13 (Ｍ-９)60-(ＢＡ)40 P-14 (Ｍ-10)60-(ＢＡ)40 Ｐ−15 (Ｍ-10)50-(ＥＭＡ)50 Ｐ−16 (Ｍ-10)40-(ＳＴ)5-(ＢＡ)55 Ｐ−17 (Ｍ-12)50-(ＢＡ)50 Ｐ−18 (Ｍ-13)50-(ＢＡ)50 Ｐ−19 (Ｍ-15)50-(ＢＡ)50 Ｐ−20 (Ｍ-17)50-(ＢＡ)50 本発明のＵＶ剤において、Ｑで表される紫外線吸収剤残
基を有する繰り返し単位は、本発明のＵＶ剤ポリマーの
５〜100重量％、好ましくは10〜90重量％、更に好まし
くは20〜85重量％である。P-1 (M-1) 50- (BA) 50 P-2 (M-1) 50- (MBA) 50 P-3 (M-1) 70- (MA) 30 P-4 (M -1) 40 - (NBAA) 60 P-5 (M-1) 60 - (EMA) 40 P-6 (M-1) 50 - (BA) 45 - (ST) 5 P-7 (M-1) 70- (MMA) 30 P-8 (M-5) 60- (BA) 40 P-9 (M-5) 40- (MA) 60 P-10 (M-5) 60- (BA) 30- ( MMA) 10 P-11 (M-8) 50- (BA) 50 P-12 (M-8) 70- (MBA) 30 P-13 (M-9) 60- (BA) 40 P-14 (M -10) 60 - (BA) 40 P-15 (M-10) 50 - (EMA) 50 P-16 (M-10) 40 - (ST) 5 - (BA) 55 P-17 (M-12) 50- (BA) 50 P-18 (M-13) 50- (BA) 50 P-19 (M-15) 50- (BA) 50 P-20 (M-17) 50- (BA) 50 In the UV agent, the repeating unit having an ultraviolet absorbent residue represented by Q is 5 to 100% by weight, preferably 10 to 90% by weight of the UV agent polymer of the present invention, and more preferably 20 to 85 percent by weight.
【００４２】本発明のポリマーＵＶ剤は公知の乳化重合
法または溶液重合法により重合されたものを用いること
ができる。乳化重合法は例えば、米国特許第4,080,211
号、同3,370,952号等に記載された方法で重合され、ま
た、米国特許第3,451,820号に記載されたように、親油
性ポリマーをゼラチン等の親水性コロイド水溶液中でラ
テックスの形で分散する事もできる。As the polymer UV agent of the present invention, those polymerized by a known emulsion polymerization method or solution polymerization method can be used. Emulsion polymerization methods are described, for example, in U.S. Pat. No. 4,080,211.
No. 3,370,952 and the like, and may be polymerized by a method described in U.S. Pat.No. 3,451,820, and a lipophilic polymer may be dispersed in the form of a latex in a hydrophilic colloid aqueous solution such as gelatin. it can.
【００４３】これら重合ホモポリマーの形成およびコポ
リマーの形成にも適用可能である。It is also applicable to the formation of these polymerized homopolymers and the formation of copolymers.
【００４４】乳化重合法において用いられる乳化剤とし
ては、界面活性剤、高分子保護コロイド、および共重合
化剤が挙げられる。界面活性剤としては公知のアニオ
ン、カチオン、及び両性活性剤が使用できる。Examples of the emulsifier used in the emulsion polymerization method include a surfactant, a polymeric protective colloid, and a copolymerizing agent. As the surfactant, known anions, cations, and amphoteric surfactants can be used.
【００４５】一方、溶液重合法によって重合する場合、
溶液重合されるポリマー単量体の良溶媒中で、重合開始
剤の存在下で溶液重合される。ポリマー単量体の良溶媒
としては、水、トルエン、アルコール類、アセトン、メ
チルエチルケトン、テトラヒドロフラン、ジオキサン、
ジメチルホルムアミド、酢酸エチル、ジメチルスルホキ
シド、アセトニトリル、塩化メチレン等を挙げることが
でき、これらの中から適宜適当な溶媒を選択して重合さ
れる。これらの溶媒は単独または２種以上併用して用い
ることもできる。On the other hand, when polymerizing by a solution polymerization method,
Solution polymerization is carried out in the presence of a polymerization initiator in a good solvent for the polymer monomer to be solution polymerized. As a good solvent for the polymer monomer, water, toluene, alcohols, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane,
Examples thereof include dimethylformamide, ethyl acetate, dimethylsulfoxide, acetonitrile and methylene chloride, and an appropriate solvent is appropriately selected from these to perform polymerization. These solvents may be used alone or in combination of two or more.
【００４６】重合温度は重合開始剤の種類、使用する溶
媒の種類等により変化するが一般的には30〜120℃であ
る。The polymerization temperature varies depending on the type of polymerization initiator, the type of solvent used, etc., but is generally 30 to 120 ° C.
【００４７】本発明のポリマーＵＶ剤の乳化重合法およ
び溶液重合法に用いられる重合開始剤としては、例え
ば、以下のものを挙げることができる。Examples of the polymerization initiator used in the emulsion polymerization method and solution polymerization method of the polymer UV agent of the present invention include the following.
【００４８】水溶性重合開始剤； 過硫酸塩（過硫酸カリウム、過硫酸アンモニウム等）、 水溶性アゾ化合物（4,4′-アゾビス-4-シアノ吉草酸ナ
トリウム、2,2′-アゾビス(2-アミノプロパン)塩酸塩
等） 過酸化水素 親油性重合開始剤； アゾ化合物（アゾビスイソブチルニトリル、2,2′-アゾ
ビス(2,4ジメチルバレロニトリル）、2,2′-アゾビスイ
ソシアノ酪酸等） 過酸化物（ベンゾイルパーオキサイド、ラウリルパーオ
キサイド、クロロベンジルパーオキサイド等） これらの重合開始剤は乳化重合法及び溶液重合法におい
て、単量体全量に対して、0.01〜10重量％の間、好まし
くは0.1〜５重量％の範囲で用いられる。Water-soluble polymerization initiators: persulfates (potassium persulfate, ammonium persulfate, etc.), water-soluble azo compounds (sodium 4,4'-azobis-4-cyanovalerate, 2,2'-azobis (2- Aminopropane) hydrochloride, etc.) Hydrogen peroxide Lipophilic polymerization initiator; Azo compounds (azobisisobutylnitrile, 2,2'-azobis (2,4dimethylvaleronitrile), 2,2'-azobisisocyanobutyric acid, etc. ) Peroxides (benzoyl peroxide, lauryl peroxide, chlorobenzyl peroxide, etc.) These polymerization initiators are used in the emulsion polymerization method and the solution polymerization method in an amount of 0.01 to 10% by weight based on the total amount of the monomers, It is preferably used in the range of 0.1 to 5% by weight.
【００４９】本発明のポリマーＵＶ剤の平均分子量は10
00〜100万の範囲であり、好ましくは2000〜50万、更に
好ましくは5000〜10万である。The polymer UV agent of the present invention has an average molecular weight of 10
It is in the range of 100 to 100,000, preferably 2000 to 500,000, and more preferably 5000 to 100,000.
【００５０】また、ポリマーＵＶ剤のＴｇは約150℃以
下、好ましくは約100℃以下、特に好ましくは約60℃以
下であることがポリマーの熱現像感光材料の構成層中で
の安定性や皮膜物性、特に、固体熱溶剤を含有する熱現
像感光材料において、皮膜の脆弱性を改良する観点から
好ましい。The Tg of the polymer UV agent is about 150 ° C. or lower, preferably about 100 ° C. or lower, and particularly preferably about 60 ° C. or lower. It is preferable from the standpoint of improving the brittleness of the film in the physical properties, especially in the photothermographic material containing a solid thermal solvent.
【００５１】本発明のＵＶ剤のＴｇの下限は特に規定さ
れないが、一般的なポリマーの特性として約-50℃以上
のものが好ましく用いられる。The lower limit of Tg of the UV agent of the present invention is not particularly specified, but as a general polymer property, a polymer having a Tg of about -50 ° C or higher is preferably used.
【００５２】本発明のポリマーＵＶ剤は熱現像感光材料
を構成する任意の構成層中に添加することができる。具
体的には、感光性層、中間層、保護層、下引き層、バッ
ク層等の任意の層中に添加される。添加量は、一般式
〔１〕で表される繰り返し単位の比率や紫外線吸収剤残
基の種類にもよるが、一般的には熱現像感光材料１m2あ
たり0.01〜５g、好ましくは0.1〜２gの範囲である。The polymer UV agent of the present invention can be added to any constituent layer constituting the photothermographic material. Specifically, it is added to any layer such as a photosensitive layer, an intermediate layer, a protective layer, an undercoat layer, and a back layer. The addition amount depends on the ratio of the repeating unit represented by the general formula [1] and the kind of the ultraviolet absorbent residue, but is generally 0.01 to 5 g, preferably 0.1 to 2 g per 1 m 2 of the photothermographic material. The range is.
【００５３】本発明のポリマーＵＶ剤を熱現像感光材料
の写真構成層中に添加する場合、それぞれの塗布液中に
適当な形で添加される。When the polymer UV agent of the present invention is added to the photographic constituent layers of the photothermographic material, it is added to each coating solution in an appropriate form.
【００５４】本発明のポリマーＵＶ剤が乳化重合された
ラテックスポリマーである場合、直接ラテックス溶液と
して塗布液中に添加されることが好ましい。When the polymer UV agent of the present invention is an emulsion-polymerized latex polymer, it is preferably added directly to the coating solution as a latex solution.
【００５５】一方、本発明のポリマーＵＶ剤が溶液重合
法によって重合された場合、水溶性ポリマーである場
合、直接塗布液中に添加される。更にポリマーＵＶ剤が
親油性である場合、適当な補助溶媒（例えば酢酸エチ
ル、アセトン、ジメチルホルムアミド等）の存在下にゼ
ラチンなどの親水性コロイド水溶液中に乳化分散して用
いられる。On the other hand, when the polymer UV agent of the present invention is polymerized by the solution polymerization method and is a water-soluble polymer, it is directly added to the coating solution. Further, when the polymer UV agent is lipophilic, it is used by emulsifying and dispersing in a hydrophilic colloid aqueous solution such as gelatin in the presence of a suitable auxiliary solvent (eg ethyl acetate, acetone, dimethylformamide etc.).
【００５６】この際、公知の高沸点有機溶媒を使用する
こともできるが、高沸点有機溶媒がポリマーでない場合
（例えばジブチルフタレート、ジオクチルフタレート、
ジイソデシルフタレート、トリクレジルホスフェート
等）にはこうした高沸点有機溶媒は用いない方が好まし
い。用いることの出来る量は、本発明のポリマーＵＶ剤
に対して50重量％以下である。At this time, a known high-boiling point organic solvent can be used, but when the high-boiling point organic solvent is not a polymer (for example, dibutyl phthalate, dioctyl phthalate,
It is preferable not to use such a high boiling point organic solvent for diisodecyl phthalate, tricresyl phosphate, etc.). The amount that can be used is not more than 50% by weight, based on the polymeric UV agent of the invention.
【００５７】本発明のポリマーＵＶ剤を乳化分散して用
いる場合、紫外線吸収性のない親油性ポリマーを用いる
ことも可能である。例えば、ポリブチルアクリレート、
ポリブチルメタアクリレート、ポチエチルアクリレー
ト、ポリ-N-ブチルアクリルアミド等のポリマーの存在
下に乳化分散することは分散粒子の安定性向上や皮膜物
性改良のためにも好ましい方法のひとつである。When the polymer UV agent of the present invention is emulsified and dispersed, it is possible to use a lipophilic polymer having no ultraviolet absorption. For example, polybutyl acrylate,
Emulsifying and dispersing in the presence of a polymer such as polybutyl methacrylate, potyethyl acrylate, poly-N-butyl acrylamide is one of the preferable methods for improving the stability of dispersed particles and improving the physical properties of the film.
【００５８】以下、本発明の熱現像感光材料についてさ
らに説明する。The photothermographic material of the present invention will be further described below.
【００５９】本発明の熱現像感光材料は、感光性ハロゲ
ン化銀及び熱現像時に拡散性色素を放出または形成する
色素供与物質を含有する少なくとも１層の感光性層を支
持体上に有するものであるが、好ましくはイエロー、マ
ゼンタ、シアンの各拡散性色素を形成ないし放出する３
つ以上の感光性層からなり、異なる色相の色素を形成な
いし放出する感光性層には好ましくは中間層が混色防止
の観点から好ましい。The heat-developable light-sensitive material of the present invention has on a support at least one light-sensitive layer containing a light-sensitive silver halide and a dye-donor substance that releases or forms a diffusible dye during heat development. However, it is preferable to form or release yellow, magenta and cyan diffusible dyes.
An intermediate layer is preferable for the photosensitive layer composed of one or more photosensitive layers and forming or releasing dyes having different hues, from the viewpoint of preventing color mixture.
【００６０】本発明の熱現像感光材料に用いられる、感
光性ハロゲン化銀としては従来公知のものを使用するこ
とができ、例えば、塩化銀、臭化銀、沃臭化銀、塩臭化
銀、塩沃臭化銀を用いることができる。As the photosensitive silver halide used in the photothermographic material of the present invention, those known in the art can be used, for example, silver chloride, silver bromide, silver iodobromide, silver chlorobromide. Alternatively, silver chloroiodobromide can be used.
【００６１】ハロゲン化銀は粒子内部から表面まで均一
な組成のもの、内部と表面で組成が連続的に又はステッ
プ状に変化しているハロゲン化銀であってもよい。The silver halide may have a uniform composition from the inside to the surface of the grain, or may have a composition which continuously or stepwise changes between the inside and the surface.
【００６２】ハロゲン化銀の形状は平板状、立方体、球
形、８面体、12面体、14面体等の明確な晶癖を有するも
の又はそうでないもの等を用いることができる。The shape of silver halide may be tabular, cubic, spherical, octahedron, dodecahedron, tetrahedron or the like having a clear crystal habit or not.
【００６３】又、例えば、米国特許2,592,250号、同3,2
20,613号、同3,271,257号、同3,317,322号、同3,511,62
2号、同3,531,291号、同3,447,927号、同3,761,266号、
同3,703,584号、同3,736,140号、同3,761,276号、特開
昭52-15661号、同55-127549号等に記載の内部潜像型ハ
ロゲン化銀乳剤も用いることができる。Also, for example, US Pat.
20,613, 3,271,257, 3,317,322, 3,511,62
No. 2, No. 3,531,291, No. 3,447,927, No. 3,761,266,
The internal latent image type silver halide emulsions described in JP-A-3,703,584, JP-A-3736,140, JP-A-3,761,276, JP-A-52-15661 and JP-A-55-127549 can also be used.
【００６４】感光性ハロゲン化銀はその粒子形成段階に
おいて、イリジウム、金、ロジウム、鉄、鉛等の金属イ
オン種を適当な塩の形で添加することができる。The light-sensitive silver halide can be added with a metal ion species such as iridium, gold, rhodium, iron and lead in the form of a suitable salt at the stage of grain formation.
【００６５】上記感光性ハロゲン化銀乳剤の粒径は約0.
02〜２μmであり、好ましくは約0.05〜0.5μmである。The photosensitive silver halide emulsion has a grain size of about 0.
The thickness is 02 to 2 μm, preferably about 0.05 to 0.5 μm.
【００６６】本発明において、感光性ハロゲン化銀の調
製方法として、水溶性ハロゲン化物などの感光性銀塩形
成成分を後述の有機銀塩と共存させ、有機銀塩の一部を
感光性ハロゲン化銀の一部に変換させて形成させること
もできる。In the present invention, as a method for preparing a photosensitive silver halide, a photosensitive silver salt forming component such as a water-soluble halide is allowed to coexist with an organic silver salt described below, and a part of the organic silver salt is subjected to photosensitive halogenation. It can also be formed by converting a part of silver.
【００６７】感光性ハロゲン化銀乳剤は公知の増感剤
（例えば、活性ゼラチン、無機硫黄、チオ硫酸ナトリウ
ム、二酸化チオ尿素、塩化金酸ナトリウム等）でハロゲ
ン化銀粒子表面を化学増感することができ、含窒素ヘテ
ロ環化合物或はメルカプト基含有ヘテロ環化合物の存在
下に化学増感をすることもできる。The photosensitive silver halide emulsion is prepared by chemically sensitizing the surface of silver halide grains with a known sensitizer (eg, active gelatin, inorganic sulfur, sodium thiosulfate, thiourea dioxide, sodium chloroaurate). It is also possible to carry out chemical sensitization in the presence of a nitrogen-containing heterocyclic compound or a mercapto group-containing heterocyclic compound.
【００６８】更に感光性ハロゲン化銀は公知のシアニ
ン、メロシアニン等の通常写真で用いられる分光増感色
素により、青、緑、赤、近赤外光への分光増感を施すこ
とができる。Further, the photosensitive silver halide can be spectrally sensitized to blue, green, red and near-infrared light by a known spectral sensitizing dye such as cyanine and merocyanine used in ordinary photography.
【００６９】これらの増感色素はハロゲン化銀１モル当
たり、１μmol〜１mol、好ましくは10μmol〜0.1mol
を、ハロゲン化銀粒子形成時、可溶性塩類の除去時、化
学増感開始前、化学増感時、或は化学増感終了時以降の
いずれにおいても添加することができる。These sensitizing dyes are used in an amount of 1 μmol to 1 mol, preferably 10 μmol to 0.1 mol, per mol of silver halide.
Can be added at any time during the formation of silver halide grains, the removal of soluble salts, before the start of chemical sensitization, at the time of chemical sensitization, or after the end of chemical sensitization.
【００７０】本発明の熱現像感光材料に用いられる色素
供与物質としては、例えば特開昭61-61157号、同61-611
58号、同62-44738号、同62-129850号、同62-129851号、
同62-129852号、同62-169158号、特願平1-200859号に記
載されている拡散性の色素を形成するカプラー、例えば
特開昭61-88254号記載のロイコ色素、米国特許4,235,95
7号に記載のアゾ色素、或は米国特許4,463,079号、同4,
439,513号、特開昭59-60434号、同59-65839号、同59-71
046号、同59-87450号、同59-123837号、同59-124329
号、同59-165054号、同59-165055号等が挙げられる。特
にカップリング反応により拡散性色素を形成する化合物
が好ましく、例えば、特開平2-863号公報９頁左下欄２
行目の一般式（イ）で表されるものである。Examples of dye-donor substances used in the photothermographic material of the present invention include those disclosed in JP-A-61-61157 and 61-611.
No. 58, No. 62-44738, No. 62-129850, No. 62-129851,
No. 62-129852, No. 62-169158, couplers forming diffusible dyes described in Japanese Patent Application No. 1-200859, for example, leuco dyes described in JP-A No. 61-88254, U.S. Pat. 95
Azo dyes described in No. 7, or U.S. Patent Nos. 4,463,079, 4,
439,513, JP-A-59-60434, 59-65839, 59-71
046, 59-87450, 59-123837, 59-124329
No. 59-165054, No. 59-165055, etc. In particular, a compound that forms a diffusible dye by a coupling reaction is preferable. For example, JP-A-2-863, page 9, lower left column 2
It is represented by the general formula (a) in the line.
【００７１】中でも同公報９頁右下欄８行目に記載され
た、一般式（ロ）で表される単量体から誘導される繰り
返し単位を有するポリマー鎖を有するポリマーカプラー
が好ましい。Among them, a polymer coupler having a polymer chain having a repeating unit derived from a monomer represented by the general formula (b) described in the lower right column, line 8 of the same publication is preferable.
【００７２】ポジ型の色素供与物質としては、例えば、
特開昭59-55430号、同59-165054号、同59-154445号、同
59-116655号、同59-124327号、同59-152440号、同64-13
546号等の各公報に記載された化合物がある。Examples of the positive type dye-providing substance include, for example,
JP 59-55430, 59-165054, 59-154445,
59-116655, 59-124327, 59-152440, 64-13
There are compounds described in each publication such as No. 546.
【００７３】上記色素供与物質は、単独で又は、２種以
上併用して用いてもよい。The above dye-providing substances may be used alone or in combination of two or more.
【００７４】又、本発明の熱現像感光材料は、例えば、
特開平2-293753号、同2-308162号公報に記載された重合
性化合物と共に、色素供与物質をマイクロカプセル中に
含有せしめ、これを熱現像することで、重合性化合物の
重合反応を像状もしくは逆像状に起こして、マイクロカ
プセルを硬化させ、色素供与物質の受像層への拡散性を
変化させて画像を形成させる方式の熱現像感光材料にも
適用できる。The photothermographic material of the present invention is, for example,
A dye-donor substance is contained in a microcapsule together with the polymerizable compound described in JP-A-2-293753 and JP-A-2-308162, and the resulting compound is thermally developed to image-wise the polymerization reaction of the polymerizable compound. Alternatively, it can also be applied to a photothermographic material of a type in which the microcapsules are cured in the reverse image to change the diffusivity of the dye-donor substance to the image receiving layer to form an image.
【００７５】本発明の熱現像感光材料には、感度の上昇
や、現像性の向上を目的として、公知の有機銀塩を用い
ることができる。In the photothermographic material of the present invention, known organic silver salts can be used for the purpose of increasing sensitivity and improving developability.
【００７６】本発明で用いることのできる有機銀塩は、
例えば、特公昭43-4921号、特開昭49-52626号、同52-14
1222号、同53-36224号、同53-37626号、同53-36224号、
同53-37610号等の各公報並びに米国特許3,330,633号、
同3,794,496号、同4,105,451号等の各公報に記載されて
いる長鎖脂肪族カルボン酸の銀塩やヘテロ環を有するカ
ルボン酸の銀塩（例えばベヘン酸銀、α-(1-フェニルテ
トラゾールチオ)酢酸銀等）、特公昭44-26582号、同45-
12700号、同45-18416号、同45-22815号、特開昭52-1373
21号、同58-118638号、同58-118639号、米国特許4,123,
274号等の公報に記載されているイミノ基を有する化合
物の銀塩、特開昭61-249044号記載のアセチレン銀等を
挙げることができる。The organic silver salt that can be used in the present invention is
For example, JP-B-43-4921, JP-A-49-52626, and JP-A-52-14
1222, 53-36224, 53-37626, 53-36224,
53-37610 and other publications and U.S. Patent 3,330,633,
No. 3,794,496, No. 4,105,451, etc., silver salts of long-chain aliphatic carboxylic acids and silver salts of carboxylic acids having a heterocycle (for example, silver behenate, α- (1-phenyltetrazolethio)). Silver acetate), Japanese Patent Publication No. 44-26582, No. 45-
No. 12700, No. 45-18416, No. 45-22815, JP-A-52-1373
No. 21, No. 58-118638, No. 58-118639, U.S. Pat.
Examples thereof include silver salts of compounds having an imino group described in JP-A No. 274 and the like, acetylene silver described in JP-A No. 61-249044, and the like.
【００７７】特にイミノ基を有する化合物の銀塩が好ま
しく、例えばベンゾトリアゾール及びその誘導体の銀塩
（例えばベンゾトリアゾール銀、5-メチルベンゾトリア
ゾール銀等）が特に好ましい。Particularly, a silver salt of a compound having an imino group is preferable, and for example, a silver salt of benzotriazole and its derivative (for example, silver benzotriazole, silver 5-methylbenzotriazole, etc.) is particularly preferable.
【００７８】本発明の熱現像感光材料は還元剤を用いる
ことが好ましい。好ましく用いられる還元剤は、現像機
構や色素形成乃至放出機構により熱現像感光材料用とし
て従来知られているものの中から選択して使用される。
ここで言う還元剤には、熱現像時に還元剤を放出する還
元剤プレカーサーも含まれる。A reducing agent is preferably used in the photothermographic material of the invention. The reducing agent preferably used is selected from those conventionally known for photothermographic materials depending on the developing mechanism and the dye forming or releasing mechanism.
The reducing agent referred to herein also includes a reducing agent precursor that releases the reducing agent during thermal development.
【００７９】本発明に用いることのできる、還元剤とし
ては、例えば、米国特許3,351,286号、同3,761,270号、
同3,764,328号、同3,342,599号、同3,719,492号明細
書、リサーチ・ディスクロージャー12,146号、同15,108
号、同15,127号、及び特開昭56-27132号、同53-135628
号、同57-79035号に記載のp-フェニレンジアミン系及
び、p-アミノフェノール系現像主薬、リン酸アミドフェ
ノール系現像主薬、スルフォンアミドアニリン系現像主
薬、及びヒドラゾン系現像主薬、フェノール類、スルフ
ォンアミドフェノール類、ポリヒドロキシベンゼン類、
ナフトール類、ヒドロキシビスナフチル類、メチレンビ
スフェノール類、アスコルビン酸類、1-アリール-3-ピ
ラゾリドン類、ヒドラゾン類、及び上記種々の還元剤の
プレカーサー類がある。Examples of the reducing agent that can be used in the present invention include US Pat. Nos. 3,351,286 and 3,761,270,
3,764,328, 3,342,599, 3,719,492, Research Disclosure 12,146, 15,108
No. 15,127, and JP-A-56-27132, 53-135628.
No. 57-79035, p-phenylenediamine and p-aminophenol-based developing agent, phosphoric acid amide phenol-based developing agent, sulfonamide aniline-based developing agent, and hydrazone-based developing agent, phenols, sulfone Amidophenols, polyhydroxybenzenes,
There are naphthols, hydroxybisnaphthyls, methylenebisphenols, ascorbic acids, 1-aryl-3-pyrazolidones, hydrazones, and precursors of the above various reducing agents.
【００８０】又、色素供与物質が還元剤を兼ねることも
できる。Further, the dye-providing substance can also serve as the reducing agent.
【００８１】特に好ましい還元剤は、特開昭56-146133
号及び同62-227141号記載のN-(p-N',N'-ジアルキルアミ
ノ)フェニルスルファミン酸塩及びその誘導体であり、
具体的には、特開平2-863号公報７頁左下欄６行目から
８頁右下欄に記載された化合物を挙げることができる。A particularly preferred reducing agent is JP-A-56-146133.
No. 62-227141 and N- (p-N ', N'-dialkylamino) phenylsulfamate and derivatives thereof,
Specific examples thereof include the compounds described in JP-A-2-863, page 7, lower left column, line 6 to page 8, lower right column.
【００８２】本発明の熱現像感光材料には色素の転写促
進その他の目的で、熱溶剤を用いることができる。熱溶
剤は熱現像時に液状化し熱現像や色素の熱転写を促進す
る作用を有する化合物であり、常温では固体状態である
ことが好ましい。A thermal solvent can be used in the photothermographic material of the present invention for the purpose of accelerating the transfer of dye and other purposes. The thermal solvent is a compound that has a function of liquefying during thermal development and promoting thermal development and thermal transfer of a dye, and is preferably in a solid state at room temperature.
【００８３】本発明で用いることのできる熱溶剤として
は、例えば米国特許3,347,675号、同3,667,959号、同3,
438,776号、同3,666,477号、リサーチ・ディスクロジャ
ーNo.17,643号、特開昭51-19525号、同53-24829号、同5
3-60223号、同58-118640号、同58-198038号、同59-2295
56号、同59-68730号、同59-84236号、同60-191251号、
同60-232547号、同60-14241号、同61-52643号、同62-78
554号、同62-42153号、同62-44737号、同63-53548号、
同63-161446号、特開平1-224751号、同2-863号、同2-12
0739号、同2-123354号等の各公報に記載された化合物が
挙げられる。Examples of the thermal solvent which can be used in the present invention include US Pat. Nos. 3,347,675, 3,667,959, and 3,347,675.
438,776, 3,666,477, Research Disclosure No. 17,643, JP-A-51-19525, 53-24829, 5
3-60223, 58-118640, 58-198038, 59-2295
No. 56, No. 59-68730, No. 59-84236, No. 60-191251,
No. 60-232547, No. 60-14241, No. 61-52643, No. 62-78
554, 62-42153, 62-44737, 63-53548,
63-161446, JP-A 1-224751, 2-863, 2-12
Examples thereof include the compounds described in each publication such as 0739 and 2-123354.
【００８４】具体的には、尿素誘導体（尿素、ジメチル
尿素、フェニル尿素等）、アミド誘導体（例えばアセト
アミド、ステアリルアミド、p-トルアミド、p-プロパノ
イルオキシエトキシベンズアミド等）、スルホンアミド
誘導体（例えば、p-トルエンスルホンアミド等）、多価
アルコール類（例えば1,6ヘキサンジオール、ペンタエ
リスリトール、ポリエチレングリコール等）が好ましく
用いられる。Specifically, urea derivatives (urea, dimethylurea, phenylurea, etc.), amide derivatives (acetamide, stearylamide, p-toluamide, p-propanoyloxyethoxybenzamide, etc.), sulfonamide derivatives (eg, P-toluenesulfonamide, etc.) and polyhydric alcohols (eg 1,6 hexanediol, pentaerythritol, polyethylene glycol etc.) are preferably used.
【００８５】上記熱溶剤は、感光性ハロゲン化銀乳剤
層、中間層、保護層、或は受像材料の受像層等任意の層
中に添加することができ、添加量は通常バインダーに対
して10重量％〜500重量％、より好ましくは20重量％〜2
00重量％である。The above thermal solvent can be added to any layer such as a light-sensitive silver halide emulsion layer, an intermediate layer, a protective layer, or an image receiving layer of an image receiving material. Wt% to 500 wt%, more preferably 20 wt% to 2
It is 00% by weight.
【００８６】本発明の熱現像感光材料に用いられるバイ
ンダーとしては、例えば、特開平2-863号公報10頁右上
欄14行目から左下欄10行目に記載されたバインダーを好
ましい組み合わせを含めて用いることができる。特に好
ましいバインダーはゼラチン、ポリビニルピロリドン及
びこれらの併用である。The binder used in the photothermographic material of the present invention includes, for example, preferable combinations of the binders described in JP-A-2-863, page 10, upper right column, line 14 to lower left column, line 10. Can be used. Particularly preferred binders are gelatin, polyvinylpyrrolidone and combinations thereof.
【００８７】本発明の熱現像感光材料には、上記以外
に、必要に応じて、各種添加剤を添加することができ
る。In addition to the above, various additives can be added to the photothermographic material of the present invention, if necessary.
【００８８】現像促進剤としては、例えば特開昭59-177
550号、同59-111636号、同59-124333号、同61-72233
号、同61-236548号、特開平1-152454号、特開昭61-1596
42号、特開平1-104645号、特願平1-110767号記載の現像
促進剤放出化合物、或は、特開平1-104645号記載の電気
陰性度が４以上の金属イオンも用いることができる。Examples of the development accelerator include, for example, JP-A-59-177.
550, 59-111636, 59-124333, 61-72233
No. 61-236548, JP-A 1-152454, JP-A 61-1596.
No. 42, JP-A-1-104645 and Japanese Patent Application No. 1-110767, or a development accelerator releasing compound, or a metal ion having an electronegativity of 4 or more described in JP-A-1-104645 can also be used. ..
【００８９】カブリ防止剤としては、例えば米国特許3,
645,739号明細書に記載されている、高級脂肪酸、特公
昭47-11113号記載の第２水銀塩、特開昭51-47419号記載
のN-ハロゲン化物、米国特許3,700,457号、特開昭51-50
725号、特願平1-69994号、同1-104271号記載のメルカプ
ト化合物放出性の化合物、特開昭49-125016号記載のア
リールスルフォン酸、同51-47419号記載のカルボン酸リ
チウム塩、英国特許1,455,271号及び特開昭50-101019号
記載の酸化剤、同53-19825号記載のスルフィン酸類及び
チオスルホン酸類、同51-3223号記載のチオウラシル
類、同51-26019号記載の硫黄、同51-42529号、同51-811
24号、及び同55-93149号記載のジスルフィド類及びポリ
スルフィド類、同51-57435号記載のロジン或はジテルペ
ン類、同51-104338号記載のカルボキシル基又はスルホ
ン酸基を有するポリマー酸、米国特許4,138,265号記載
のチアゾリチオン、特開昭54-51821号、同55-142,331
号、米国特許4,137,079号記載のトリアゾール類、特開
昭55-140883号記載のチオスルフィン酸エステル類、特
開昭59-46641号、同59-57233号、同59-57234号記載のジ
-又はトリ-ハロゲン化物、特開昭59-111636号記載のチ
オール化合物、同60-198540号及び同60-227255号記載の
ハイドロキノン誘導体、特開昭62-78554号に記載の親水
性基を有するカブリ防止剤、特開昭62-121452号記載の
ポリマーカブリ防止剤、特開昭62-123456号記載のバラ
スト基を有するカブリ防止剤、特開平1-161239号記載の
無呈色カプラー等が挙げられる。Examples of the antifoggant include US Pat.
645,739, higher fatty acids, secondary mercury salts described in JP-B-47-11113, N-halides described in JP-A-51-47419, US Pat. No. 3,700,457, JP-A-51- Fifty
No. 725, Japanese Patent Application No. 1-69994, mercapto compound-releasing compounds described in 1-104271; arylsulfonic acid described in JP-A-49-125016; lithium carboxylate described in 51-47419; British Patent 1,455,271 and oxidizers described in JP-A-50-101019, sulfinic acids and thiosulfonic acids described in 53-19825, thiouracils described in 51-3223, sulfur described in 51-26019, sulfur, No. 51-42529, No. 51-811
No. 24, and No. 55-93149, disulfides and polysulfides, No. 51-57435, rosins or diterpenes, No. 51-104338, polymer acids having a carboxyl group or a sulfonic acid group, U.S. Pat. Thiazolythion described in 4,138,265, JP-A-54-51821 and JP-A-55-142,331.
No. 3, U.S. Pat. No. 4,137,079, triazoles, JP-A-55-140883, thiosulfinic acid esters, JP-A-59-46641, 59-57233, and 59-57234.
-Or tri-halide, a thiol compound described in JP-A-59-111636, a hydroquinone derivative described in JP-A-60-198540 and 60-227255, and a hydrophilic group described in JP-A-62-78554 Antifoggants, polymer antifoggants described in JP-A No. 62-121452, anti-foggants having a ballast group described in JP-A No. 62-123456, and colorless couplers described in JP-A No. 1-161239. Be done.
【００９０】塩基プレカーサーとしては、例えば、特開
昭56-130745号、同59-157637号、同59-166943号、同59-
180537号、同59-174830号、同59-195237号、同62-10824
9号、同62-174745号、同62-187847号、同63-97942号、
同63-96159号、特開平1-68746号等の各公報に記載され
ている化合物乃至塩基放出技術が挙げられる。Examples of the base precursor include, for example, JP-A Nos. 56-130745, 59-157637, 59-166943 and 59-59.
180537, 59-174830, 59-195237, 62-10824
No. 9, No. 62-174745, No. 62-187847, No. 63-97942,
The compounds and base-releasing techniques described in JP-A-63-96159 and JP-A-1-68746 are cited.
【００９１】本発明の熱現像感光材料には上記した以外
の各種の公知の写真用添加剤を用いることができ、例え
ば、ハレーション防止染料、イラジエーション防止染
料、コロイド銀、蛍光増白剤、硬膜剤、帯電防止剤、界
面活性剤、無機及び有機のマット剤、退色防止剤、紫外
線吸収剤、カビ防止剤、白地色調調整剤、活性炭等の汚
染物質吸着性固体微粒子を含有することができる。Various known photographic additives other than those mentioned above can be used in the photothermographic material of the present invention. Examples thereof include antihalation dyes, antiirradiation dyes, colloidal silver, optical brighteners and hardeners. Can contain solid fine particles adsorbing pollutants such as film agents, antistatic agents, surfactants, inorganic and organic matting agents, antifading agents, UV absorbers, antifungal agents, white background color adjusting agents, and activated carbon. ..
【００９２】これらの各種添加剤は感光性層のみなら
ず、中間層、下引き層、保護層或はバッキング層等任意
の構成層中に適宜添加することができる。These various additives can be appropriately added not only to the photosensitive layer but also to any constituent layer such as an intermediate layer, an undercoat layer, a protective layer or a backing layer.
【００９３】本発明の熱現像感光材料に用いられる支持
体は、例えば特開平2-863号公報12頁、左上欄15行目か
ら右上欄１行目に記載された支持体を用いることができ
る。好ましくはポリエチレンテレフタレート支持体又は
キャストコート紙やバライタ紙等の紙支持体が用いられ
る。As the support used in the photothermographic material of the invention, for example, the supports described in JP-A-2-863, page 12, upper left column, line 15 to upper right column, line 1 can be used. .. Preferably, a polyethylene terephthalate support or a paper support such as cast coated paper or baryta paper is used.
【００９４】本発明の熱現像感光材料と組み合わせて用
いられる受像材料は、支持体とこの上に設けられた色素
受容能を有する受像層とから構成されるが、支持体自身
が色素受容能のある受像層を兼ねることもできる。The image-receiving material used in combination with the photothermographic material of the present invention comprises a support and an image-receiving layer provided thereon, which has a dye-receiving ability. The support itself has a dye-receiving ability. It can also serve as a certain image receiving layer.
【００９５】受像層はそれを構成するバインダー自身が
色素受容能を有する場合と、色素を受容し得る媒染剤が
バインダー中に含有されている場合とに大きく分けられ
る。The image-receiving layer is roughly classified into the case where the binder itself constituting the image-receiving layer has a dye-receiving ability and the case where a mordant capable of receiving the dye is contained in the binder.
【００９６】バインダーが色素受容能を有する場合、好
ましく用いられる物質は、ガラス転移温度が約40℃以
上、約250℃以下のポリマーで形成されているものが好
ましく、具体的には、「ポリマーハンドブック セカン
ド エディッション」（ジョイ・ブランドラップ、イー
・エイチ・インマーガット編）、ジョン ウィリー ア
ンド サンズ出版｛Polymer Handbook ２nd. ed. (J.Br
andrup, E.H.Immergut編）John Wily ＆ Sons｝に記載
されているガラス転移温度が約40℃以上の合成ポリマー
が有用であり、一般的には、ポリマーの分子量として、
2,000〜200,000程度のものが有用である。これらのポリ
マーは単独でも２種以上を併用してもよく、また２種以
上の繰り返し単位を有する共重合性のポリマーであって
もよい。When the binder has a dye receiving ability, the substance preferably used is preferably one formed of a polymer having a glass transition temperature of about 40 ° C. or higher and about 250 ° C. or lower. Second Edition "(Joy Brand Wrap, EH Inmargat), John Willie & Sons Publishing {Polymer Handbook 2nd. Ed. (J.Br.
andrup, EHImmergut ed.) John Wily & Sons} synthetic polymers having a glass transition temperature of about 40 ° C. or higher are useful, and generally, as the molecular weight of the polymer,
Those of about 2,000 to 200,000 are useful. These polymers may be used alone or in combination of two or more kinds, and may be a copolymerizable polymer having two or more kinds of repeating units.
【００９７】具体的には特開平2-863号公報14頁左上欄1
4行目から右上欄14行目に記載されたポリマーを好まし
いポリマーを含めて用いることができる。Specifically, JP-A-2-863, page 14, upper left column 1
The polymers described from the 4th line to the 14th line in the upper right column can be used including the preferable polymers.
【００９８】又、受像層がバインダー中に媒染剤を含有
する受像材料において、媒染剤としては、３級アミン又
は４級アンモニウム塩を含むポリマーが好ましく用いら
れ、例えば米国特許3,709,690号明細書及び、特開昭64-
13546号公報等に記載の化合物が挙げられる。又、これ
らの媒染剤を保持するのに用いられるバインダーとして
は、例えばゼラチンやポリビニルアルコール等の親水性
バインダーが好ましく用いられる。Further, in the image receiving material in which the image receiving layer contains a mordant in the binder, a polymer containing a tertiary amine or a quaternary ammonium salt is preferably used as the mordant. For example, US Pat. 64-64
Examples thereof include compounds described in Japanese Patent No. 13546. As the binder used for holding these mordants, hydrophilic binders such as gelatin and polyvinyl alcohol are preferably used.
【００９９】上記媒染剤をバインダー中に有する受像層
と似た形で、色素受容能を有する疎水性ポリマーラテッ
クスを親水性バインダー中に分散してなる色素受容層も
本発明で用いることができる。A dye receiving layer obtained by dispersing a hydrophobic polymer latex having dye receiving ability in a hydrophilic binder in a form similar to the image receiving layer having the mordant in the binder can also be used in the present invention.
【０１００】本発明の受像材料は支持体上に単一の受像
層が設けられた場合であってもよく、また複数の構成層
が塗設されていてもよく、この場合、その全てが色素受
像層であることも、また構成層の一部のみが受像層であ
ることもできる。The image-receiving material of the present invention may have a single image-receiving layer provided on a support, or may have a plurality of constituent layers coated, in which case all of them are dyes. It can be an image receiving layer, or only a part of the constituent layers can be an image receiving layer.
【０１０１】本発明の受像部材に公知の各種添加剤を添
加することができる。そのような添加剤としては、例え
ば、汚染防止剤、紫外線吸収剤、蛍光増白剤、画像安定
剤、現像促進剤、カブリ防止剤、pH調節剤（酸及び酸プ
レカーサー、塩基プレカーサー等）、熱溶剤、有機フッ
素系化合物、油滴、界面活性剤、硬膜剤、マット剤及び
各種金属イオン等が挙げられる。Various known additives can be added to the image-receiving member of the present invention. Examples of such additives include stain inhibitors, ultraviolet absorbers, optical brighteners, image stabilizers, development accelerators, antifoggants, pH regulators (acid and acid precursors, base precursors, etc.), heat Solvents, organic fluorine compounds, oil droplets, surfactants, hardeners, matting agents, various metal ions and the like can be mentioned.
【０１０２】本発明の熱現像感光材料は、感光材料の感
色性に適した公知の露光手段に依って露光されることが
できる。The photothermographic material of the present invention can be exposed by a known exposure means suitable for the color sensitivity of the photosensitive material.
【０１０３】用いることのできる露光光源としては、特
開平2-863号公報12頁左下欄13行目から16行目に記載の
ものを用いることができ、好ましくはレーザー光源、CR
T光源、LEDが用いられる。又、半導体レーザーとSHG素
子（第２高調波発生素子）と本発明の熱現像感光材料
は、像様露光後又は露光と同時に、好ましくは、70〜20
0℃、更に好ましくは90〜170℃で、好ましくは１〜180
秒間、更に好ましくは２〜120秒間加熱現像され、色素
画像が形成される。拡散性色素の受像材料への転写は熱
現像時に、受像材料の受像層面を感光材料の感光層側に
密着させることにより、熱現像と同時に行ってもよく、
又、熱現像後に受像材料を感光材料に密着させて色素を
転写させてもよく、更に、水を供給した後、感光材料と
受像材料とを密着させてもよい。又、露光前に70〜160
℃の範囲で感光材料を予備加熱したり、特開昭60-14333
8号及び同61-162041号に記載されている様に、現像直前
に、感光材料と受像材料の少なくとも一方を80〜120℃
の温度範囲で予備加熱することもできる。As an exposure light source that can be used, those described in JP-A-2-863, page 12, lower left column, lines 13 to 16 can be used, and preferably a laser light source, CR
T light source and LED are used. The semiconductor laser, SHG element (second harmonic generating element) and the photothermographic material of the present invention are preferably 70 to 20 after imagewise exposure or at the same time as exposure.
0 ℃, more preferably 90 ~ 170 ℃, preferably 1 ~ 180
It is heat-developed for 2 seconds, more preferably 2 to 120 seconds to form a dye image. The transfer of the diffusible dye to the image receiving material may be carried out at the same time as the heat developing by bringing the image receiving layer surface of the image receiving material into close contact with the photosensitive layer side of the photosensitive material during the heat developing,
Further, the dye may be transferred by bringing the image-receiving material into close contact with the photosensitive material after heat development, and further, after supplying water, the photosensitive material and the image-receiving material may be brought into close contact with each other. In addition, 70-160 before exposure
Preheat the light-sensitive material in the range of ℃, or JP-A-60-14333
As described in No. 8 and No. 61-162041, immediately before development, at least one of the light-sensitive material and the image-receiving material is heated at 80 to 120 ° C.
It is also possible to preheat in the temperature range of.
【０１０４】本発明の熱現像感光材料を熱現像する際に
は、公知の加熱手段を適用することができ、例えば、特
開平2-863号公報13頁左上欄12行目から19行目に記載さ
れた方法、及び遠赤外線加熱による方法等を用いること
ができる。When the heat-developable photosensitive material of the present invention is thermally developed, known heating means can be applied. For example, JP-A-2-863, page 13, upper left column, lines 12 to 19 The described method, the method by far infrared heating, etc. can be used.
【０１０５】[0105]
【実施例】以下本発明の実施例を示すが、本発明の実施
態様は、これに限定されるものではない。EXAMPLES Examples of the present invention will be shown below, but the embodiments of the present invention are not limited thereto.
【０１０６】実施例１ 〔熱現像感光材料の作製〕厚さ160μmの写真用バライタ
紙上に下記に示す層構成を有する比較熱現像感光材料Ａ
を作製した。Example 1 [Preparation of Photothermographic Material] Comparative photothermographic material A having the layer structure shown below on a photographic baryter paper having a thickness of 160 μm.
Was produced.
【０１０７】ここで、各素材の添加量は、熱現像感光材
料１m2当たりの量で示した。Here, the addition amount of each material is shown by the amount per 1 m 2 of the photothermographic material.
【０１０８】感光性ハロゲン化銀乳剤及び有機銀塩はそ
れぞれ銀に換算して表した。（以下の全ての添加剤の使
用量も同じ。） （比較熱現像感光材料Ａの層構成） 下引層 ポリフェニレンエーテル 2.0g ポリスチレン 2.0g カブリ防止剤−２ 1.0g 第１層（赤感光層） ベンゾトリアゾール銀 1.6g 色素供与物質（３） 1.2g 赤感性ハロゲン化銀乳剤 0.68g(Ag) ゼラチン 1.3g ポリビニルピロリドン（K-30） 0.6g 熱溶剤−Ａ 4.5g イラジエーション防止染料−２ 0.01g FR-1 0.005g ポリマーラテックス 0.5g スカベンジャーＡ 0.1g 第２層（第１中間層） ゼラチン 0.8g 還元剤 1.12g ポリマーラテックス 0.6g 第３層（緑感光層） ベンゾトリアゾール銀 0.8g 色素供与物質（２） ０．９ｇ 緑感性ハロゲン化銀乳剤 ０．４７ｇ
（Ａｇ） ゼラチン 2.0g PVP(K-30） 0.3g 熱溶剤−Ａ 3.45g イラジエーション防止染料 0.02g FR-1 0.003g ポリマーラテックス 0.4g スカベンジャーＡ 0.08g 第４層（第２中間層） ゼラチン 1.55g 還元剤 1.5g 紫外線吸収剤（表１） 高沸点有機溶媒（表１） イエローフィルター染料 0.26g 第５層（青感光層） ベンゾトリアゾール銀 1.5g ポリマーラテックス 0.5g 色素供与物質（１） 1.2g 青感性ハロゲン化銀乳剤 0.45g(Ag) ゼラチン 1.6g PVP（K-30) 0.4g 熱溶剤−Ａ 4.0g FR-1 0.002g スカベンジャーＡ 0.1g 第６層（保護層） ゼラチン 1.0g ポリビニルピロリドン(K-30) 0.2g ZnSO4 0.65g 還元剤 ０．３４
ｇ 紫外線吸収剤（表１） なお、各添加量は、１ｍ２当たりの付量を表す。各層
共、ゼラチン１g当たり0.03gのビスビニルスルホニルメ
チルエーテルを硬化剤として含有し、また塗布に必要な
界面活性剤−１を含有する。還元剤は還元剤−１と還元
剤−２の７：３（重量比）の混合物である。The photosensitive silver halide emulsion and the organic silver salt are each expressed in terms of silver. (The same applies to all of the following additives.) (Layer constitution of comparative photothermographic material A) Subbing layer Polyphenylene ether 2.0 g Polystyrene 2.0 g Antifoggant-2 1.0 g First layer (red photosensitive layer) Benzotriazole silver 1.6g Dye donor (3) 1.2g Red-sensitive silver halide emulsion 0.68g (Ag) Gelatin 1.3g Polyvinylpyrrolidone (K-30) 0.6g Thermal solvent-A 4.5g Anti-irradiation dye-2 0.01g FR-1 0.005g Polymer latex 0.5g Scavenger A 0.1g Second layer (first intermediate layer) Gelatin 0.8g Reducing agent 1.12g Polymer latex 0.6g Third layer (green photosensitive layer) Benzotriazole silver 0.8g Dye donating substance ( 2) 0.9g Green-sensitive silver halide emulsion 0.47g
(Ag) Gelatin 2.0g PVP (K-30) 0.3g Hot solvent-A 3.45g Anti-irradiation dye 0.02g FR-1 0.003g Polymer latex 0.4g Scavenger A 0.08g 4th layer (2nd intermediate layer) Gelatin 1.55 g Reducing agent 1.5g UV absorber (Table 1) High boiling point organic solvent (Table 1) Yellow filter dye 0.26g Fifth layer (blue photosensitive layer) Benzotriazole silver 1.5g Polymer latex 0.5g Dye donating substance (1) 1.2g Blue-sensitive silver halide emulsion 0.45g (Ag) Gelatin 1.6g PVP (K-30) 0.4g Hot solvent-A 4.0g FR-1 0.002g Scavenger A 0.1g 6th layer (protective layer) Gelatin 1.0g Polyvinylpyrrolidone ( K-30) 0.2g ZnSO 4 0.65g Reducing agent 0.34
g Ultraviolet absorber (Table 1) In addition, each addition amount represents a coating amount per 1 m 2 . Each layer contains 0.03 g of bisvinylsulfonylmethyl ether per 1 g of gelatin as a hardening agent and also contains surfactant-1 necessary for coating. The reducing agent is a 7: 3 (weight ratio) mixture of reducing agent-1 and reducing agent-2.
【０１０９】紫外線吸収剤は以下の方法で乳化分散して
用いた。The ultraviolet absorber was emulsified and dispersed by the following method.
【０１１０】（紫外線吸収剤分散）紫外線吸収剤10gお
よび表１に示す高沸点有機溶媒（添加量は紫外線吸収剤
に対する比率が表１になるように加える。）を酢酸エチ
ル30ccに加熱溶解し、４％ゼラチン水溶液50cc（0.6gの
トリイソプロピルナフタレンスルホン酸ナトリウム含
有）に混合して高速ホモミキサーで乳化分散後減圧下で
酢酸エチルを除去し総量を72ccにした。(Ultraviolet Absorber Dispersion) 10 g of the ultraviolet absorber and the high-boiling organic solvent shown in Table 1 (the addition amount is such that the ratio to the ultraviolet absorber is in Table 1) are dissolved by heating in 30 cc of ethyl acetate, The mixture was mixed with 50 ml of a 4% gelatin aqueous solution (containing 0.6 g of sodium triisopropylnaphthalenesulfonate), emulsified and dispersed by a high-speed homomixer, and ethyl acetate was removed under reduced pressure to bring the total amount to 72 cc.
【０１１１】熱現像感光材料の感光性層に用いた添加剤
の構造式を以下に示す。The structural formulas of the additives used in the photosensitive layer of the photothermographic material are shown below.
【０１１２】[0112]
【化１０】 [Chemical 10]
【０１１３】[0113]
【化１１】 [Chemical 11]
【０１１４】[0114]
【化１２】 [Chemical 12]
【０１１５】〔ベンゾトリアゾール銀乳剤〕50℃のフェ
ニルカルバモイルゼラチン10％水溶液中にアンモニア性
硝酸銀水溶液、及びベンゾトリアゾール（ベンゾトリア
ゾールに対して0.2モルのアンモニア水含有）の同時混
合により調整し、添加終了後液のpHを低下させて、凝集
・脱塩して針状結晶（巾0.1〜0.2μm、長さ0.5〜２μ
m）を得た。[Benzotriazole silver emulsion] Preparation was completed by simultaneous mixing of an aqueous solution of ammoniacal silver nitrate and benzotriazole (containing 0.2 mol of ammonia water with respect to benzotriazole) in a 10% aqueous solution of phenylcarbamoyl gelatin at 50 ° C., and the addition was completed. Needle-like crystals (width 0.1-0.2μm, length 0.5-2μ)
m) got.
【０１１６】これに安定剤としてST-2をベンゾトリアゾ
ール銀１モル当たり20mg添加した。To this was added ST-2 as a stabilizer in an amount of 20 mg per mol of benzotriazole silver.
【０１１７】使用した感光性ハロゲン化銀乳剤（AgclB
r）を下表に示す。The photosensitive silver halide emulsion used (AgclB
r) is shown in the table below.
【０１１８】 項 目 青感光性 緑感光性(GEM-1) 赤感光性 ハロゲン組成(Brモル％) 70 60 70 粒子形状 六方晶 立方晶 立方晶 平均粒径＊１ 0.30μm 0.19μm 0.20μm 粒径分布係数＊２ 0.15 0.17 0.13 表面化学増感方法＊３ Ｓ＋Au Ｓ Ｓ＋Au 安定剤 ST-1 ST-1 ST-2 増感色素 BSD-1 GSD-1 RSD-1 ＊１ 球換算時の直径 ＊２ 粒径分布係数＝（粒径分布標準偏差）／（平均粒
径） ＊３ Ｓ＋Au：チオ硫酸ナトリウムと塩化金酸カリウム
による金−硫黄増感 Ｓ ：チオ硫酸ナトリウムによる硫黄増感 上記各感光性ハロゲン化銀乳剤はそれぞれ粒子形成時に
ハロゲン化銀１モル当たり10-6モルの６塩化イリジウム
（ＩＶ）ナトリウムを添加した。 Item Blue-sensitive green-sensitive (GEM-1) Red-sensitive halogen composition (Br mol%) 70 60 70 Particle shape Hexagonal cubic cubic Cubic average particle size * 1 0.30 μm 0.19 μm 0.20 μm Particle size Distribution coefficient * 2 0.15 0.17 0.13 Surface chemical sensitization method * 3 S + Au S S + Au Stabilizer ST-1 ST-1 ST-2 Sensitizing dye BSD-1 GSD-1 RSD-1 * 1 Diameter in sphere conversion * 2 grains Diameter distribution coefficient = (particle size distribution standard deviation) / (average particle size) * 3 S + Au: gold-sulfur sensitization with sodium thiosulfate and potassium chloroaurate S: sulfur sensitization with sodium thiosulfate To each silver emulsion, 10 -6 mol of sodium iridium (IV) chloride was added per 1 mol of silver halide during grain formation.
【０１１９】ST-1:5-メチル-1,3,3a,7-テトラザインデ
ン 又、各々の化学増感はそれぞれ増感色素の存在下で行っ
た。ST-1: 5-methyl-1,3,3a, 7-tetrazaindene Each chemical sensitization was carried out in the presence of a sensitizing dye.
【０１２０】[0120]
【化１３】 [Chemical 13]
【０１２１】〔受像剤材料の作成〕熱現像感光材料を作
成したのと同じ写真用バライタ支持体上に、以下の組成
からなる受像層を塗設して受像材料−１を作成した。
（添加量は受像材料１m2当たりの量を示す。） ポリ塩化ビニル（平均重合度 500） 10g ポリマーＵＶ剤（Ｐ−18） 1.1g 画像安定剤−２ 0.3g 画像安定剤−３ 0.5g 画像安定剤−４ 0.5g 画像安定剤−５ 0.3g 熱溶剤−Ｂ ４．２ｇ[Preparation of Image Receiving Material] An image receiving material-1 was prepared by coating an image receiving layer having the following composition on the same photographic baryter support as that used for preparing the photothermographic material.
(The amount added is the amount per 1 m 2 of the image receiving material.) Polyvinyl chloride (average degree of polymerization 500) 10 g Polymer UV agent (P-18) 1.1 g Image stabilizer-2 0.3 g Image stabilizer-3 0.5 g Image Stabilizer-4 0.5g Image stabilizer-5 0.3g Thermal solvent-B 4.2g
【０１２２】[0122]
【化１４】 [Chemical 14]
【０１２３】〔熱現像感光材料の評価〕得られた熱現像
感光材料の各々について、５０℃、相対湿度60％で３日
間保存した。[Evaluation of Photothermographic Material] Each of the obtained photothermographic materials was stored at 50 ° C. and 60% relative humidity for 3 days.
【０１２４】一方、比較熱現像感光材料Ａにおいて、第
４層及び第６層の紫外線吸収剤を表１に示すように変化
させた熱現像感光材料を熱現像感光材料Ａと同様にして
作成した。On the other hand, in the comparative photothermographic material A, a photothermographic material in which the ultraviolet absorbers of the fourth and sixth layers were changed as shown in Table 1 was prepared in the same manner as the photothermographic material A. ..
【０１２５】得られた熱現像感光材料にそれぞれ像様露
光を行った後、150℃で60秒間熱現像を行った。Each of the resulting photothermographic materials was imagewise exposed and then heat-developed at 150 ° C. for 60 seconds.
【０１２６】次いで熱現像感光材料を受像材料−１と重
ね合せ、120℃で20秒間加圧、加熱転写して色素画像を
受像材料に転写した。転写画像の耐光性を調べるため各
々をキセノンフェードメーターで光照射（200時間）し
初濃度1.0における色濃度を測定し、色素残存率を求め
た。（耐光性） 色素残存率（％）＝100×（光照射後の反射濃度）／1.0 更に転写した色素受像層を40℃、相対湿度60％で１日間
保存し、その後５℃の冷蔵庫で１日保存するサイクルを
５回繰り返し２日毎に表面の光沢を目視で調べた。結果
を表１に示す。Then, the photothermographic material was superposed on the image receiving material-1, and the dye image was transferred onto the image receiving material by heating and transferring under pressure at 120 ° C. for 20 seconds. In order to examine the light resistance of the transferred images, each was irradiated with light with a xenon fade meter (200 hours), the color density at an initial density of 1.0 was measured, and the residual dye ratio was obtained. (Light resistance) Dye residual ratio (%) = 100 × (reflection density after light irradiation) /1.0 The transferred dye image receiving layer was stored at 40 ° C. and 60% relative humidity for 1 day, and then stored in a refrigerator at 5 ° C. The cycle of storage for 5 days was repeated and the gloss of the surface was visually inspected every 2 days. The results are shown in Table 1.
【０１２７】更に上記熱現像感光材料を、20℃相対湿度
20％で１各液調湿したのち、感光層表面を裏面と重ね合
せて、20回擦り合せ、その後未露光のまま、熱現像並び
に色素転写を行った。受像層面には、静電気によるカブ
リの発生が認められたが、試料サイズ（８cm×1.8cm）
の中の任意の点50点をランダムに赤色光で濃度測定し、
その平均を求めた。そして、静電気による処理のないも
のに対する濃度との差を求め、これを表１に示した。Further, the above photothermographic material was processed at 20 ° C. relative humidity.
After conditioning each liquid at 20%, the surface of the photosensitive layer was overlapped with the back surface and rubbed 20 times, and thereafter, heat development and dye transfer were carried out with no exposure. Fog was observed to be generated on the image-receiving layer surface due to static electricity, but the sample size (8 cm x 1.8 cm)
At any 50 points in the, the density is randomly measured with red light,
The average was calculated. Then, the difference from the density of the sample that was not treated by static electricity was determined and is shown in Table 1.
【０１２８】[0128]
【表１】 [Table 1]
【０１２９】表１に示す結果から、熱現像感光材料に紫
外線吸収剤を用いない試料Ａはスタッチによる激しいカ
ブリの発生が認められるが紫外線吸収剤を用いた熱現像
感光材料は、カブリの発生が少ないことがわかる。From the results shown in Table 1, in Sample A in which no UV absorber is used in the photothermographic material, severe fog is observed due to touch, but in the photothermographic material using the UV absorber, fog is not generated. You can see that there are few.
【０１３０】一方紫外吸収剤として、ポリマーでないも
のも用いた比較熱現像感光材料Ｂ，Ｃ，Ｄは転写後のプ
リントの画像表面の光沢が保存中に劣化していくことが
わかる。On the other hand, it can be seen that the comparative photothermographic materials B, C and D, which also used non-polymer UV absorbers, deteriorated the gloss of the image surface of the print after transfer during storage.
【０１３１】実施例２ 実施例１で便用した受像材料−１を下記の受像材料−２
に変更し、実施例１を繰り返した。Example 2 The image receiving material-1 used in Example 1 was replaced with the following image receiving material-2.
And Example 1 was repeated.
【０１３２】受像材料−２ 受像材料−１で使用したバライタ紙支持体上に以下の層
を、塗布して受像材料−２を作成した。Image Receiving Material-2 Image Receiving Material-2 was prepared by coating the following layers on the baryta paper support used in Image Receiving Material-1.
【０１３３】ゼラチン 4.9g ポリ塩化ビニル 12.3g 画像安定剤−２ 0.3g 〃 −３ 0.5g 〃 −４ 0.5g 〃 −５ 0.3g 熱溶剤−Ｂ 6.2g 塗布して得られた受像材料−２は40℃相対湿度80℃で24
時間保存した。Gelatin 4.9 g Polyvinyl chloride 12.3 g Image stabilizer-2 0.3 g 〃 -3 0.5 g 〃 -4 0.5 g 〃 -5 0.3 g Thermal solvent-B 6.2 g The image receiving material-2 obtained by coating is 24 at 40 ° C relative humidity 80 ° C
Saved for hours.
【０１３４】実施例１同様に、耐光性、表面析出性、ス
タッチカブリを評価し、結果を表２に示した。In the same manner as in Example 1, the light resistance, the surface precipitation property and the touch fog were evaluated, and the results are shown in Table 2.
【０１３５】[0135]
【表２】 [Table 2]
【０１３６】表２に示す結果から、受像材料を変更して
も、本発明の熱現感光材料は表面析出性とスタッチカブ
リのいずれもが良好であることがわかる。From the results shown in Table 2, it can be seen that even if the image receiving material is changed, the thermographic photosensitive material of the present invention has good surface depositability and good touch fog.
【０１３７】実施例３ 実施例２で使用した受像材料２において熱溶剤−Ｂを除
去した、受像材料３を作成した。Example 3 An image receiving material 3 was prepared by removing the thermal solvent-B from the image receiving material 2 used in Example 2.
【０１３８】実施例１に記載の方法で熱現像、転写後、
転写済の受像材料の光沢性試験を行なった。ただし、こ
こでは20サイクルまで行った。After thermal development and transfer by the method described in Example 1,
A gloss test of the transferred image receiving material was conducted. However, up to 20 cycles were performed here.
【０１３９】結果を表３に示す。The results are shown in Table 3.
【０１４０】[0140]
【表３】 [Table 3]
【０１４１】表３の結果から低分子量の高沸点有機溶媒
を用いない、熱現像感光材料−１〜５，７は受像材料−
２を用いても長期の表面析出がないことがわかる。又、
受像材料−２と３の比較から、本発明の熱現像感光材料
を用いた場合、受像材料が熱溶剤を含有した場合であっ
ても、保存による光沢性劣化効果が大きいことがわか
る。From the results shown in Table 3, the photothermographic materials-1 to 5 and 7, which do not use a low-boiling point high-boiling organic solvent, are image-receiving materials-
It can be seen that even when 2 is used, there is no long-term surface precipitation. or,
From a comparison of Image Receiving Materials-2 and 3, it can be seen that when the photothermographic material of the present invention is used, the effect of deterioration in glossiness due to storage is great even when the image receiving material contains a thermal solvent.
【０１４２】[0142]
【発明の効果】本発明により色素受像表面の光沢性を長
期間劣化させることなく、熱現像感光材料を製造する際
のスタチックカブリを防止した熱現像感光材料を提供す
ることができた。According to the present invention, it is possible to provide a photothermographic material capable of preventing static fog during production of the photothermographic material without deteriorating the glossiness of the dye image receiving surface for a long period of time.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｇ０３Ｃ 1/815 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI technical display area // G03C 1/815
Claims (1)
ン化銀、熱現像処理により拡散性色素を放出または形成
する色素供与物質、及び下記一般式〔１〕で表される繰
り返し単位を有するポリマー紫外線吸収剤を含有するこ
とを特徴とする熱現像感光材料。 【化１】 〔式中、Ｒ1、Ｒ2及びＲ3はそれぞれ同じであっても、
異なっていても良く、水素原子または炭素原子数１〜４
のアルキル基を表す。Ｌは-CONH-、-COO-またはフェニ
レン基を表す。Ａは炭素原子数１〜20のアルキレン基ま
たは炭素原子数６〜20のアリーレン基を表し、Ｂは-NR4
CO-、-COO-、-OCO-、CONR4-、-SO2NR4-、-NR4SO2-、-SO
2-または-O-基を表す。Ｒ4は水素原子または炭素原子数
１〜20のアルキル基または炭素原子数６〜20のアリール
基を表す。ｍとｎはそれぞれ独立に０または１を表す。
Ｑは紫外線吸収剤残基を表す。〕1. A polymer having, on a support, a binder, a photosensitive silver halide, a dye-donor substance that releases or forms a diffusible dye by heat development, and a repeating unit represented by the following general formula [1]. A photothermographic material comprising an ultraviolet absorber. [Chemical 1] [Wherein R 1 , R 2 and R 3 are the same,
May be different, and has 1 to 4 hydrogen atoms or carbon atoms
Represents an alkyl group. L represents -CONH-, -COO- or a phenylene group. A represents an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms, and B represents -NR 4
CO -, - COO -, - OCO-, CONR 4 -, - SO 2 NR 4 -, - NR 4 SO 2 -, - SO
Represents a 2- or -O- group. R 4 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. m and n each independently represent 0 or 1.
Q represents an ultraviolet absorber residue. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3316794A JPH05150433A (en) | 1991-11-29 | 1991-11-29 | Heat developable photosensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3316794A JPH05150433A (en) | 1991-11-29 | 1991-11-29 | Heat developable photosensitive material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05150433A true JPH05150433A (en) | 1993-06-18 |
Family
ID=18081004
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3316794A Pending JPH05150433A (en) | 1991-11-29 | 1991-11-29 | Heat developable photosensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05150433A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11209392A (en) * | 1998-01-27 | 1999-08-03 | Nippon Paper Industries Co Ltd | Benzotriazole derivative and heat-sensitive recording unit using the same |
| EP2103445A1 (en) | 2008-03-18 | 2009-09-23 | Ricoh Company, Ltd. | Heat resistance improver and reversible thermosensitive recording medium |
-
1991
- 1991-11-29 JP JP3316794A patent/JPH05150433A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11209392A (en) * | 1998-01-27 | 1999-08-03 | Nippon Paper Industries Co Ltd | Benzotriazole derivative and heat-sensitive recording unit using the same |
| EP2103445A1 (en) | 2008-03-18 | 2009-09-23 | Ricoh Company, Ltd. | Heat resistance improver and reversible thermosensitive recording medium |
| US8324399B2 (en) | 2008-03-18 | 2012-12-04 | Ricoh Company, Ltd. | Heat resistance improver and reversible thermosensitive recording medium |
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