JPH0690487B2 - Photothermographic material - Google Patents
Photothermographic materialInfo
- Publication number
- JPH0690487B2 JPH0690487B2 JP60019399A JP1939985A JPH0690487B2 JP H0690487 B2 JPH0690487 B2 JP H0690487B2 JP 60019399 A JP60019399 A JP 60019399A JP 1939985 A JP1939985 A JP 1939985A JP H0690487 B2 JPH0690487 B2 JP H0690487B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver
- dye
- gelatin
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000463 material Substances 0.000 title claims description 70
- 229920000642 polymer Polymers 0.000 claims description 79
- -1 silver halide Chemical class 0.000 claims description 79
- 229910052709 silver Inorganic materials 0.000 claims description 55
- 239000004332 silver Substances 0.000 claims description 55
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 39
- 125000003010 ionic group Chemical group 0.000 claims description 9
- 229920001400 block copolymer Polymers 0.000 claims description 6
- 239000000975 dye Substances 0.000 description 80
- 108010010803 Gelatin Proteins 0.000 description 78
- 239000008273 gelatin Substances 0.000 description 78
- 229920000159 gelatin Polymers 0.000 description 78
- 235000019322 gelatine Nutrition 0.000 description 78
- 235000011852 gelatine desserts Nutrition 0.000 description 78
- 150000001875 compounds Chemical class 0.000 description 49
- 238000000034 method Methods 0.000 description 46
- 239000004372 Polyvinyl alcohol Substances 0.000 description 35
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000000126 substance Substances 0.000 description 30
- 238000000576 coating method Methods 0.000 description 25
- 238000012546 transfer Methods 0.000 description 25
- 239000011248 coating agent Substances 0.000 description 23
- 238000006116 polymerization reaction Methods 0.000 description 23
- 239000007864 aqueous solution Substances 0.000 description 22
- 239000000839 emulsion Substances 0.000 description 22
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 21
- 239000000178 monomer Substances 0.000 description 20
- 230000001681 protective effect Effects 0.000 description 20
- 238000011161 development Methods 0.000 description 17
- 230000018109 developmental process Effects 0.000 description 17
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 17
- 239000002253 acid Substances 0.000 description 16
- 230000035699 permeability Effects 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000011230 binding agent Substances 0.000 description 15
- 239000003638 chemical reducing agent Substances 0.000 description 14
- 238000007127 saponification reaction Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 125000003396 thiol group Chemical group [H]S* 0.000 description 10
- 229920003169 water-soluble polymer Polymers 0.000 description 10
- 238000005859 coupling reaction Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 8
- 150000003573 thiols Chemical class 0.000 description 8
- 229920001567 vinyl ester resin Polymers 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 230000008878 coupling Effects 0.000 description 7
- 238000010168 coupling process Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000004800 polyvinyl chloride Substances 0.000 description 7
- 229920000915 polyvinyl chloride Polymers 0.000 description 7
- 238000011160 research Methods 0.000 description 7
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 229910021612 Silver iodide Inorganic materials 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 6
- 229920001290 polyvinyl ester Polymers 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 229940045105 silver iodide Drugs 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- IBWXIFXUDGADCV-UHFFFAOYSA-N 2h-benzotriazole;silver Chemical group [Ag].C1=CC=C2NN=NC2=C1 IBWXIFXUDGADCV-UHFFFAOYSA-N 0.000 description 5
- AHHQDHCTHYTBSV-UHFFFAOYSA-N 3-methylpentane-1,3,5-triol Chemical compound OCCC(O)(C)CCO AHHQDHCTHYTBSV-UHFFFAOYSA-N 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 239000000499 gel Substances 0.000 description 5
- 125000000623 heterocyclic group Chemical group 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- 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 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 230000006870 function Effects 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 229920000831 ionic polymer Polymers 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- 150000003378 silver Chemical class 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 description 3
- WXTMDXOMEHJXQO-UHFFFAOYSA-N 2,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC=C1O WXTMDXOMEHJXQO-UHFFFAOYSA-N 0.000 description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 3
- MVYVKSBVZFBBPL-UHFFFAOYSA-N 2-(prop-2-enoylamino)propane-1-sulfonic acid Chemical compound OS(=O)(=O)CC(C)NC(=O)C=C MVYVKSBVZFBBPL-UHFFFAOYSA-N 0.000 description 3
- WVKWKEWFTVEVCF-UHFFFAOYSA-N 2h-benzotriazole-4-sulfonic acid Chemical class OS(=O)(=O)C1=CC=CC2=NNN=C12 WVKWKEWFTVEVCF-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 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
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- 229910001864 baryta Inorganic materials 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 3
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 3
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920002689 polyvinyl acetate Polymers 0.000 description 3
- 239000011118 polyvinyl acetate Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical class O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- HVOMZNUEIIDPOH-UHFFFAOYSA-N 1,3-thiazole-4-thione Chemical class S=C1CSC=N1 HVOMZNUEIIDPOH-UHFFFAOYSA-N 0.000 description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 2
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- SGWZVZZVXOJRAQ-UHFFFAOYSA-N 2,6-Dimethyl-1,4-benzenediol Chemical compound CC1=CC(O)=CC(C)=C1O SGWZVZZVXOJRAQ-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- PLYFWZGSBMDRKW-UHFFFAOYSA-N 2h-benzotriazole-4-sulfonic acid;silver Chemical group [Ag].OS(=O)(=O)C1=CC=CC2=NNN=C12 PLYFWZGSBMDRKW-UHFFFAOYSA-N 0.000 description 2
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-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
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 2
- RFOIWENXLZSKSY-UHFFFAOYSA-N 4-ethenylpyrrolidin-2-one Chemical compound C=CC1CNC(=O)C1 RFOIWENXLZSKSY-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 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
- 150000000996 L-ascorbic acids Chemical class 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- JRNVZBWKYDBUCA-UHFFFAOYSA-N N-chlorosuccinimide Chemical compound ClN1C(=O)CCC1=O JRNVZBWKYDBUCA-UHFFFAOYSA-N 0.000 description 2
- LQZMLBORDGWNPD-UHFFFAOYSA-N N-iodosuccinimide Chemical compound IN1C(=O)CCC1=O LQZMLBORDGWNPD-UHFFFAOYSA-N 0.000 description 2
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methyl urea Chemical compound CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 206010034972 Photosensitivity reaction Diseases 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
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- 239000010419 fine particle Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- ICPGNGZLHITQJI-UHFFFAOYSA-N iminosilver Chemical class [Ag]=N ICPGNGZLHITQJI-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910001502 inorganic halide Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 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
- XUPFNPFFFUXGMP-UHFFFAOYSA-N isoindole-1,3-dione;silver Chemical compound [Ag].C1=CC=C2C(=O)NC(=O)C2=C1 XUPFNPFFFUXGMP-UHFFFAOYSA-N 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- AZEPWULHRMVZQR-UHFFFAOYSA-M lithium;dodecanoate Chemical compound [Li+].CCCCCCCCCCCC([O-])=O AZEPWULHRMVZQR-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical class N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BBBWQGQLFSDGIQ-UHFFFAOYSA-N methyl(3-phenylpropyl)sulfanium bromide Chemical compound [Br-].C(C1=CC=CC=C1)CC[SH+]C BBBWQGQLFSDGIQ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- OTVPURYEWXIAKH-UHFFFAOYSA-N n,n-dibromobenzenesulfonamide Chemical compound BrN(Br)S(=O)(=O)C1=CC=CC=C1 OTVPURYEWXIAKH-UHFFFAOYSA-N 0.000 description 1
- SQARMCGNIUBXAJ-UHFFFAOYSA-N n-(2-hydroxyphenyl)benzenesulfonamide Chemical compound OC1=CC=CC=C1NS(=O)(=O)C1=CC=CC=C1 SQARMCGNIUBXAJ-UHFFFAOYSA-N 0.000 description 1
- HAYLIGDJFXRLMU-UHFFFAOYSA-N n-(3,5-dibromo-4-hydroxyphenyl)-4-methylbenzenesulfonamide Chemical compound C1=CC(C)=CC=C1S(=O)(=O)NC1=CC(Br)=C(O)C(Br)=C1 HAYLIGDJFXRLMU-UHFFFAOYSA-N 0.000 description 1
- KFPBEVFQCXRYIR-UHFFFAOYSA-N n-(3,5-dichloro-4-hydroxyphenyl)benzenesulfonamide Chemical compound C1=C(Cl)C(O)=C(Cl)C=C1NS(=O)(=O)C1=CC=CC=C1 KFPBEVFQCXRYIR-UHFFFAOYSA-N 0.000 description 1
- BVWUEIUNONATML-UHFFFAOYSA-N n-benzylethenamine Chemical compound C=CNCC1=CC=CC=C1 BVWUEIUNONATML-UHFFFAOYSA-N 0.000 description 1
- UMBBGOALZMAJSF-UHFFFAOYSA-N n-benzylethenamine;hydrochloride Chemical compound [Cl-].C=C[NH2+]CC1=CC=CC=C1 UMBBGOALZMAJSF-UHFFFAOYSA-N 0.000 description 1
- DVNYDODOESWBJY-UHFFFAOYSA-N n-bromo-n-methylbenzenesulfonamide Chemical compound CN(Br)S(=O)(=O)C1=CC=CC=C1 DVNYDODOESWBJY-UHFFFAOYSA-N 0.000 description 1
- FWLGGSWAIHNLLW-UHFFFAOYSA-N n-bromo-n-phenylacetamide Chemical compound CC(=O)N(Br)C1=CC=CC=C1 FWLGGSWAIHNLLW-UHFFFAOYSA-N 0.000 description 1
- VBTQNRFWXBXZQR-UHFFFAOYSA-N n-bromoacetamide Chemical compound CC(=O)NBr VBTQNRFWXBXZQR-UHFFFAOYSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 150000002791 naphthoquinones Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001005 nitro dye Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- BIAGWOZIXODKKS-UHFFFAOYSA-N oxadiazole-4-thiol;silver Chemical compound [Ag].SC1=CON=N1 BIAGWOZIXODKKS-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- FCJSHPDYVMKCHI-UHFFFAOYSA-N phenyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC1=CC=CC=C1 FCJSHPDYVMKCHI-UHFFFAOYSA-N 0.000 description 1
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical compound C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 description 1
- 239000001007 phthalocyanine dye Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920000205 poly(isobutyl methacrylate) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002776 polycyclohexyl methacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006324 polyoxymethylene 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
- 229920001447 polyvinyl benzene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- RGBXDEHYFWDBKD-UHFFFAOYSA-N propan-2-yl propan-2-yloxy carbonate Chemical compound CC(C)OOC(=O)OC(C)C RGBXDEHYFWDBKD-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- ZMRUPTIKESYGQW-UHFFFAOYSA-N propranolol hydrochloride Chemical compound [H+].[Cl-].C1=CC=C2C(OCC(O)CNC(C)C)=CC=CC2=C1 ZMRUPTIKESYGQW-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- MCJGNVYPOGVAJF-UHFFFAOYSA-N quinolin-8-ol Chemical compound C1=CN=C2C(O)=CC=CC2=C1 MCJGNVYPOGVAJF-UHFFFAOYSA-N 0.000 description 1
- GJAWHXHKYYXBSV-UHFFFAOYSA-N quinolinic acid Chemical compound OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920013730 reactive polymer Polymers 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical class O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 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
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- NUMJVUZSWZLKTF-XVSDJDOKSA-M silver;(5z,8z,11z,14z)-icosa-5,8,11,14-tetraenoate Chemical compound [Ag+].CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC([O-])=O NUMJVUZSWZLKTF-XVSDJDOKSA-M 0.000 description 1
- SPIDTRPQUQLJAY-UHFFFAOYSA-N silver;1h-1,2,4-triazole Chemical compound [Ag].C=1N=CNN=1 SPIDTRPQUQLJAY-UHFFFAOYSA-N 0.000 description 1
- VMPMKNVWTFEJAO-UHFFFAOYSA-N silver;2h-tetrazole Chemical compound [Ag].C=1N=NNN=1 VMPMKNVWTFEJAO-UHFFFAOYSA-N 0.000 description 1
- CLDWGXZGFUNWKB-UHFFFAOYSA-M silver;benzoate Chemical compound [Ag+].[O-]C(=O)C1=CC=CC=C1 CLDWGXZGFUNWKB-UHFFFAOYSA-M 0.000 description 1
- MNMYRUHURLPFQW-UHFFFAOYSA-M silver;dodecanoate Chemical compound [Ag+].CCCCCCCCCCCC([O-])=O MNMYRUHURLPFQW-UHFFFAOYSA-M 0.000 description 1
- LTYHQUJGIQUHMS-UHFFFAOYSA-M silver;hexadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCC([O-])=O LTYHQUJGIQUHMS-UHFFFAOYSA-M 0.000 description 1
- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 description 1
- OHGHHPYRRURLHR-UHFFFAOYSA-M silver;tetradecanoate Chemical compound [Ag+].CCCCCCCCCCCCCC([O-])=O OHGHHPYRRURLHR-UHFFFAOYSA-M 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- RKSOPLXZQNSWAS-UHFFFAOYSA-N tert-butyl bromide Chemical compound CC(C)(C)Br RKSOPLXZQNSWAS-UHFFFAOYSA-N 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- LIXPXSXEKKHIRR-UHFFFAOYSA-M tetraethylphosphanium;bromide Chemical compound [Br-].CC[P+](CC)(CC)CC LIXPXSXEKKHIRR-UHFFFAOYSA-M 0.000 description 1
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- 150000007970 thio esters Chemical group 0.000 description 1
- ZEMGGZBWXRYJHK-UHFFFAOYSA-N thiouracil Chemical compound O=C1C=CNC(=S)N1 ZEMGGZBWXRYJHK-UHFFFAOYSA-N 0.000 description 1
- 229950000329 thiouracil Drugs 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- ILJSQTXMGCGYMG-UHFFFAOYSA-N triacetic acid Chemical compound CC(=O)CC(=O)CC(O)=O ILJSQTXMGCGYMG-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- YFDSDPIBEUFTMI-UHFFFAOYSA-N tribromoethanol Chemical compound OCC(Br)(Br)Br YFDSDPIBEUFTMI-UHFFFAOYSA-N 0.000 description 1
- 229950004616 tribromoethanol Drugs 0.000 description 1
- GNMJFQWRASXXMS-UHFFFAOYSA-M trimethyl(phenyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)C1=CC=CC=C1 GNMJFQWRASXXMS-UHFFFAOYSA-M 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 description 1
- INDZTCRIYSRWOH-UHFFFAOYSA-N undec-10-enyl carbamimidothioate;hydroiodide Chemical compound I.NC(=N)SCCCCCCCCCC=C INDZTCRIYSRWOH-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000002699 waste material Substances 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/498—Photothermographic systems, e.g. dry silver
- G03C1/49836—Additives
- G03C1/49863—Inert additives, e.g. surfactants, binders
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
Description
【発明の詳細な説明】 [産業上の利用分野] 本発明は熱現像感光材料に関し、特にゼラチン等との相
溶性の優れた変性ポリビニルアルコール系重合体を含有
する層を有する熱現像感光材料に関するものである。TECHNICAL FIELD The present invention relates to a photothermographic material, and more particularly to a photothermographic material having a layer containing a modified polyvinyl alcohol polymer having excellent compatibility with gelatin and the like. It is a thing.
[従来技術] 従来から知られている感光性ハロゲン化銀を使用する写
真法は感光性、階調性および画像保存性等において他の
写真法に勝るものであり、最も広く実用化されてきた写
真法である。[Prior Art] The conventionally known photographic method using photosensitive silver halide is superior to other photographic methods in terms of photosensitivity, gradation and image storability, and has been most widely used. It is a photographic method.
しかしながら、この方法においては現像、定着および水
洗などの処理工程に湿式処理法を用いるために、処理に
時間と手間がかかり、また処理薬品による人体への影響
が懸念されたり、或いは処理室や作業者に対する上記薬
品による汚染が心配されたり、更には廃液による公害の
発生への配慮といった多くの問題が存在している。従っ
て感光性ハロゲン化銀を用いかつ乾式処理が可能である
感光性材料の開発が望まれていた。However, in this method, since a wet processing method is used for processing steps such as development, fixing, and washing with water, the processing takes time and labor, and there is concern that the processing chemicals may affect the human body, or the processing room or work There are many problems such as concern about contamination of the person by the above chemicals, and consideration of pollution caused by waste liquid. Therefore, it has been desired to develop a photosensitive material which uses photosensitive silver halide and which can be dry-processed.
上記乾式処理写真法に関しては多くの提案が行なわれて
いるが、なかでも現像工程を熱処理で行ない得る熱現像
感光材料は上記要望に適った感光材料として注目を集め
ている。Although many proposals have been made regarding the above dry processing photographic method, a photothermographic material capable of performing a developing step by heat treatment has been attracting attention as a photosensitive material satisfying the above demand.
この様な熱現像感光材料については、例えば特公昭43-4
921号および同43-4924号公報にその記載があり、有機銀
塩、ハロゲン化銀および還元剤から成る感光材料が開示
されている。For such a photothermographic material, for example, Japanese Patent Publication No. 43-4
Nos. 921 and 43-4924 disclose the same, and a light-sensitive material comprising an organic silver salt, a silver halide and a reducing agent is disclosed.
かかる熱現像感光材料に改良を加え、種々の方法によっ
て色画像を得る試みがなされている。Attempts have been made to improve the photothermographic material and obtain a color image by various methods.
例えば、米国特許第3,531,286号、同第3,761,270号およ
び同第3,764,328号等の各明細書中に芳香族第1級アミ
ン現像主薬の酸化体とカプラーとの反応によって色画像
を形成させる熱現像カラー感光材料が開示されている。For example, in U.S. Pat. Nos. 3,531,286, 3,761,270, 3,764,328 and the like, heat-developable color sensitizers for forming a color image by reacting an oxidant of an aromatic primary amine developing agent with a coupler. Materials are disclosed.
また、リサーチ・ディスクロージャー15108号および同1
5127号には、スルホンアミドフェノール或いはスルホン
アミドアニリンの誘導体現像主薬の酸化体とカプラーと
の反応によって色画像を形成させる熱現像カラー感光材
料が開示されている。しかし、これらの方法において
は、熱現像後、露光部に還元銀の像と色画像とが同時に
生ずるため、色画像が濁るという問題点があり、この問
題点を解決する方法として、銀像を液体処理により取り
除くか、色素のみを他の層、例えば受像層を有する受像
シートに転写する方法がある。Research Disclosure No. 15108 and 1
Japanese Patent No. 5127 discloses a heat-developable color light-sensitive material which forms a color image by reacting an oxidized product of a sulfonamidephenol or sulfonamideaniline derivative developing agent with a coupler. However, in these methods, after heat development, an image of reduced silver and a color image are simultaneously generated in the exposed area, so that there is a problem that the color image becomes turbid. As a method for solving this problem, a silver image is formed. There is a method of removing it by liquid treatment or transferring only the dye to another layer, for example, an image receiving sheet having an image receiving layer.
また、リサーチ・ディスクロージャー16966号に色素部
を有する有機イミノ銀塩を用い、熱現像によって露光部
でイミノ基を遊離させ、溶剤を用いて転写紙としての受
像層上に色画像を形成させる熱現像カラー感光材料が開
示されている。In addition, in Research Disclosure No. 16966, an organic imino silver salt having a dye part is used, and the imino group is released in the exposed part by heat development, and a solvent is used to form a color image on the image receiving layer as a transfer paper. A color light-sensitive material is disclosed.
また、特開昭52-105821号、同52-105822号、同56-50328
号各公報、米国特許第4,235,957号明細書、リサーチ・
ディスクロージャー14448号、同15227号および同18137
号等に感熱銀色素漂白法によってポジ色画像を形成させ
る熱現像カラー感光材料が開示されている。Further, JP-A-52-105821, JP-A-52-105822 and JP-A-56-50328
Publications, U.S. Pat.No. 4,235,957, Research
Disclosure 14448, 15227 and 18137
U.S. Pat. No. 4,968,961 discloses a heat-developable color light-sensitive material capable of forming a positive color image by a heat-sensitive silver dye bleaching method.
また、米国特許第3,180,732号、同第3,985,565号および
同第4,022,617号の各明細書中並びにリサーチ・ディス
クロージャー12533号にロイコ色素を利用して色画像を
形成させる熱現像カラー感光材料が開示されている。Further, in U.S. Pat.Nos. 3,180,732, 3,985,565 and 4,022,617 and Research Disclosure 12533, a heat-developable color photosensitive material for forming a color image using a leuco dye is disclosed. .
更にまた、特開昭57-179840号公報には、色素放出助剤
および拡散性色素を放出する還元性色素供与物質を用い
て色画像を形成させる熱現像カラー感光材料が開示され
ている。Furthermore, JP-A-57-179840 discloses a heat-developable color light-sensitive material in which a color image is formed by using a dye-releasing aid and a reducing dye-donor substance that releases a diffusible dye.
更にまた、特開昭57-186744号、同58-123533号、同58-1
49046号各公報には、熱現像により拡散性色素を放出又
は形成させ転写色画像を得る熱現像カラー感光材料が開
示されている。Furthermore, JP-A-57-186744, JP-A-58-123533, and JP-A-58-1
Each publication of 49046 discloses a heat-developable color light-sensitive material for obtaining a transferred color image by releasing or forming a diffusible dye by heat development.
熱現像感光材料の感光層のバインダーとしては従来ゼラ
チンが使用されていたが、熱可塑性でないために熱現像
性が悪いという欠点を有していた。また特に転写型の熱
現像感光材料の感光層のバインダーとしてゼラチンを使
用した場合には色素透過性が悪いという欠点を有してい
た。これを改良するためにゼラチンにポリビニルアルコ
ール、又はポリビニルピロリドン、或いはポリビニルブ
チラールを混合して用いる方法がある。この方法による
とゼラチンのみ使用した場合に比べ熱現像性、色素透過
性が多少改良されるがまだ充分ではなく、さらにゼラチ
ンと混合される上記ポリマーとの相溶性が悪いため転写
型のものにおいては転写ムラが生じやすい。Gelatin has conventionally been used as a binder for the photosensitive layer of a heat-developable light-sensitive material, but it has the drawback of poor heat developability because it is not thermoplastic. In particular, when gelatin is used as a binder of the photosensitive layer of a transfer type photothermographic material, the dye permeability is poor. In order to improve this, there is a method in which gelatin is mixed with polyvinyl alcohol, polyvinyl pyrrolidone, or polyvinyl butyral. According to this method, the heat developability and the dye permeability are slightly improved as compared with the case where only gelatin is used, but it is still insufficient, and the compatibility with the above-mentioned polymer mixed with gelatin is poor, so that in the transfer type. Transfer unevenness is likely to occur.
また一般に重層されたフルカラー感光材料はそれぞれ3
種の異なった分光感度領域に感度を有する感光層の外に
この感光層間を隔てる中間層を有するのが普通である。
通常のカラー感材においては、アルカリ水溶液の浸透
性、セット塗布性等を考慮して乳剤層と同じゼラチンが
用いられている。しかしながら転写型熱現像感光材料に
おいては色素を重層された膜中を実質的に水のない状態
で拡散させるために放出乃至形成された色素の透過性の
よい膜が必要とされる。Generally, three layers of full-color light-sensitive materials are layered.
It is common to have an intermediate layer separating the photosensitive layers in addition to the photosensitive layers sensitive to different types of spectral sensitivity regions.
In a normal color light-sensitive material, the same gelatin as that of the emulsion layer is used in consideration of the permeability of an alkaline aqueous solution, the set coatability and the like. However, in the transfer type photothermographic material, a film having good permeability of the released or formed dye is required in order to diffuse the dye in the layered film in a substantially water-free state.
感光層との同時重層塗布性やセット塗布出来るために膜
の均一性が高いという点からはゼラチンが有利である
が、ドライ膜中での放出乃至形成された色素の透過性が
ゼラチンの場合は低いために例えば特願昭58-223274号
等に記載された様にゼラチンと他のポリマーとの併用等
が提案されている。Gelatin is advantageous in that the film is highly uniform because it can be coated in multiple layers at the same time as the photosensitive layer and can be set-coated, but in the case where the release in the dry film or the permeability of the formed dye is gelatin. Since it is low, it has been proposed to use gelatin in combination with other polymers, as described in Japanese Patent Application No. 58-223274.
特にゼラチンと他の水溶性熱可塑性ポリマー、例えばポ
リビニルアセタール、ポリビニルアルコール、ポリビニ
ルピロリドン等を併用し、ゼラチンを用いた上記利点を
保持しつつ、色素の透過性を改善しようという試みがな
されているが、均一な塗布が難しかったり、色素透過性
もさらに向上したものが望まれている。In particular, an attempt has been made to improve the permeability of the dye while maintaining the above advantages of using gelatin by using gelatin in combination with other water-soluble thermoplastic polymer such as polyvinyl acetal, polyvinyl alcohol, polyvinylpyrrolidone. However, it is desired that uniform coating is difficult and that the dye permeability is further improved.
また一般に感光材料に保護膜を設けることは知られてい
る。熱現像感光材料においてもスリ傷防止、現像性改良
あるいは発煙防止等の目的で保護膜が塗設される。保護
膜として例えばゼラチンを使用した場合、均一な塗布が
出来るという特徴があるが、放出された色素の熱転写を
妨げてしまうし、又膜のベトつきに対しては余り効果が
ない。又、ポリビニルアルコール等は色素の転写性阻害
が少なく保護膜としてかなりの性能を有するが、一方塗
布性においてはゼラチンに劣る。ゼラチンが塗布性が良
好なのはセット塗布出来るという特性を有するためで、
一般にはゼラチンと他の水溶液ポリマーを混合して塗布
する事も行われる。Further, it is generally known to provide a protective film on a photosensitive material. Also in the photothermographic material, a protective film is coated for the purpose of preventing scratches, improving developability, and preventing smoke emission. When gelatin, for example, is used as the protective film, it is characterized in that it can be applied uniformly, but it hinders the thermal transfer of the released dye and is not very effective for the stickiness of the film. Further, polyvinyl alcohol and the like have little inhibition of the transferability of the dye and have a considerable performance as a protective film, but are inferior to gelatin in coating property. Gelatin has good coating properties because it has the property of being set-coatable.
Generally, gelatin and other aqueous polymer are mixed and applied.
しかしながら、ゼラチンと例えばポリビニルアルコール
を混合し塗布しても余り均一な皮膜をつくりにくく満足
な性能は得られない。However, even if gelatin and polyvinyl alcohol are mixed and applied, it is difficult to form a very uniform film and satisfactory performance cannot be obtained.
他の水溶性ポリマーとゼラチンの混合皮膜においても上
記目的を充分に達成するものはないのが現状である。The present situation is that none of the mixed films of other water-soluble polymers and gelatin can sufficiently achieve the above object.
[発明の目的] 本発明は上記従来の欠点に鑑み、ゼラチン等との相溶性
の優れた変性ポリビニルアルコール系重合体を特に感光
層のバインダー、感光層間に設けられる中間層、或いは
保護膜等に含有し、熱現像性及び色素透過性が良好であ
り、転写ムラがなく、かつ製造時の塗布性にも優れた熱
現像感光材料を提供することを目的とする。[Object of the Invention] In view of the above-mentioned conventional drawbacks, the present invention provides a modified polyvinyl alcohol-based polymer having excellent compatibility with gelatin or the like as a binder of a photosensitive layer, an intermediate layer provided between photosensitive layers, or a protective film. It is an object of the present invention to provide a photothermographic material containing the photothermographic material, which has good heat developability and dye permeability, has no transfer unevenness, and has excellent coatability during production.
[発明の構成] 本発明の上記目的は、支持体上に、少なくともハロゲン
化銀粒子を含有する感光層を有する熱現像感光材料にお
いて、該感光材料が、ポリビニルアルコール系重合体
(以下PVA系重合体と称する)を一成分とし、イオン性
基を有する重合体を他成分とする水溶性又は水分散性の
ブロック共重合体を含有する層を有し、前記イオン性基
を有する重合体に対するPVA系重合体の重量比率が0.2以
上50以下である熱現像感光材料を提供することによって
達成される。[Constitution of Invention] The above object of the present invention is to provide a photothermographic material having a photosensitive layer containing at least silver halide grains on a support, wherein the photosensitive material is a polyvinyl alcohol polymer (hereinafter referred to as PVA-based polymer). PVA for a polymer having an ionic group, which has a layer containing a water-soluble or water-dispersible block copolymer containing a polymer having an ionic group as another component This is achieved by providing a photothermographic material in which the weight ratio of the system polymer is 0.2 or more and 50 or less.
[発明の具体的構成] 本発明において使用される上記のPVA系重合体を一成分
とし、イオン性基を有する重合体を他成分とする水溶性
又は水分散性のブロック共重合体(以下単に変性PVA系
重合体と称する)は、種々の任意の方法により製造する
ことができるが、例えば、末端にチオール酸エステル基
を有するポリビニルエステル系重合体をケン化すること
により得られる末端にメルカプト基を有するPVA系重合
体の存在下に、ラジカル重合可能な、イオン性基を有す
るモノマーをラジル重合して製造する方法が最も好まし
い。[Concrete Structure of the Invention] A water-soluble or water-dispersible block copolymer (hereinafter simply referred to as “the PVA polymer used in the present invention as one component and a polymer having an ionic group as another component” The modified PVA-based polymer) can be produced by various arbitrary methods, for example, a mercapto group at the terminal obtained by saponifying a polyvinyl ester-based polymer having a thiol ester group at the terminal. Most preferred is a method of producing a radically polymerizable monomer having an ionic group by radical polymerization in the presence of a PVA-based polymer having
その方法の詳細を以下に説明する。The details of the method will be described below.
まず第1に、末端にメルカプト基を有するPVA系重合体
はチオール酸の存在下にビニルエステル類モノマーを主
体とするビニルモノマーを重合して得たポリビニルエス
テル系重合体を常法によりけん化して得られる。First of all, the PVA-based polymer having a mercapto group at the terminal is obtained by polymerizing a vinyl monomer mainly composed of vinyl ester monomers in the presence of thiol acid to saponify the polyvinyl ester-based polymer by a conventional method. can get.
ここで使用するチオール酸には−COSH基を有する有機チ
オール酸が包含される。例えばチオール酢酸、チオール
プロピオン酸、チオール酪酸、チオール吉草酸等があげ
られるが、チオール酢酸が分解性もよく特に好ましい。The thiol acid used here includes an organic thiol acid having a -COSH group. Examples thereof include thiol acetic acid, thiol propionic acid, thiol butyric acid, and thiol valeric acid. Thiol acetic acid is particularly preferable because of its degradability.
チオール酸の重合系への添加量、添加方法には特に制限
はなく、目的とするPVA系重合体の物性値によって適宜
決定されるものである。The amount of thiol acid added to the polymerization system and the method of addition are not particularly limited and are appropriately determined depending on the physical properties of the desired PVA polymer.
またビニルエステルはラジカル重合可能なビニルエステ
ルであれば使用でき、例えばギ酸ビニル、酢酸ビニル、
プロピオン酸ビニル、バーサテイック酸ビニル、ラウリ
ン酸ビニル、ステアリン酸ビニル等があげられ、特に酢
酸ビニルが最も重合性がよく、好ましい。Further, the vinyl ester can be used as long as it is a radically polymerizable vinyl ester, for example, vinyl formate, vinyl acetate,
Examples thereof include vinyl propionate, vinyl versatate, vinyl laurate, vinyl stearate and the like, and vinyl acetate is particularly preferred because it has the highest polymerizability.
チオール酸の存在下における酢酸ビニル等のビニルエス
テル類を主体とするビニルモノマーの重合はラジカル重
合開始剤の存在下、塊状重合法、溶液重合法、パール重
合法、乳剤重合法などいずれの方法でも行なうことがで
きるが、メタノールを溶媒とする溶液重合法が工業的に
は最も有利である。重合プロセスとしては回分法、半連
続法、連続法等公知のプロセスを採用することが出来
る。Polymerization of vinyl monomers mainly composed of vinyl esters such as vinyl acetate in the presence of thiol acid can be carried out by any method such as bulk polymerization method, solution polymerization method, pearl polymerization method and emulsion polymerization method in the presence of a radical polymerization initiator. Although it can be carried out, the solution polymerization method using methanol as a solvent is industrially most advantageous. A known process such as a batch process, a semi-continuous process, or a continuous process can be adopted as the polymerization process.
ラジカル重合開始剤としては2,2′−アゾビスイソブチ
ロニトリル、過酸化ベンゾイル、過酸化カーボネート等
公知のラジカル重合開始剤が挙げられるが、2,2′−ア
ゾビスイソブチロニトリル等のアゾ系開始剤が取扱いや
すく特に好ましい。また放射線、電子線等を使用して重
合を行なうこともできる。重合温度は使用する開始剤の
種類により適当な温度を採用することが望ましいが、通
常30〜90℃の範囲から選ばれる。所定時間重合した後未
重合のビニルエステル類を通常の方法で除去することに
より末端にチオール酸エステル基を有するポリビニルエ
ステル系重合体がえられる。Examples of the radical polymerization initiator include known radical polymerization initiators such as 2,2′-azobisisobutyronitrile, benzoyl peroxide, and carbonate carbonate, and 2,2′-azobisisobutyronitrile and the like. Azo initiators are particularly preferable because they are easy to handle. Also, the polymerization can be carried out by using radiation, electron beam or the like. The polymerization temperature is preferably selected from the range of 30 to 90 ° C, although it is desirable to adopt an appropriate temperature depending on the kind of the initiator used. After polymerization for a predetermined period of time, unpolymerized vinyl esters are removed by a usual method to obtain a polyvinyl ester polymer having a thiolate ester group at the terminal.
このようにして得られたポリビニルエステル系重合体は
常法によりけん化されるが、通常ポリビニルエステル系
重合体をアルコール溶液特にメタノール溶液として実施
するのが有利である。アルコールは無水物のみならず少
量の含水系のものも目的に応じて用いられ、また酢酸メ
チル、酢酸エチルなどの有機溶媒を任意に含有せしめて
もよい。けん化温度は通常10〜70℃の範囲から選ばれ
る。けん化触媒としては水酸化ナトリウム、水酸化カリ
ウム、ナトリウムメチラート、カリウムメチラート等の
アルカリ性触媒が好ましい。けん化触媒の使用量はけん
化度の大小および水分量等により適宜決められるが、ビ
ニルエステル単位に対しモル比で0.001以上、好ましく
は0.002以上用いることが望ましい。一方、残存アルカ
リをポリマー中より除去することから、モル比で0.2以
下にすることが望ましい。The polyvinyl ester-based polymer thus obtained is saponified by a conventional method, but it is usually advantageous to carry out the polyvinyl ester-based polymer as an alcohol solution, particularly a methanol solution. As the alcohol, not only an anhydride but also a small amount of a water-containing alcohol may be used according to the purpose, and an organic solvent such as methyl acetate or ethyl acetate may be optionally contained. The saponification temperature is usually selected from the range of 10 to 70 ° C. As the saponification catalyst, alkaline catalysts such as sodium hydroxide, potassium hydroxide, sodium methylate and potassium methylate are preferable. The amount of the saponification catalyst used is appropriately determined depending on the degree of saponification, the amount of water, etc., but it is desirable to use 0.001 or more, preferably 0.002 or more in molar ratio to the vinyl ester unit. On the other hand, since the residual alkali is removed from the polymer, the molar ratio is preferably 0.2 or less.
このけん化反応により末端にチオール酸エステル基を有
するポリビニルエステル系重合体の末端のチオール酸エ
ステルと主鎖のビニルエステル結合がけん化され、ポリ
マー末端はメルカプト基に、主鎖はビニルアルコールに
なるが、主鎖のビニルエステル単位のけん化度は使用目
的に応じて変えられるが、20モル%以上が好ましく、よ
り好ましくは50モル%以上、更に好ましくは70モル%以
上であれば特に制限はない。けん化反応後析出した重合
体を、例えばメタノールで洗浄する等公知の方法で精製
し、残存アルカリ、酢酸のアルカリ金属塩等の不純物を
除去して乾燥することにより通常白色粉末として末端に
メルカプト基を有するPVA系重合体が得られる。This saponification reaction saponifies the terminal thiolate ester of the polyvinyl ester polymer having a thiolate ester group at the end and the vinyl ester bond of the main chain, the polymer end is a mercapto group, and the main chain becomes vinyl alcohol, The degree of saponification of the vinyl ester unit in the main chain can be changed according to the purpose of use, but is preferably 20 mol% or more, more preferably 50 mol% or more, and further preferably 70 mol% or more, without any particular limitation. The polymer precipitated after the saponification reaction is purified by a known method such as washing with methanol, residual alkali, and impurities such as an alkali metal salt of acetic acid are removed and dried to usually obtain a mercapto group at the end as a white powder. A PVA-based polymer having is obtained.
次に、この末端にメルカプト基を有するPVA系重合体の
存在下に、イオン性基を有するモノマーのラジカル重合
を行なう方法について述べる。重合方法としては、通常
の公知の方法、たとえば塊状重合、溶液重合、パール重
合、および乳化重合などいずれの方法も採用されうる
が、PVA系重合体を溶解しうる溶剤、たとえば水やジメ
チルスルホキシドを主体とする媒体中で重合を行うの
が、特に好ましい。また重合プロセスとしては回分法、
半回分法、連続法のいずれも採用することができる。Next, a method of radically polymerizing a monomer having an ionic group in the presence of a PVA-based polymer having a mercapto group at the terminal will be described. As the polymerization method, a generally known method, for example, any method such as bulk polymerization, solution polymerization, pearl polymerization, and emulsion polymerization can be adopted, but a solvent capable of dissolving the PVA-based polymer, such as water or dimethyl sulfoxide, can be used. It is particularly preferred to carry out the polymerization in a predominant medium. As the polymerization process, the batch method,
Both the semi-batch method and the continuous method can be adopted.
上記ラジカル重合のラジカル重合開始剤としては、たと
えば2,2′−アゾビスイソブチロニトリル、ベンゾイル
パーオキサイド、ラウロイルパーオキサイド、ジイソプ
ロピルパーオキシカーボネート、過硫酸カリウム、過硫
酸アンモニウム等の中から重合系に合ったものが使用さ
れるが、水系での重合の場合、PVA末端のメルカプト基
と臭素酸カリウム、過硫酸カリウム、過硫酸アンモニウ
ム、過酸化水素等の酸化剤によるレドックス開始も可能
である。この中でも臭素酸カリウムは、通常の重合条件
下では単独ではラジカルを発生させず、PVA末端のメル
カプト基とのレドックス反応によってのみ分解、ラジカ
ルを発生することから、上記のブロック共重合体を合成
する上で特に好ましい開始剤である。Examples of the radical polymerization initiator for the radical polymerization include, for example, 2,2′-azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, diisopropyl peroxycarbonate, potassium persulfate, ammonium persulfate, etc. In the case of water-based polymerization, redox initiation is also possible with a mercapto group at the PVA end and an oxidizing agent such as potassium bromate, potassium persulfate, ammonium persulfate, or hydrogen peroxide. Among them, potassium bromate does not generate a radical by itself under ordinary polymerization conditions, and decomposes only by a redox reaction with a mercapto group at the PVA terminal to generate a radical, thereby synthesizing the above block copolymer. Above all, it is a particularly preferable initiator.
上記した末端にメルカプト基を有するPVA系重合体の存
在下にラジカル重合を行なうに際し、重合系が酸性であ
ることが望ましい。これはメルカプト基が塩基性下にお
いては、モノマーの二重結合へイオン的に付加、消失す
る速度が大きく、重合効率が著しく低下するためであ
り、水系の重合であれば、全ての重合操作をpH4以下で
実施することが望ましい。When radical polymerization is carried out in the presence of the above-mentioned PVA-based polymer having a mercapto group, the polymerization system is preferably acidic. This is because when the mercapto group is basic, the rate of ionic addition to and disappearance from the double bond of the monomer is large, and the polymerization efficiency is significantly reduced. It is desirable to carry out at pH 4 or less.
なお本発明で言うところのPVA系重合体とは、ビニルア
ルコール単位を20モル%以上が好ましく、より好ましく
は50モル%以上、更に好ましくは70モル%以上含有する
重合体をさすものであり、他の単量体成分として、たと
えば酢酸ビニル、ギ酸ビニル、プロピオン酸ビニル、バ
ーサティック酸ビニル、エチレン、プロピレン、(メ
タ)アクリル酸及びその塩、イタコン酸、マレイン酸、
フマル酸及びそれらの塩、2−アクリルアミドプロパン
スルホン酸及びその塩、(メタ)アクリルアミドプロピ
ルトリメチルアンモニウムクロリド等を含んでいても良
い。重合度は10以上3500以下の範囲にあるものが好まし
いが特に制限はない。The PVA-based polymer as referred to in the present invention is preferably a polymer containing 20 mol% or more of vinyl alcohol units, more preferably 50 mol% or more, and further preferably 70 mol% or more, As other monomer components, for example, vinyl acetate, vinyl formate, vinyl propionate, vinyl versatate, ethylene, propylene, (meth) acrylic acid and salts thereof, itaconic acid, maleic acid,
It may contain fumaric acid and salts thereof, 2-acrylamidopropanesulfonic acid and salts thereof, (meth) acrylamidopropyltrimethylammonium chloride and the like. The degree of polymerization is preferably 10 or more and 3500 or less, but is not particularly limited.
上記変性PVA系重合体において、PVA系重合体成分以外の
他成分については、イオン性基を含有する重合体であれ
ば特に制限はなく、例えばラジカル(共)重合可能なイ
オン性モノマー、例えばアクリル酸、メタクリル酸、イ
タコン酸、マレイン酸、フマル酸、ビニル硫酸、ビニル
スルホン酸、p−スチレンスルホン酸、2−アクリルア
ミドプロパンスルホン酸、2−アクリロイルオキシエチ
ルリン酸等およびこれらの金属塩やアンモニウム塩のア
ニオン性モノマー、(メタ)アクリル酸ジメチルアミノ
エチルや(メタ)アクリルアミドプロピルトリメチルア
ンモニウムクロリド等のカチオン性モノマーの単独重合
体あるいは共重合体、または前記イオン性モノマーとア
クリルアミド、メタアクリルアミド、N,N−ジメチルア
クリルアミド、N−ビニルピロリドン、(メタ)アクリ
ル酸メチル、(メタ)アクリル酸エチル、(メタ)アク
リロニトリル、エチレン、プロピレン等のラジカル
(共)重合可能なノニオン性モノマーとの共重合体によ
って構成される。In the modified PVA-based polymer, other components than the PVA-based polymer component are not particularly limited as long as they are polymers containing an ionic group, and for example, radical (co) polymerizable ionic monomers such as acryl Acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl sulfuric acid, vinyl sulfonic acid, p-styrene sulfonic acid, 2-acrylamido propane sulfonic acid, 2-acryloyloxyethyl phosphoric acid, etc., and their metal salts and ammonium salts. Anionic monomer, a homopolymer or copolymer of a cationic monomer such as dimethylaminoethyl (meth) acrylate or (meth) acrylamidopropyltrimethylammonium chloride, or the above ionic monomer and acrylamide, methacrylamide, N, N -Dimethylacrylamide, N-bi Rupiroridon, (meth) acrylate, (meth) acrylate, (meth) acrylonitrile, ethylene, composed of a copolymer of radically (co) polymerizable nonionic monomers such as propylene.
上記ラジカル(共)重合可能なイオン性モノマーの内、
特にアクリル酸、メタクリル酸等のカルボキシル基(金
属塩およびアンモニウム塩を含む)を含有するモノマ
ー、またはビニルスルホン酸、p−スチレンスルホン
酸、2−アクリルアミドプロパンスルホン酸等のスルホ
ン酸基(金属塩およびアンモニウム塩を含む)を含有す
るモノマー等が、またこれらイオン性モノマーと共重合
し得るノニオン性モノマーの内、特にアクリルアミド、
メタクリルアミド、N,N−ジメチルアクリルアミド、N
−ビニルピロリドン等がイオン性重合体を構成する単量
体として好ましい。またイオン性重合体中のイオン性基
の量はゼラチン等と相互作用をもつために、0.5モル%
以上、好ましくは1モル%以上、更に好ましくは2モル
%以上が望ましい。Of the above radical (co) polymerizable ionic monomers,
In particular, monomers containing a carboxyl group (including metal salt and ammonium salt) such as acrylic acid and methacrylic acid, or sulfonic acid groups (metal salt and metal carboxylic acid) such as vinyl sulfonic acid, p-styrene sulfonic acid, and 2-acrylamido propane sulfonic acid. (Including ammonium salts), etc., and among the nonionic monomers that can be copolymerized with these ionic monomers, especially acrylamide,
Methacrylamide, N, N-dimethylacrylamide, N
-Vinylpyrrolidone and the like are preferable as the monomer constituting the ionic polymer. The amount of ionic groups in the ionic polymer is 0.5 mol% because it interacts with gelatin.
The amount is preferably 1 mol% or more, more preferably 2 mol% or more.
また上記変性PVA系重合体中のPVA系重合体成分と他成分
であるイオン性重合体との重量比率は特に制限はない
が、好ましくは、 0.2≦(PVA系重合体)/(イオン性重合体)≦50 更に好ましくは、 0.3≦(PVA系重合体)/(イオン性重合体)≦40 であり、この時に特にゼラチン等との相溶性にすぐれ
る。The weight ratio of the PVA polymer component in the modified PVA polymer and the ionic polymer which is another component is not particularly limited, but preferably 0.2 ≦ (PVA polymer) / (ionic weight). Combined) ≦ 50, more preferably 0.3 ≦ (PVA-based polymer) / (ionic polymer) ≦ 40, and at this time, the compatibility with gelatin and the like is particularly excellent.
本発明の熱現像感光材料の感光層に用いられるバインダ
ーとしては、上記変性PVA系重合体あるいは上記変性PVA
系重合体とポリビニルブチラール、ポリ酢酸ビニル、エ
チルセルロース、ポリメチルメタクリレート、セルロー
スアセテートブチレート、ポリビニルアルコール、ポリ
ビニルピロリドン、ゼラチンおよびフタル化ゼラチン等
の合成或いは天然の高分子物質を1又は2以上組合せて
用いるこことができる。特に、ゼラチンまたはその誘導
体と変性PVA系重合体とを併用することが好ましい。The binder used in the photosensitive layer of the photothermographic material of the present invention includes the modified PVA polymer or the modified PVA.
Polymers and polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethylmethacrylate, cellulose acetate butyrate, polyvinyl alcohol, polyvinylpyrrolidone, gelatin and phthalated gelatin are used in combination with one or more polymer substances. I can do this. Particularly, it is preferable to use gelatin or a derivative thereof and a modified PVA polymer in combination.
上記高分子物質と変性PVA系重合体とを併用する場合、
この重量比率は高分子物質:変性PVA系重合体=1:9〜9:
1が好ましく、さらに好ましくは2:8〜7:3である。In the case of using the above polymeric substance and a modified PVA polymer in combination,
This weight ratio is as follows: Polymer: Modified PVA polymer = 1: 9-9:
1 is preferable, and more preferably 2: 8 to 7: 3.
ゼラチンは石灰処理によるものでも酸処理によるもので
もよく、オセインゼラチン、ピッグスキンゼラチン、ハ
イドゼラチン又はこれらをエステル化、フェニルカルバ
モイル化等とした変性ゼラチンであってもよい。The gelatin may be lime-treated or acid-treated, and may be ossein gelatin, pigskin gelatin, hide gelatin or modified gelatin obtained by esterification or phenylcarbamoylation thereof.
バインダーの使用量は、通常1層当たり1m2に対して0.
05g〜50gであり、好ましくは0.1g〜10gである。また、
バインダーは、色素供与物質モノマー単位1gに対して0.
1〜10g用いることが好ましく、より好ましくは0.25〜4g
である。The amount of binder used is usually 0 per 1 m 2 per layer.
05g to 50g, preferably 0.1g to 10g. Also,
The binder is 0 for 1 g of the dye-donor monomer unit.
It is preferable to use 1 to 10 g, more preferably 0.25 to 4 g
Is.
本発明の熱現像感光材料に必要に応じて用いられる中間
層としては、前記変性PVA系重合体を単独で用いても良
いが、好ましくはゼラチン、ゼラチン誘導体、あるいは
水溶性高分子物質と併用される。As the intermediate layer which is optionally used in the photothermographic material of the present invention, the modified PVA polymer may be used alone, but is preferably used in combination with gelatin, a gelatin derivative or a water-soluble polymer substance. It
併用されるゼラチンとしては、石灰処理によるものでも
酸処理によるものでもよく、オセインゼラチン、ピッグ
スキンゼラチン、ハイドゼラチン又はこれらをエステル
化、フェニルカルバモイル化等とした変性ゼラチンであ
ってもよい。The gelatin used in combination may be lime-treated or acid-treated, and may be ossein gelatin, pigskin gelatin, hide gelatin, or modified gelatin obtained by esterification or phenylcarbamoylation thereof.
併用される水溶性高分子物質としては、ポリビニルブチ
ラール、ポリ酢酸ビニル、エチルセルロース、ポリメチ
ルメタクリレート、セルロースアセテートブチレート、
ポリビニルアルコール、ポリビニルピロリドン等が挙げ
られ、これらを1又は2以上組合せて用いることが出来
る。As the water-soluble polymer substance used in combination, polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate,
Examples thereof include polyvinyl alcohol and polyvinylpyrrolidone, and these can be used alone or in combination of two or more.
中間層として上記ゼラチン等と変性PVA系重合体とを併
用する場合、変性PVA系重合体は10〜90重量%含有する
のが好ましく、さらに好ましくは40〜90重量%である。When the gelatin or the like and a modified PVA-based polymer are used in combination as the intermediate layer, the modified PVA-based polymer is preferably contained in an amount of 10 to 90% by weight, more preferably 40 to 90% by weight.
中間層の塗布量は、通常1層当り1m2に対して0.01g〜1
0gであり、好ましくは0.05g〜5gである。The coating amount of the intermediate layer is usually 0.01 g to 1 per 1 m 2 per layer.
It is 0 g, preferably 0.05 g to 5 g.
本発明の熱現像感光材料に必要に応じて用いられる保護
膜としては、前記変性PVA系重合体を単独で用いても良
いが、好ましくはゼラチン、ゼラチン誘導体あるいはそ
の他の水溶性高分子物質と併用される。As the protective film optionally used in the photothermographic material of the present invention, the modified PVA polymer may be used alone, but is preferably used in combination with gelatin, a gelatin derivative or another water-soluble polymer substance. To be done.
併用されるゼラチンとしては、石灰処理によるものでも
酸処理によるものでもよく、オセインゼラチン、ピッグ
スキンゼラチン、ハイドゼラチン又はこれらをエステル
化、フェニルカルバモイル化等とした変性ゼラチンであ
ってもよい。The gelatin used in combination may be lime-treated or acid-treated, and may be ossein gelatin, pigskin gelatin, hide gelatin, or modified gelatin obtained by esterification or phenylcarbamoylation thereof.
併用される水溶性高分子物質としては、ポリビニルブチ
ラール、ポリ酢酸ビニル、エチルセルロース、ポリメチ
ルメタクリレート、セルロースアセテートブチレート、
ポリビニルアルコール、ポリビニルピロリドン等が挙げ
られ、これらを1又は2以上組合せて用いることが出来
る。As the water-soluble polymer substance used in combination, polyvinyl butyral, polyvinyl acetate, ethyl cellulose, polymethyl methacrylate, cellulose acetate butyrate,
Examples thereof include polyvinyl alcohol and polyvinylpyrrolidone, and these can be used alone or in combination of two or more.
保護膜として上記ゼラチン等と変性PVA系重合体とを併
用する場合、変性PVA系重合体は10〜90重量%含有する
のが好ましく、さらに好ましくは30〜80重量%である。When the gelatin or the like and a modified PVA-based polymer are used together as a protective film, the modified PVA-based polymer is preferably contained in an amount of 10 to 90% by weight, more preferably 30 to 80% by weight.
保護膜の塗布量は、通常1層当たり1m2に対して0.1〜2
0gであり、好ましくは1g〜5gである。The coating amount of the protective film is usually 0.1 to 2 per 1 m 2 per layer.
It is 0 g, preferably 1 g to 5 g.
保護膜中には熱溶剤、有機銀塩、還元剤等、ハロゲン化
銀以外の成分を添加しても良く、また熱現像感光材料が
転写型の場合、受像層との密着性及び転写後の剥離性を
改良するためにマット剤を併用したり、あるいは熱溶融
性化合物、例えばワックス等を混入しても良い。A component other than silver halide, such as a thermal solvent, an organic silver salt, a reducing agent, etc., may be added to the protective film. When the photothermographic material is a transfer type, the adhesion to the image receiving layer and the property after transfer are A matting agent may be used in combination for improving the peelability, or a heat-melting compound such as wax may be mixed.
本発明に用いることのできる色素供与物質について説明
する。色素供与物質としては、感光性ハロゲン化銀及び
/又は必要に応じて用いられる有機銀塩の還元反応に関
与し、その反応の関数として拡散性の色素を形成または
放出できるものであれば良く、その反応形態に応じて、
正の関数に作用するネガ型の色素供与物質(すなわち、
ネガ型のハロゲン化銀を用いた場合にネガの色素画像を
形成する)と負の関数に作用するポジ型の色素供与物質
(すなわち、ネガ型のハロゲン化銀を用いた場合にポジ
の色素画像を形成する)に分類できる。ネガ型の色素供
与物質はさらに以下のように分類される。The dye-providing substance that can be used in the present invention will be described. The dye-donating substance may be any one as long as it can participate in the reduction reaction of the photosensitive silver halide and / or the organic silver salt optionally used and can form or release a diffusible dye as a function of the reaction, Depending on the reaction mode,
Negative-type dye-donors that act on positive functions (ie,
A negative dye image is formed when a negative silver halide is used) and a positive dye-donor which acts on a negative function (that is, a positive dye image when a negative silver halide is used) Form)). Negative type dye-donor substances are further classified as follows.
すなわちネガ型色素供与物質には、酸化されると拡散性
色素を放出する化合物(還元性色素放出化合物)と還元
剤とのカップリング反応により拡散性色素を形成する化
合物とに分けられ、そして後者はさらに、カップリング
色素放出型化合物とカップリング色素形成型化合物とに
分けることができる。That is, the negative dye-providing substance is divided into a compound that releases a diffusible dye when oxidized (a reducing dye-releasing compound) and a compound that forms a diffusible dye by a coupling reaction with a reducing agent, and the latter. Can be further divided into coupling dye releasing compounds and coupling dye forming compounds.
各々の色素供与物質についてさらに説明する。Each dye-donor will be further described.
還元性色素放出化合物としては、例えば一般式(1)で
示される化合物が挙げられる。Examples of the reducing dye releasing compound include compounds represented by the general formula (1).
一般式(1) Car−NHSO2−Dye 式中Carは、感光性ハロゲン化銀及び/又は必要に応じ
て用いられる有機銀塩の還元に際し、酸化され色素を放
出する還元性の基質(所謂キャリアー)であり、Dyeは
拡散性の色素残基である。Formula (1) Car-NHSO 2 -Dye wherein Car, upon reduction of the organic silver salt used in accordance with the photosensitive silver halide and / or necessary, reducing the substrate (so-called carrier that releases the oxidized dye ), And Dye is a diffusible dye residue.
上記の還元性色素放出化合物の具体例としては、特開昭
57−179840号、同58−116537号、同59−60434号、同59
−65839号、同59−71046号、同59−87450号、同59−887
30号、同59−123837号、同59−165054号、同59−165055
号各明細書等に記載されており、例えば以下の化合物が
挙げられる。Specific examples of the above reducing dye-releasing compound include those disclosed in JP-A-
57-179840, 58-116537, 59-60434, 59
-65839, 59-71046, 59-87450, 59-887
No. 30, 59-123837, 59-165054, 59-165055
The following compounds are mentioned, for example.
別の還元性色素放出化合物としては例えば一般式(2)
で示される化合物が挙げられる。 As another reducing dye-releasing compound, for example, general formula (2)
The compound shown by is mentioned.
一般式(2) 式中、A1、A2は、各々水素原子、ヒドロキシ基又はアミ
ノ基を示し、Dyeは一般式(1)で示されたDyeと同義で
ある。上の化合物の具体例は特開昭59−124329に示され
ている。General formula (2) In the formula, A 1 and A 2 each represent a hydrogen atom, a hydroxy group or an amino group, and Dye has the same meaning as Dye represented by the general formula (1). Specific examples of the above compounds are shown in JP-A-59-124329.
カップリング色素放出型化合物としては、一般式(3)
で示される化合物が挙げられる。As the coupling dye-releasing compound, a compound represented by the general formula (3)
The compound shown by is mentioned.
一般式(3) Cp1JnDye 式中、Cp1は還元剤の酸化体と反応して拡散性の色素を
放出することができる有機基(いわゆるカプラー残基)
であり、Jは2価の結合基であり、還元剤の酸化体との
反応によりCp1とJとの結合が開裂する。nは0又は1
を表わし、Dyeは一般式(1)で定義されたものと同義
である。またCp1はカップリング色素放出型化合物を非
拡散性にする為に各種のバラスト基で置換されているこ
とが好ましく、バラスト基としては用いられる感光材料
の形態に応じて炭素原子数8個以上(より好ましくは12
個以上)の有機基、又はスルホ基、カルボキシ基等の親
水性基、或いは8個以上(より好ましくは12個以上)の
炭素原子とスルホ基、カルボキシ基等の親水性基を共に
有する基である。別の特に好ましいバラスト基としては
ポリマー鎖を挙げることができる。General formula (3) Cp 1 J n Dye In the formula, Cp 1 is an organic group capable of reacting with an oxidant of a reducing agent to release a diffusible dye (so-called coupler residue).
And J is a divalent linking group, and the bond between Cp 1 and J is cleaved by the reaction with the oxidized form of the reducing agent. n is 0 or 1
And Dye has the same meaning as defined in the general formula (1). Further, Cp 1 is preferably substituted with various ballast groups in order to make the coupling dye-releasing compound non-diffusible. The ballast group has 8 or more carbon atoms depending on the form of the photosensitive material used. (More preferably 12
Or more) organic groups, or hydrophilic groups such as sulfo groups and carboxy groups, or groups having both 8 or more (more preferably 12 or more) carbon atoms and hydrophilic groups such as sulfo groups and carboxy groups. is there. Another particularly preferred ballast group may include a polymer chain.
上記の一般式(3)で示される化合物の具体例として
は、特開昭57−186744号、同57−122596号、同57−1606
98号、同59−174834号、同57−224883号、同59−159159
号、特願昭59−104901号各明細書に記載されており、例
えば以下の化合物が挙げられる。Specific examples of the compound represented by the above general formula (3) include JP-A Nos. 57-186744, 57-122596, and 57-1606.
98, 59-174834, 57-224883, 59-159159
And Japanese Patent Application No. 59-104901, and examples thereof include the following compounds.
カップリング色素形成化合物としては、一般式(4)で
示される化合物が挙げられる。 Examples of the coupling dye forming compound include compounds represented by the general formula (4).
一般式(4) Cp2XQ) 同義であり、Yはアルキレン基、アリレーン基又はアラ
ルキレン基を表わし、Zは2価の有機基を表わし、Lは
エチレン性不飽和基又はエチレン性不飽和基を有する基
を表わす。General formula (4) Cp 2 XQ) has the same meaning, Y represents an alkylene group, an arylene group or an aralkylene group, Z represents a divalent organic group, and L represents an ethylenically unsaturated group or an ethylenically unsaturated group. Represents a group having.
一般式(4)及び(5)で表わされるカップリング色素
形成化合物の具体例としては、特開昭59−124339号、同
59−181345号、特願昭58−109293号、同59−179657号、
同59−181604号、同59−182506号、同59−182507号の各
明細書等に記載されており、例えば以下の化合物が挙げ
られる。Specific examples of the coupling dye-forming compounds represented by the general formulas (4) and (5) are described in JP-A-59-124339 and JP-A-59-124339.
59-181345, Japanese Patent Application No. 58-109293, 59-179657,
No. 59-181604, No. 59-182506, No. 59-182507, and the like, and the following compounds are exemplified.
式中、Cp2は還元剤の酸化体と反応(カップリング反
応)して拡散性の色素を形成することができる有機基
(いわゆるカプラー残基)であり、Xは二価の結合基を
表わし、Qはバラスト基を表わす。 In the formula, Cp 2 is an organic group (so-called coupler residue) capable of reacting with an oxidized form of a reducing agent (coupling reaction) to form a diffusible dye, and X represents a divalent linking group. , Q represents a ballast group.
Cp2で表わされるカプラー残基としては形成される色素
の拡散性の為にその分子量が700以下が好ましく、より
好ましくは500以下である。The coupler residue represented by Cp 2 has a molecular weight of preferably 700 or less, more preferably 500 or less because of the diffusibility of the dye formed.
また、バラスト基は一般式(3)で定義されたバラスト
基と同じバラスト基が好ましく、特に8個以上(より好
ましくは12個以上)の炭素原子とスルホ基、カルボキシ
基等の親水性基を共に有する基が好ましく、さらにポリ
マー鎖がより好ましい。Further, the ballast group is preferably the same ballast group as the ballast group defined by the general formula (3), particularly 8 or more (more preferably 12 or more) carbon atoms and a hydrophilic group such as a sulfo group or a carboxy group. A group having both groups is preferable, and a polymer chain is more preferable.
このポリマー鎖を有するカップリング色素形成化合物と
しては、一般式(5)で表わ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が好ましい。As the coupling dye forming compound having this polymer chain, a polymer having a repeating unit derived from the monomer represented by the general formula (5) is preferable.
一般式(5) Cp2XYlZL) 式中、Cp2、Xは一般式(4)で定義されたものと ポリマー 上述の一般式(3)、(4)及び(5)において、Cp1
又はCp2で定義されるカプラー残基について更に詳述す
ると、下記一般式で表わされる基が好ましい。General formula (5) Cp 2 XY l ZL) In the formula, Cp 2 and X are as defined in the general formula (4). polymer In the above general formulas (3), (4) and (5), Cp 1
Further, the coupler residue defined by Cp 2 will be described in more detail, and a group represented by the following general formula is preferred.
式中、R1、R2、R3及びR4はそれぞれ水素原子、ハロゲン
原子、アルキル基、シクロアルキル基、アリール基、ア
シル基、アルキルオキシカルボニル基、アリールオキシ
カルボニル基、アルキルスルホニル基、アリールスルホ
ニル基、カルバモイル基、スルフアモイル基、アシルオ
キシ基、アミノ基、アルコキシ基、アリールオキシ基、
シアノ基、ウレイド基、アルキルチオ基、アリールチオ
基、カルボキシ基、スルホ基又は複素環残基を表わし、
これらはさらに水酸基、カルボキシ基、スルホ基、アル
コキシ基、シアノ基、ニトロ基、アルキル基、アリール
基、アリールオキシ基、アシルオキシ基、アシル基、ス
ルフアモイル基、カルバモイル基、イミド基、ハロゲン
原子等で置換されていてもよい。 In the formula, R 1 , R 2 , R 3 and R 4 are each a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an acyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, aryl. Sulfonyl group, carbamoyl group, sulfamoyl group, acyloxy group, amino group, alkoxy group, aryloxy group,
Represents a cyano group, a ureido group, an alkylthio group, an arylthio group, a carboxy group, a sulfo group or a heterocyclic residue,
These are further substituted with hydroxyl group, carboxy group, sulfo group, alkoxy group, cyano group, nitro group, alkyl group, aryl group, aryloxy group, acyloxy group, acyl group, sulfamoyl group, carbamoyl group, imide group, halogen atom, etc. It may have been done.
これらの置換基はCp1及びCp2の目的に応じて選択され、
前述の如くCp1においては置換基の一つはバラスト基で
あることが好ましく、Cp2においては形成される色素の
拡散性を高めるために分子量が700以下、より好ましく
は500以下になるよう置換基が選択されることが好まし
い。These substituents are selected according to the purpose of Cp 1 and Cp 2 ,
As described above, in Cp 1 , one of the substituents is preferably a ballast group, and in Cp 2 , it is substituted so that the molecular weight is 700 or less, more preferably 500 or less in order to enhance the diffusibility of the dye formed. It is preferred that a group is selected.
ポジ型の色素供与物質としては、例えば下記一般式(1
6)で表わされる酸化性色素放出化合物がある。As the positive type dye-donating substance, for example, the following general formula (1
There are oxidizing dye-releasing compounds represented by 6).
一般式(16) 式中、W1はキノン環(この環上に置換基を有していても
良い)を形成するのに必要な原子の集まりを表わし、R5
はアルキル基又は水素原子を表わし、Eは (式中R6はアルキル基又は水素原子を表わし、R7は酸素
原子又は を表わす。)又は−SO2−を表わし、rは0又は1を表
わし、Dyeは一般式(1)で定義されたものと同義であ
る。この化合物の具体例は特開昭59−166954号、同59−
154445号等の明細書に記載されており、例えば以下の化
合物がある。General formula (16) In the formula, W 1 represents a group of atoms necessary for forming a quinone ring (which may have a substituent on this ring), and R 5
Represents an alkyl group or a hydrogen atom, and E represents (In the formula, R 6 represents an alkyl group or a hydrogen atom, and R 7 represents an oxygen atom or Represents ) Or —SO 2 —, r represents 0 or 1, and Dye has the same meaning as defined in formula (1). Specific examples of this compound are disclosed in JP-A-59-166954 and JP-A-59-166954.
No. 154445 and the like, and examples thereof include the following compounds.
別のポジ型色素供与物質としては、下記一般式(17)で
表わされる化合物で代表される酸化されると色素放出能
力を失う化合物がある。 Another positive dye-donating substance is a compound represented by the following general formula (17), which loses its dye releasing ability when oxidized.
一般式(17) 式中W2はベンゼン環(環上に置換基を有していても良
い)を形成するのに必要な原子の集まりを表わし、R5、
E、Dyeは一般式(16)で定義されたものと同義であ
る。この化合物の具体例は特開昭59−124329号、同59−
154445号等の明細書に記載されており、例えば以下の化
合物がある。General formula (17) In the formula, W 2 represents a group of atoms necessary for forming a benzene ring (which may have a substituent on the ring), R 5 ,
E and Dye have the same meaning as defined by the general formula (16). Specific examples of this compound are disclosed in JP-A-59-124329 and 59-124.
No. 154445 and the like, and examples thereof include the following compounds.
さらに別のポジ型色素供与物質としては、下記一般式
(18)で表わされる化合物が挙げられる。 Still another positive type dye-providing substance is a compound represented by the following general formula (18).
一般式(18) 上式において、W2、R5、Dyeは一般式(17)において定
義されたものと同義である。この化合物の具体例は特開
昭59−154445号等に記載されており、例えば以下の化合
物がある。General formula (18) In the above formula, W 2 , R 5 and Dye have the same meanings as defined in the general formula (17). Specific examples of this compound are described in JP-A-59-154445 and the like, for example, the following compounds.
上述の一般式(1)、(2)、(3)、(16)、(17)
及び(18)においてDyeで表わされる拡散性色素の残基
についてさらに詳述する。拡散性色素の残基としては、
色素の拡散性の為に分子量が800以下、より好ましくは6
00以下であることが好ましく、アゾ色素、アゾメチン色
素、アントラキノン色素、ナフトキノン色素、スチリル
色素、ニトロ色素、キノリン色素、カルボニル色素、フ
タロシアニン色素等の残基が挙げられる。これらの色素
残基は、熱現像時或いは転写時に複色可能な一時短波化
された形でもよい。また、これらの色素残基は画像の耐
光性を上げる目的で、例えば特開昭59-48765号、同59-1
24337号公報に記載されているキレート可能な色素残基
も好ましい一形態である。 The above general formulas (1), (2), (3), (16), (17)
Further, the residue of the diffusible dye represented by Dye in (18) will be described in more detail. As the residue of the diffusible dye,
Due to the diffusibility of the dye, the molecular weight is 800 or less, more preferably 6
It is preferably 00 or less, and examples thereof include residues of azo dyes, azomethine dyes, anthraquinone dyes, naphthoquinone dyes, styryl dyes, nitro dyes, quinoline dyes, carbonyl dyes, phthalocyanine dyes and the like. These dye residues may be in the form of a temporary short-wave that allows multiple colors during heat development or transfer. Further, these dye residues are used for the purpose of improving the light resistance of an image, for example, JP-A-59-48765 and 59-1.
The chelatable dye residue described in JP 24337 is also a preferred form.
これらの色素供与物質は単独で用いてもよいし、2つ以
上併用してもよい。その使用量は限定的でなく、色素供
与物質の種類、単用かまたは2種以上の併用使用か、或
いは本発明の熱現像感光材料の感光層が単層かまたは2
層以上の重層か等に応じて決定すればよいが、例えばそ
の使用量は1m2当たり0.005g〜50g、好ましくは0.1g〜1
0g用いることができる。These dye-providing substances may be used alone or in combination of two or more. The amount thereof is not limited, and may be one kind of dye-donating substance, one kind or a combination of two or more kinds, or a single photosensitive layer of the photothermographic material of the present invention.
It may be determined according to the number of layers or more, but the amount used is, for example, 0.005 g to 50 g, preferably 0.1 g to 1 g per m 2.
0g can be used.
色素供与物質を熱現像感光材料の感光層に含有せしめる
方法は任意であり、例えば低沸点溶媒(メタノール、エ
タノール、酢酸エチル等)または高沸点溶媒(ジブチル
フタレート、ジオクチルフタレート、トリクレジルホス
フェート等)に溶解した後、超音波分散するか、あるい
はアルカリ水溶液(例えば、水酸化ナトリウム10%水溶
液等)に溶解した後、鉱酸(例えば、塩酸または硝酸
等)にて中和して用いるか、あるいは適当なポリマーの
水溶液(例えば、ゼラチン、ポリビニルブチラール、ポ
リビニルピロリドン等)と共にボールミルを用いて分散
させた後、使用することができる。The method of incorporating the dye-donor substance into the photosensitive layer of the photothermographic material is arbitrary, and examples include low-boiling point solvents (methanol, ethanol, ethyl acetate, etc.) or high-boiling point solvents (dibutyl phthalate, dioctyl phthalate, tricresyl phosphate, etc.). Or ultrasonically dispersed or dissolved in an alkaline aqueous solution (for example, 10% sodium hydroxide aqueous solution) and then neutralized with a mineral acid (for example, hydrochloric acid or nitric acid), or It can be used after being dispersed with a suitable polymer aqueous solution (eg, gelatin, polyvinyl butyral, polyvinyl pyrrolidone, etc.) using a ball mill.
本発明の熱現像感光材料には、上記の色素供与物質と共
に感光性ハロゲン化銀を含有する。The heat-developable light-sensitive material of the present invention contains a light-sensitive silver halide together with the above-mentioned dye-providing substance.
本発明に用いられる感光性ハロゲン化銀としては、塩化
銀、臭化銀、沃化銀、塩臭化銀、塩沃化銀、沃臭化銀、
塩沃臭化銀等があげられる。該感光性ハロゲン化銀は、
写真技術分野のシングルジェット法やダブルジェット法
等の任意の方法で調製することができるが、本発明に於
いては、通常のハロゲン化銀ゼラチン乳剤の調製方法に
従って調製した感光性ハロゲン化銀を含む感光性ハロゲ
ン化銀乳剤が好ましい結果を与える。The photosensitive silver halide used in the present invention includes silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide,
Examples thereof include silver chloroiodobromide. The photosensitive silver halide is
Although it can be prepared by any method such as a single jet method and a double jet method in the field of photographic technology, in the present invention, a photosensitive silver halide prepared according to a usual method for preparing a silver halide gelatin emulsion is used. A light-sensitive silver halide emulsion containing the same gives favorable results.
該感光性ハロゲン化銀乳剤は、写真技術分野の任意の方
法で化学的に増感しても良い。かかる増感法としては、
金増感、イオウ増感、金−イオウ増感、還元増感等各種
の方法があげられる。The photosensitive silver halide emulsion may be chemically sensitized by any method in the photographic art. As such a sensitizing method,
Various methods such as gold sensitization, sulfur sensitization, gold-sulfur sensitization and reduction sensitization can be used.
上記感光性乳剤中のハロゲン化銀は、粗粒子であっても
微粒子であっても良いが、好ましい粒子サイズは、その
径が約0.001μm〜約1.5μmであり、さらに好ましくは
約0.01μm〜約0.5μmである。The silver halide in the above light-sensitive emulsion may be coarse particles or fine particles, but the preferable grain size is about 0.001 μm to about 1.5 μm, and more preferably about 0.01 μm to about 0.01 μm. It is about 0.5 μm.
上記のように調製された感光性ハロゲン化銀乳剤を本発
明の熱現像感光材料の構成層である熱現像性感光層に最
も好ましく適用することができる。The light-sensitive silver halide emulsion prepared as described above can be most preferably applied to the heat-developable light-sensitive layer which is a constituent layer of the heat-developable light-sensitive material of the present invention.
本発明において、他の感光性ハロゲン化銀の調製法とし
て、感光性銀塩形成成分を後述する有機銀塩と共存さ
せ、有機銀塩の一部に感光性ハロゲン化銀を形成させる
こともできる。この調製法に用いられる感光性銀塩形成
成分としては、無機ハロゲン化物、例えば、MXnで表わ
されるハロゲン化物(ここで、MはH原子、NH4基また
は金属原子を表わし、XはCl、BrまたはIを表わし、n
はMがH原子、NH4基の時は1、Mが金属原子の時はそ
の原子価を示す。金属原子としては、リチウム、ナトリ
ウム、カリウム、ルビジウム、セシウム、銅、金、ベリ
リウム、、マグネシウム、カルシウム、ストロンチウ
ム、バリウム、亜鉛、カドミウム、水銀、アルミニウ
ム、インジウム、ランタン、ルテニウム、タリウム、ゲ
ルマニウム、錫、鉛、アンチモン、ビスマス、クロム、
モリブデン、タングステン、マンガン、レニウム、鉄、
コバルト、ニッケル、ロジウム、パラジウム、オスミウ
ム、イリジウム、白金、セリウム等があげられる。)、
含ハロゲン金属錯体(例えば、,K2PtCl6,K2PtBr6,HA
uCl4,(NH4)2IrCl6,(NH4)3IrCl6,(NH4)2RuCl6,(NH4)
3RuCl6,(NH4)3RhCl6,(NH4)3RuBr6等)、オニウムハラ
イド(例えば、テトラメチルアンモニウムブロマイド、
トリメチルフェニルアンモニウムブロマイド、セチルエ
チルジメチルアンモニウムブロマイド、3−メチルチア
ゾリウムブロマイド、トリメチルベンジルアンモニウム
ブロマイドのような4級アンモニウムハライド、テトラ
エチルフォスフォニウムブロマイドのような4級フォス
フォニウムハライド、ベンジルエチルメチルスルホニウ
ムブロマイド、1−エチルチアゾリウムブロマイドのよ
うな3級スルホニウムハライド等)、ハロゲン化炭化水
素(例えば、ヨードホルム、ブロモホルム、四臭化炭
素、2−ブロモ−2−メチルプロパン等)、N−ハロゲ
ン化合物(N−クロロコハク酸イミド、N−ブロモコハ
ク酸イミド、N−ブロモフタル酸イミド、N−ブロモア
セトアミド、N−ヨードコハク酸イミド、N−ブロモフ
タラジノン、N−クロロフタラジノン、N−ブロモアセ
トアニリド、N,N−ジブロモベンゼンスルホンアミド、
N−ブロモ−N−メチルベンゼンスルホンアミド、1,3
−ジブロモ−4,4−ジメチルヒダントイン等)、その他
の含ハロゲン化合物(例えば塩化トリフェニルメチル、
臭化トリフェニルメチル、2−ブロモ酪酸、2−ブロモ
エタノール等)などをあげることができる。In the present invention, as another method for preparing photosensitive silver halide, a photosensitive silver salt-forming component may be allowed to coexist with an organic silver salt described below to form photosensitive silver halide on a part of the organic silver salt. . As the photosensitive silver salt forming component used in this preparation method, an inorganic halide, for example, a halide represented by MXn (wherein M represents an H atom, an NH 4 group or a metal atom, and X represents Cl, Br Or I, n
Indicates 1 when M is an H atom or an NH 4 group, and its valence when M is a metal atom. As the metal atom, lithium, sodium, potassium, rubidium, cesium, copper, gold, beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, mercury, aluminum, indium, lanthanum, ruthenium, thallium, germanium, tin, Lead, antimony, bismuth, chrome,
Molybdenum, tungsten, manganese, rhenium, iron,
Examples thereof include cobalt, nickel, rhodium, palladium, osmium, iridium, platinum and cerium. ),
Halogen-containing metal complex (eg, K 2 PtCl 6 , K 2 PtBr 6 , HA
uCl 4, (NH 4) 2 IrCl 6, (NH 4) 3 IrCl 6, (NH 4) 2 RuCl 6, (NH 4)
3 RuCl 6 , (NH 4 ) 3 RhCl 6 , (NH 4 ) 3 RuBr 6, etc.), onium halides (eg, tetramethylammonium bromide,
Quaternary ammonium halides such as trimethylphenylammonium bromide, cetylethyldimethylammonium bromide, 3-methylthiazolium bromide, trimethylbenzylammonium bromide, quaternary phosphonium halides such as tetraethylphosphonium bromide, benzylethylmethylsulfonium Bromide, tertiary sulfonium halides such as 1-ethylthiazolium bromide), halogenated hydrocarbons (eg, iodoform, bromoform, carbon tetrabromide, 2-bromo-2-methylpropane, etc.), N-halogen compounds (N-chlorosuccinimide, N-bromosuccinimide, N-bromophthalimide, N-bromoacetamide, N-iodosuccinimide, N-bromophthalazinone, N-ku Rofutarajinon, N- bromo acetanilide, N, N- dibromo benzenesulfonamide,
N-bromo-N-methylbenzenesulfonamide, 1,3
-Dibromo-4,4-dimethylhydantoin, etc.), other halogen-containing compounds (for example, triphenylmethyl chloride,
Triphenylmethyl bromide, 2-bromobutyric acid, 2-bromoethanol, etc.) and the like.
これら感光性ハロゲン化銀および感光性銀塩形成成分
は、種々の方法において組合せて使用でき、使用量は、
一層当り1m2に対して、0.001g〜50gであることが好ま
しく、より好ましくは、0.1g〜10gである。These photosensitive silver halide and photosensitive silver salt-forming component can be used in combination in various methods, and the amount used is
It is preferably 0.001 g to 50 g, and more preferably 0.1 g to 10 g per 1 m 2 per layer.
本発明の熱現像感光材料は、青色光、緑色光、赤色光に
感光性を有する各層、即ち熱現像青感光性層、熱現像緑
感光性層、熱現像赤感光性層として多層構成とすること
もできる。また、同色感光性層を2層以上(例えば、高
感度層と低感度層)に分割して設けることもできる。The photothermographic material of the present invention has a multi-layered structure as each layer having photosensitivity to blue light, green light and red light, that is, a photothermographic blue photosensitive layer, a photothermographic green photosensitive layer and a photothermographic red photosensitive layer. You can also Further, the photosensitive layer of the same color may be divided into two or more layers (for example, a high sensitivity layer and a low sensitivity layer).
上記の場合、各々用いられる青感光性ハロゲン化銀乳
剤、緑感光性ハロゲン化銀乳剤、赤感光性ハロゲン化銀
乳剤は、前記ハロゲン化銀乳剤に各種の分光増感色素を
加えることによって得ることができる。In the above case, the blue-sensitive silver halide emulsion, green-sensitive silver halide emulsion and red-sensitive silver halide emulsion used in each case are obtained by adding various spectral sensitizing dyes to the silver halide emulsion. You can
本発明に用いられる代表的な分光増感色素としては、例
えばシアニン、メロシアニン、コンプレックス(3核又
は4核の)シアニン、ホロボーラーシアニン、スチリ
ル、ヘミシアニン、オキソノール等があげられる。シア
ニン類の色素のうちでチアゾリン、オキサゾリン、ピロ
リン、ピリジン、オキサゾール、チアゾール、セレナゾ
ール、イミダゾールの様な塩基性核を有するものが、よ
り好ましい。この様な核にはアルキル基、アルキレン
基、ヒドロキシアルキル基、スルホアルキル基、カルボ
キシアルキル基、アミノアルキル基または縮合炭素環式
または複素環色環を作る事の出来るエナミン基を有して
いてもよい。また対称形でも非対称形でもよく、またメ
チン鎖、ポリメチン鎖にアルキル基、フェニル基、エナ
ミン基、ヘテロ環置換基を有していてもよい。Representative spectral sensitizing dyes used in the present invention include, for example, cyanine, merocyanine, complex (trinuclear or tetranuclear) cyanine, holobora cyanine, styryl, hemicyanine, oxonol and the like. Among the cyanine dyes, those having a basic nucleus such as thiazoline, oxazoline, pyrroline, pyridine, oxazole, thiazole, selenazole, and imidazole are more preferable. Such a nucleus may have an alkyl group, an alkylene group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, an aminoalkyl group or an enamine group capable of forming a condensed carbocyclic or heterocyclic ring. Good. Further, it may be symmetrical or asymmetrical, and the methine chain or polymethine chain may have an alkyl group, a phenyl group, an enamine group or a heterocyclic substituent.
メロシアニン色素は上記塩基性核の他に、例えばチオヒ
ダントイン核、ローダニン核、オキサゾツール酸核、チ
アゾリンチオン核、マロノニトリル核、ピラゾロン核の
様な酸性核を有していてもよい。これらの酸性核は更に
アルキル基、アルキレン基、フェニル基、カルボキシア
ルキル基、スルホアルキル基、ヒドロキシアルキル基、
アルコキシアルキル基、アルキルアミン基又はヘテロ環
式核で置換されていてもよい。又必要ならばこれらの色
素を組合わせて使用してもよい。更にアスコルビン酸誘
導体、アザインデンカドミウム塩、有機スルホン酸等、
例えば米国特許第2,933,390号、同第2,937,089号の明細
書等に記載されている様な可視光を吸収しない超増感性
添加剤を併用することができる。The merocyanine dye may have, in addition to the basic nucleus, an acidic nucleus such as a thiohydantoin nucleus, a rhodanine nucleus, an oxazotool acid nucleus, a thiazoline thione nucleus, a malononitrile nucleus, and a pyrazolone nucleus. These acidic nuclei are further alkyl group, alkylene group, phenyl group, carboxyalkyl group, sulfoalkyl group, hydroxyalkyl group,
It may be substituted with an alkoxyalkyl group, an alkylamine group or a heterocyclic nucleus. If necessary, these dyes may be used in combination. Furthermore, ascorbic acid derivatives, azaindene cadmium salts, organic sulfonic acids, etc.
For example, a supersensitizing additive which does not absorb visible light as described in the specifications of US Pat. Nos. 2,933,390 and 2,937,089 can be used in combination.
これら色素の添加量はハロゲン化銀またはハロゲン化銀
形成成分1モル当り1×10-4モル〜1モルである。更に
好ましくは、1×10-4モル〜1×10-1モルである。The addition amount of these dyes is 1 × 10 −4 to 1 mol per mol of silver halide or a silver halide-forming component. More preferably, it is 1 × 10 -4 mol to 1 × 10 -1 mol.
本発明の熱現像感光材料においては、必要に応じて感度
の上昇や現像性の向上を目的として各種の有機銀塩を用
いることができる。In the photothermographic material of the present invention, various organic silver salts can be used, if necessary, for the purpose of increasing sensitivity and improving developability.
本発明の熱現像感光材料に用いられる有機銀塩として
は、特公昭43-4921号、同44-26582号、同45-18416号、
同45-12700号、同45-22185号、特開昭49-52626号、同52
-31728号、同52-137321号、同52-141222号、同53-36224
号および同53-37610号等の各公報ならびに米国特許第3,
330,633号、同第3,794,496号、同第4,105,451号、同第
4,123,274号、同第4,168,980号等の各明細書中に記載さ
れているような脂肪族カルボン酸の銀塩、例えばラウリ
ン酸銀、ミリスチン酸銀、パルミチン酸銀、ステアリン
酸銀、アラキドン酸銀、ベヘン酸銀、α−(1−フェニ
ルテトラゾールチオ)酢酸銀など、芳香族カルボン酸
銀、例えば安息香酸銀、フタル酸銀など、特公昭44-265
82号、同45-12700号、同45-18416号、同45-22185号、特
開昭52-31728号、同52-137321号、特開昭58-118638号、
同58-118639号等の各公報に記載されているようなイミ
ノ基の銀塩、例えばベンゾトリアゾール銀、5−ニトロ
ベンゾトリアゾール銀、5−クロロベンゾトリアゾール
銀、5−メトキシベンゾトリアゾール銀、4−スルホベ
ンゾトリアゾール銀、4−ヒドロキシベンゾトリアゾー
ル銀、5−アミノベンゾトリアゾール銀、5−カルボキ
シベンゾトリアゾール銀、イミダゾール銀、ベンズイミ
ダゾール銀、6−ニトロベンズイミダゾール銀、ピラゾ
ール銀、ウラゾール銀、1,2,4−トリアゾール銀、1H−
テトラゾール銀、3−アミノ−5−ベンジルチオ−1,2,
4−トリアゾール銀、サッカリン銀、フタラジノン銀、
フタルイミド銀など、その他2−メルカプトベンゾオキ
サゾール銀、メルカプトオキサジアゾール銀、2−メル
カプトベンゾチアゾール銀、2−メルカプトベンズイミ
ダゾール銀、3−メルカプト−4−フェニル−1,2,4−
トリアゾール銀、4−ヒドロキシ−6−メチル−1,3,3
a,7−テトラザインデン銀および5−メチル−7−ヒド
ロキシ−1,2,3,4,6−ペンタザインデン銀などが挙げら
れる。以上の有機銀塩のうちでもイミノ基の銀塩が好ま
しく、特にベンゾトリアゾール誘導体の銀塩、より好ま
しくはスルホベンゾトリアゾール誘導体の銀塩が好まし
い。Examples of the organic silver salt used in the photothermographic material of the present invention include JP-B-43-4921, JP-B-44-26582, and JP-B-45-18416.
45-12700, 45-22185, JP-A-49-52626, 52
-31728, 52-137321, 52-141222, 53-36224
No. 53-37610 and other publications and U.S. Pat.
330,633, 3,794,496, 4,105,451, and
4,123,274, silver salts of aliphatic carboxylic acids as described in each specification such as 4,168,980, etc., for example, silver laurate, silver myristate, silver palmitate, silver stearate, silver arachidonate, behen. Acid silver, α- (1-phenyltetrazolethio) acetic acid silver, etc., aromatic carboxylic acid silver salts such as silver benzoate, silver phthalate, etc.
No. 82, No. 45-12700, No. 45-18416, No. 45-22185, JP-A-52-31728, JP-A-52-137321, JP-A-58-118638,
No. 58-118639 and the like, silver salts of imino groups such as silver benzotriazole, silver 5-nitrobenzotriazole, silver 5-chlorobenzotriazole, silver 5-methoxybenzotriazole, and 4- Sulfobenzotriazole silver, 4-hydroxybenzotriazole silver, 5-aminobenzotriazole silver, 5-carboxybenzotriazole silver, imidazole silver, benzimidazole silver, 6-nitrobenzimidazole silver, pyrazole silver, urazole silver, 1,2, 4-triazole silver, 1H-
Tetrazole silver, 3-amino-5-benzylthio-1,2,
4-triazole silver, saccharin silver, phthalazinone silver,
Others such as silver phthalimide, 2-mercaptobenzoxazole silver, mercaptooxadiazole silver, 2-mercaptobenzothiazole silver, 2-mercaptobenzimidazole silver, 3-mercapto-4-phenyl-1,2,4-
Triazole silver, 4-hydroxy-6-methyl-1,3,3
Examples thereof include a, 7-tetrazaindene silver and 5-methyl-7-hydroxy-1,2,3,4,6-pentazaindene silver. Among the above organic silver salts, the silver salt of imino group is preferable, the silver salt of benzotriazole derivative is more preferable, and the silver salt of sulfobenzotriazole derivative is more preferable.
本発明に用いられる有機銀塩は、単独でも或いは2種以
上併用して用いてもよく、単離したものを適当な手段に
よりバインダー中に分散して使用に供してもよいし、ま
た適当なバインダー中で銀塩を調製し、単離せずにその
まま使用に供してもよい。The organic silver salt used in the present invention may be used alone or in combination of two or more kinds, and the isolated silver salt may be dispersed in a binder by a suitable means before use. The silver salt may be prepared in a binder and used as it is without isolation.
該有機銀塩の使用量は、感光性ハロゲン化銀1モル当り
0.01〜500モルであることが好ましく、より好ましくは
0.1モル〜100モルである。The amount of the organic silver salt used is 1 mol of photosensitive silver halide.
It is preferably 0.01 to 500 mol, more preferably
It is 0.1 mol to 100 mol.
本発明の熱現像感光材料に用いられる還元剤は、熱現像
感光材料の分野で通常用いられるものを用いることがで
き、例えば米国特許第3,531,286号、同第3,761,270号、
同第3,764,328号各明細書、またリサーチ・ディスクロ
ージャーNo.12146、同No.15108、同No.15127および特開
昭56-27132号公報等に記載のp−フェニレンジアミン系
およびp−アミノフェノール系現像主薬、フォスフォロ
アミドフェノール系およびスルホンアミドフェノール系
現像主薬、またヒドラゾン系発色現像主薬が挙げられ
る。また、米国特許第3,342,599号、同第3,719,492号、
特開昭53-135628号、同54-79035号等に記載されている
発色現像主薬プレカーサー等も有利に用いることができ
る。The reducing agent used in the photothermographic material of the present invention, it is possible to use those usually used in the field of photothermographic material, for example, U.S. Patent No. 3,531,286, the same 3,761,270,
Nos. 3,764,328, Research Disclosure Nos. 12146, No. 15108, No. 15127, and p-phenylenediamine-based and p-aminophenol-based developments described in JP-A-56-27132. Examples include main agents, phosphoramidophenol-based and sulfonamidephenol-based developing agents, and hydrazone-based color developing agents. Also, U.S. Pat.Nos. 3,342,599 and 3,719,492,
The color developing agent precursors described in JP-A-53-135628 and JP-A-54-79035 can also be advantageously used.
特に好ましい還元剤として、特開昭56-146133号明細書
に記載されている下記一般式(19)で表わされる還元剤
が挙げられる。Particularly preferred reducing agents include reducing agents represented by the following general formula (19) described in JP-A-56-146133.
一般式(19) 式中、R8およびR9は水素原子、または置換基を有しても
よい炭素原子数1〜30(好ましくは1〜4)のアルキル
基を表わし、R8とR9とは閉環して複素環を形成してもよ
い。R10,R11R12およびR13は水素原子、ハロゲン原子、
ヒドロキシ基、アミノ基、アルコキシ基、アシルアミド
基、スルホンアミド基、アルキルスルホンアミド基また
は置換基を有してもよい炭素原子数1〜30(好ましくは
1〜4)のアルキル基を表わし、R10とR8およびR12とR9
はそれぞれ閉環して複素環を形成してもよい。Mはアル
カリ金属原子、アンモニウム基、含窒素有機塩基または
第4級窒素原子を含む化合物を表わす。General formula (19) In the formula, R 8 and R 9 represent a hydrogen atom or an alkyl group having 1 to 30 (preferably 1 to 4) carbon atoms which may have a substituent, and R 8 and R 9 are ring-closed. A heterocycle may be formed. R 10 , R 11 R 12 and R 13 are a hydrogen atom, a halogen atom,
R 10 represents a hydroxy group, an amino group, an alkoxy group, an acylamide group, a sulfonamide group, an alkylsulfonamide group or an optionally substituted alkyl group having 1 to 30 carbon atoms (preferably 1 to 4), and R 10 And R 8 and R 12 and R 9
May each be ring-closed to form a heterocycle. M represents a compound containing an alkali metal atom, an ammonium group, a nitrogen-containing organic base or a quaternary nitrogen atom.
上記一般式(19)における含窒素有機塩基とは無機酸と
塩を生成し得る塩基性を示す窒素原子を含む有機化合物
であり、特に重要な有機塩基としてはアミン化合物が挙
げられる。そして鎖状のアミン化合物としては第1級ア
ミン、第2級アミン、第3級アミンなどが、また環状の
アミン化合物としては典型的なヘテロ環式有機塩基の例
として著名なピリジン、キノリン、ピペリジン、イミダ
ゾール等が挙げられる。この他ヒドロキシルアミン、ヒ
ドラジン、アミジンなどの化合物も鎖状のアミンとして
有用である。また含窒素有機塩基の塩としては上記のよ
うな有機塩基の無機酸塩(例えば塩酸塩、硫酸塩、硝酸
塩等)が好ましく用いられる。The nitrogen-containing organic base in the above general formula (19) is an organic compound containing a nitrogen atom showing basicity capable of forming a salt with an inorganic acid, and particularly important organic bases include amine compounds. Primary amines, secondary amines, tertiary amines, and the like are used as chain amine compounds, and pyridine, quinoline, and piperidine, which are prominent examples of typical heterocyclic organic bases, are used as cyclic amine compounds. , Imidazole and the like. In addition, compounds such as hydroxylamine, hydrazine and amidine are also useful as chain amines. As the salt of the nitrogen-containing organic base, the inorganic acid salt of the above-mentioned organic base (for example, hydrochloride, sulfate, nitrate, etc.) is preferably used.
一方、上記一般式(19)における第4級窒素を含む化合
物としては、4価の共有結合を有する窒素化合物の塩ま
たは水酸化物等が挙げられる。On the other hand, examples of the compound containing a quaternary nitrogen in the general formula (19) include salts or hydroxides of nitrogen compounds having a tetravalent covalent bond.
上記一般式(19)で表わされる還元剤は、公知の方法、
例えばホイベン−ベイル(Houben−Weyl),メソデン・
デア・オルガニッシェン・ケミ(Methoden der Organis
chen Chemie),バンド(Band)XI/2, 645〜703頁に記
載されている方法に従って合成できる。The reducing agent represented by the general formula (19) can be produced by a known method,
For example, Houben-Weyl, Mesoden
Der Organischen Kemi (Methoden der Organis
Chen Chemie), Band XI / 2, pages 645 to 703.
その他以下に述べるような還元剤を用いることもでき
る。Other reducing agents such as those described below can also be used.
例えば、フェノール類(例えばp−フェニルフェノー
ル、p−メトキシフェノール、2,6−ジ−tert−ブチル
−p−クレゾール、N−メチル−p−アミノフェノール
等)、スルホンアミドフェノール類[例えば4−ベンゼ
ンスルホンアミドフェノール、2−ベンゼンスルホンア
ミドフェノール、2,6−ジクロロ−4−ベンゼンスルホ
ンアミドフェノール、2,6−ジブロモ−4−(p−トル
エンスルホンアミド)フェノール等]、またはポリヒド
ロキシベンゼン類(例えばハイドロキノン、tert−ブチ
ルハイドロキノン、2,6−ジメチルハイドロキノン、ク
ロロハイドロキノン、カルボキシハイドロキノン、カテ
コール、3−カルボキシカテコール等)、ナフトール類
(例えばα−ナフトール、β−ナフトール、4−アミノ
ナフトール、4−メトキシナフトール等)、ヒドロキシ
ビナフチル類およびメチレンビスナフトール類[例えば
1,1′−ジヒドロキシ−2,2′−ビナフチル、6,6′−ジ
ブロモ−2,2′−ジヒドロキシ−1,1′−ビナフチル、6,
6−ジニトロ−2,2′−ジヒドロキシ−1,1′−ビナフチ
ル、4,4′−ジメトキシ−1,1′−ジヒドロキシ−2,2′
−ビナフチル、ビス(2−ヒドロキシ−1−ナフチル)
メタン等]、メチレンビスフェノール類[例えば1,1−
ビス(2−ヒドロキシ−3,5−ジメチルフェニル)−3,
5,5−トリメチルヘキサン、1,1−ビス(2−ヒドロキシ
−3−tert−ブチル−5−メチルフェニル)メタン、1,
1−ビス(2−ヒドロキシ−3,5−ジ−tert−ブチルフェ
ニル)メタン、2,6−メチレンビス(2−ヒドロキシ−
3−tert−ブチル−5−メチルフェニル)−4−メチル
フェノール、α−フェニル−α,α−ビス(2−ヒドロ
キシ−3,5−ジ−tert−ブチルフェニル)メタン、α−
フェニル−α,α−ビス(2−ヒドロキシ−3−tert−
ブチル−5−メチルフェニル)メタン、1,1−ビス(2
−ヒドロキシ−3,5−ジメチルフェニル)−2−メチル
プロパン、1,1,5,5−テトラキス(2−ヒドロキシ−3,5
−ジメチルフェニル)−2,4−エチルペンタン、2,2−ビ
ス(4−ヒドロキシ−3,5−ジメチルフェニル)プロパ
ン、2,2−ビス(4−ヒドロキシ−3−メチル−5−ter
t−ブチルフェニル)プロパン、2,2−ビス(4−ヒドロ
キシ−3,5−ジ−tert−ブチルフェニル)プロパン
等]、アスコルビン酸類、3−ピラゾリドン類、ピラゾ
ロン類、ヒドラゾン類およびパラフェニレンジアミン類
が挙げられる。For example, phenols (for example, p-phenylphenol, p-methoxyphenol, 2,6-di-tert-butyl-p-cresol, N-methyl-p-aminophenol, etc.), sulfonamide phenols [for example, 4-benzene Sulfonamidophenol, 2-benzenesulfonamidophenol, 2,6-dichloro-4-benzenesulfonamidophenol, 2,6-dibromo-4- (p-toluenesulfonamido) phenol, etc.], or polyhydroxybenzenes (eg, Hydroquinone, tert-butylhydroquinone, 2,6-dimethylhydroquinone, chlorohydroquinone, carboxyhydroquinone, catechol, 3-carboxycatechol, etc., naphthols (for example, α-naphthol, β-naphthol, 4-aminonaphthol, 4-methoxynaphtho). Le etc.), hydroxy binaphthyls and methylene bis naphthols [e.g.
1,1'-dihydroxy-2,2'-binaphthyl, 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 6,
6-dinitro-2,2'-dihydroxy-1,1'-binaphthyl, 4,4'-dimethoxy-1,1'-dihydroxy-2,2 '
-Binaphthyl, bis (2-hydroxy-1-naphthyl)
Methane, etc.], methylenebisphenols [eg 1,1-
Bis (2-hydroxy-3,5-dimethylphenyl) -3,
5,5-trimethylhexane, 1,1-bis (2-hydroxy-3-tert-butyl-5-methylphenyl) methane, 1,
1-bis (2-hydroxy-3,5-di-tert-butylphenyl) methane, 2,6-methylenebis (2-hydroxy-
3-tert-butyl-5-methylphenyl) -4-methylphenol, α-phenyl-α, α-bis (2-hydroxy-3,5-di-tert-butylphenyl) methane, α-
Phenyl-α, α-bis (2-hydroxy-3-tert-
Butyl-5-methylphenyl) methane, 1,1-bis (2
-Hydroxy-3,5-dimethylphenyl) -2-methylpropane, 1,1,5,5-tetrakis (2-hydroxy-3,5
-Dimethylphenyl) -2,4-ethylpentane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3-methyl-5-ter
t-butylphenyl) propane, 2,2-bis (4-hydroxy-3,5-di-tert-butylphenyl) propane, etc.], ascorbic acids, 3-pyrazolidones, pyrazolones, hydrazones and paraphenylenediamines Is mentioned.
これら還元剤は単独、或いは2種以上組合せて用いるこ
ともできる。還元剤の使用量は、使用される感光性ハロ
ゲン化銀の種類、有機酸銀塩の種類およびその他の添加
剤の種類などに依存するが、通常は感光性ハロゲン化銀
1モルに対して0.01〜1500モルの範囲であり、好ましく
は0.1〜200モルである。These reducing agents may be used alone or in combination of two or more. The amount of the reducing agent used depends on the type of the photosensitive silver halide used, the type of the organic acid silver salt and the type of other additives, but is usually 0.01 per 1 mol of the photosensitive silver halide. The range is ˜1500 mol, preferably 0.1-200 mol.
本発明の熱現像感光材料に用いられる支持体としては、
例えばポリエチレンフィルム、セルロースアセテートフ
ィルムおよびポリエチレンテレフタレートフィルム、ポ
リ塩化ビニル等の合成プラスチックフィルム、並びに写
真用原紙、印刷用紙、バライタ紙およびレジンコート紙
等の紙支持体、並びに上記の合成プラスチックフィルム
に反射層を設けた支持体等が挙げられる。The support used in the photothermographic material of the present invention includes
For example, a polyethylene film, a cellulose acetate film and a polyethylene terephthalate film, a synthetic plastic film such as polyvinyl chloride, and a paper support such as photographic base paper, printing paper, baryta paper and resin coated paper, and a reflective layer on the above synthetic plastic film. And a support provided with.
本発明の熱現像感光材料には、上記各成分以外に必要に
応じ各種添加剤を添加することができる。例えば現像促
進剤としては、米国特許第3,220,840号、同第3,531,285
号、同第4,012,260号、同第4,060,420号、同第4,088,49
6号、同第4,207,392号各明細書、リサーチ・ディスクロ
ージャーNo.15733、同No.15734、同No.15776、特開昭56
-130745号、同56-132332号等に記載された尿素、グアニ
ジウムトリクロロアセテート等のアルカリ放出剤、特公
昭45-12700号記載の有機酸、米国特許第3,667,959号記
載の−CO−,−SO2−,−SO−基を有する非水性極性溶
媒化合物、米国特許第3,438,776号記載のメルトフォー
マー、米国特許第3,666,477号、特開昭51-19525号に記
載のポリアルキレングリコール類等がある。また色調剤
としては、例えば特開昭46-4928号、同46-6077号、同49
-5019号、同49-5020号、同49-91215号、同49-107727
号、同50-2524号、同50-67132号、同50-67641号、同50-
114217号、同52-33722号、同52-99813号、同53-1020
号、同53-55115号、同53-76020号、同53-125014号、同5
4-156523号、同54-156524号、同54-156525号、同54-156
526号、同55-4060号、同55-4061号、同55−32015号等の
公報ならびに西独特許第2,140,406号、同第2,147,063
号、同2,220,618号、米国特許第3,080,254号、同第3,84
7,612号、同第3,782,941号、同第3,994,732号、同第4,1
23,282号、同第4,201,582号等の各明細書に記載されて
いる化合物であるフタラジノン、フタルイミド、ピラゾ
ロン、キナゾリノン、N−ヒドロキシナフタルイミド、
ベンツオキサジン、ナフトオキサジンジオン、2,3−ジ
ヒドロ−フタラジンジオン、2,3−ジヒドロ−1,3−オキ
サジン−2,4−ジオン、オキシピリジン、アミノピリジ
ン、ヒドロキシキノリン、アミノキノリン、イソカルボ
スチリル、スルホンアミド、2H−1,3−ベンゾチアジン
−2,4−(3H)ジオン、ベンゾトリアジン、メルカプト
トリアゾール、ジメルカプトテトラザペンタレン、フタ
ル酸、ナフタル酸、フタルアミン酸等があり、これらの
1つまたは、それ以上とイミダゾール化合物との混合
物、またフタル酸、ナフタル酸等の酸または酸無水物の
少なくとも1つおよびフタラジン化合物の混合物、さら
には、フタラジンとマレイン酸、イタコン酸、キノリン
酸、ゲンチジン酸等の組合せ等を挙げることができる。
また、特開昭58-189628号、同58-193460号公報に記載さ
れた、3−アミノ−5−メルカプト−1,2,4−トリアゾ
ール類、3−アシルアミノ−5−メルカプト−1,2,4−
トリアゾール類も有効である。Various additives may be added to the photothermographic material of the present invention, if necessary, in addition to the above components. For example, as a development accelerator, U.S. Patent Nos. 3,220,840 and 3,531,285
No. 4,012,260, No. 4,060,420, No. 4,088,49
No. 6, No. 4,207,392 specifications, Research Disclosure No. 15733, No. 15734, No. 15776, JP-A-56
Urea described in No. 130745 and No. 56-132332, alkali releasing agents such as guanidinium trichloroacetate, organic acids described in JP-B-45-12700, -CO- described in U.S. Pat. No. 3,667,959. SO 2 -, - SO- non-aqueous polar solvent a compound having a group, U.S. Patent No. 3,438,776 No. described melt formers, U.S. Patent No. 3,666,477, polyalkylene glycols and the like is described in JP-a-51-19525 . Examples of color toning agents include JP-A-46-4928, JP-A-46-6077, and JP-A-46-6077.
-5019, 49-5020, 49-91215, 49-107727
No. 50, No. 50-2524, No. 50-67132, No. 50-67641, No. 50-
114217, 52-33722, 52-99813, 53-1020
No. 53, No. 53-55115, No. 53-76020, No. 53-125014, No. 5
4-156523, 54-156524, 54-156525, 54-156
No. 526, No. 55-4060, No. 55-4061, No. 55-32015, etc. and West German Patent No. 2,140,406, No. 2,147,063
No. 2,220,618, U.S. Pat.Nos. 3,080,254, 3,84
No. 7,612, No. 3,782,941, No. 3,994,732, No. 4,1
23,282, 4,201,582 and the like, which are compounds described in each specification, such as phthalazinone, phthalimide, pyrazolone, quinazolinone, N-hydroxynaphthalimide,
Benzoxazine, naphthoxazinedione, 2,3-dihydro-phthalazinedione, 2,3-dihydro-1,3-oxazine-2,4-dione, oxypyridine, aminopyridine, hydroxyquinoline, aminoquinoline, isocarbostyryl , Sulfonamide, 2H-1,3-benzothiazine-2,4- (3H) dione, benzotriazine, mercaptotriazole, dimercaptotetrazapentalene, phthalic acid, naphthalic acid, phthalamic acid, etc., one of these Alternatively, a mixture of more than one and an imidazole compound, a mixture of at least one of an acid or an acid anhydride such as phthalic acid and naphthalic acid, and a phthalazine compound, and further a mixture of phthalazine and maleic acid, itaconic acid, quinolinic acid, gentisic acid. And the like.
Further, 3-amino-5-mercapto-1,2,4-triazoles, 3-acylamino-5-mercapto-1,2, described in JP-A Nos. 58-189628 and 58-193460 are disclosed. 4-
Triazoles are also effective.
またさらに、カブリ防止剤としては、例えば、特公昭47
-11113号、特開昭49-90118号、同49-10724号、同49-976
13号、同50-101019号、同49-130720号、同50-123331
号、同51-47419号、同51-57435号、同51-78227号、同51
-104338号、同53-19825号、同53-20923号、同51-50725
号、同51-3223号、同51-42529号、同51-81124号、同54-
51821号、同55-93149号等の公報、ならびに英国特許第
1,455,271号、米国特許第3,885,968号、同第3,700,457
号、同第4,137,079号、同第4,138,265号、西独特許第2,
617,907号等の各明細書に記載されている化合物である
第2水銀塩、或いは酸化剤(例えば、N−ハロゲノアセ
トアミド、N−ハロゲノコハク酸イミド、過塩素酸およ
びその塩類、無機過酸化物、過硫酸塩等)、或いは、酸
およびその塩(例えば、スルフィン酸、ラウリン酸リチ
ウム、ロジン、ジテルペン類、チオスルホン酸等)、或
いはイオウ含有化合物(例えば、メルカプト化合物放出
性化合物、チオウラシル、ジスルフィド、イオウ単体、
メルカプト−1,2,4−トリアゾール、チアゾリンチオ
ン、ポリスルフィド化合物等)、その他、オキサゾリ
ン、1,2,4−トリアゾール、フタルイミド等の化合物が
挙げられる。さらに別のカブリ防止剤として特開昭59-1
11636号に記載されているチオール(好ましくはチオフ
ェノール化合物)化合物も有効である。Further, as the antifoggant, for example, Japanese Patent Publication No.
-11113, JP-A-49-90118, 49-10724, 49-976
No. 13, No. 50-101019, No. 49-130720, No. 50-123331
No. 51, No. 51-47419, No. 51-57435, No. 51-78227, No. 51
-104338, 53-19825, 53-20923, 51-50725
No. 51, No. 51-3223, No. 51-42529, No. 51-81124, No. 54-
Publications such as 51821 and 55-93149, as well as British Patent No.
1,455,271, U.S. Pat.Nos. 3,885,968, 3,700,457
No. 4,137,079, No. 4,138,265, West German Patent No. 2,
No. 617, 907, a mercuric salt which is a compound described in each specification, or an oxidizing agent (for example, N-halogenoacetamide, N-halogenosuccinimide, perchloric acid and salts thereof, inorganic peroxides, Persulfate, etc.), or acid and salts thereof (eg, sulfinic acid, lithium laurate, rosin, diterpenes, thiosulfonic acid, etc.), or sulfur-containing compounds (eg, mercapto compound-releasing compound, thiouracil, disulfide, sulfur) Single,
Mercapto-1,2,4-triazole, thiazoline thione, polysulfide compound and the like), and other compounds such as oxazoline, 1,2,4-triazole and phthalimide. As another antifoggant, JP-A-59-1
The thiol (preferably thiophenol compound) compounds described in 11636 are also effective.
また、他のカブリ防止剤として、特願昭59-56506号に記
載のハイドロキノン誘導体(例えば、ジ−t−オクチル
ハイドロキノン、ドデカニルハイドロキノン等)や特願
昭59-66380号に記載のハイドロキノン誘導体とベンゾト
リアゾール誘導体(例えば、4−スルホベンゾトリアゾ
ール、5−カルボキシベンゾトリアゾール等)との併用
が好ましく用いることができる。Other antifoggants include hydroquinone derivatives described in Japanese Patent Application No. 59-56506 (for example, di-t-octylhydroquinone, dodecanylhydroquinone, etc.) and hydroquinone derivatives described in Japanese Patent Application No. 59-66380. A combination with a benzotriazole derivative (for example, 4-sulfobenzotriazole, 5-carboxybenzotriazole, etc.) can be preferably used.
また安定剤として特に処理後のプリントアウト防止剤を
同時に用いてもよく、例えば特開昭48-45228号、同50-1
19624号、同50-120328号、同53-46020号公報等に記載の
ハロゲン化炭化水素類、具体的にはテトラブロモブタ
ン、トリブロモエタノール、2−ブロモ−2−トリルア
セトアミド、2−ブロモ−2−トリルスルホニルアセト
アミド、2−トリブロモメチルスルホニルベンゾチアゾ
ール、2,4−ビス(トリブロモメチル)−6−メチルト
リアジンなどがあげられる。In addition, a printout preventing agent after treatment may be used as a stabilizer at the same time, and examples thereof include JP-A-48-45228 and JP-A-50-1.
No. 19624, No. 50-120328, No. 53-46020 and the like halogenated hydrocarbons, specifically tetrabromobutane, tribromoethanol, 2-bromo-2-tolylacetamide, 2-bromo- 2-tolylsulfonylacetamide, 2-tribromomethylsulfonylbenzothiazole, 2,4-bis (tribromomethyl) -6-methyltriazine and the like can be mentioned.
特に本発明の熱現像感光材料には各種の熱溶剤が添加さ
れることが好ましい。この熱溶剤とは熱現像および/ま
たは熱転写を促進する物質であればよく、好ましくは常
温下では固体、半固体又は液体(好ましくは、常圧にお
いて沸点100℃以上、より好ましくは150℃以上)であっ
て加熱することによってバインダー中で溶解又は溶融す
る物質であって、好ましくは尿素誘導体(例えば、ジメ
チルウレア、ジエチルウレア、フェニルウレア等)、ア
ミド誘導体(例えば、アセトアミド、ベンズアミド
等)、多価アルコール類(例えば、1,5−ペンタンジオ
ール、1,6−ペンタンジオール、1,2−シクロヘキサンジ
オール、ペンタエリスリトール、トリメチロールエタン
等)、又はポリエチレングリコール類が挙げられる。詳
しい具体例としては、特願昭58-104249に記載されてい
る。これらの熱溶剤は単独でも二種以上併用して用いて
も良い。In particular, it is preferable to add various thermal solvents to the photothermographic material of the present invention. The hot solvent may be a substance that promotes heat development and / or heat transfer, and is preferably a solid, a semisolid or a liquid at room temperature (preferably a boiling point of 100 ° C. or higher at atmospheric pressure, more preferably 150 ° C. or higher). Which is a substance which dissolves or melts in a binder upon heating, and is preferably a urea derivative (eg, dimethylurea, diethylurea, phenylurea, etc.), an amide derivative (eg, acetamide, benzamide, etc.), polyvalent Examples thereof include alcohols (for example, 1,5-pentanediol, 1,6-pentanediol, 1,2-cyclohexanediol, pentaerythritol, trimethylolethane, etc.) and polyethylene glycols. A detailed specific example is described in Japanese Patent Application No. 58-104249. These hot solvents may be used alone or in combination of two or more.
また特公昭46-5393号、特開昭50-54329号、同50-77034
号各公報記載のように含イオウ化合物を用いて後処理を
行なってもよい。Also, Japanese Patent Publication No. 46-5393, Japanese Patent Laid-Open Nos. 50-54329 and 50-77034.
Post-treatment may be carried out using a sulfur-containing compound as described in each publication.
さらには、米国特許第3,301,678号、同第3,506,444号、
同第3,824,103号、同第3,844,788号各明細書に記載のイ
ソチウロニウム系スタビライザープレカーサー、また米
国特許第3,669,670号、同第4,012,260号、同第4,060,42
0号明細書等に記載されたアクチベータースタビライザ
ープレカーサー等を含有してもよい。Furthermore, U.S. Pat.Nos. 3,301,678 and 3,506,444,
No. 3,824,103, No. 3,844,788 isothiuronium-based stabilizer precursor described in each specification, also U.S. Patent No. 3,669,670, No. 4,012,260, No. 4,060,42
The activator stabilizer precursor described in the specification No. 0 and the like may be contained.
また、ショ糖、NH4Fe(SO2)2・12H2O等の水放出剤を用い
てもよく、さらにまた、特開昭56-132332号のように水
を供給し熱現像を行なってもよい。Further, a water-releasing agent such as sucrose, NH 4 Fe (SO 2 ) 2 · 12H 2 O may be used, and further, as described in JP-A-56-132332, water is supplied for thermal development. Good.
本発明の熱現像感光材料には、さらに上記成分以外に必
要に応じて、分光増感染料、ハレーション防止染料、蛍
光増白剤、硬膜剤、帯電防止剤、可塑剤、延展剤等各種
の添加剤、塗布助剤等が添加される。In addition to the above components, the photothermographic material of the present invention may further contain various agents such as spectral sensitizing dyes, antihalation dyes, optical brighteners, hardeners, antistatic agents, plasticizers, and spreaders. Additives, coating aids, etc. are added.
本発明の熱現像感光材料は、基本的には同一層中に
(1)感光性ハロゲン化銀、(2)還元剤、(3)色素
供与物質、(4)バインダーを含有し、さらに必要に応
じて(5)有機銀塩を含有することが好ましい。The photothermographic material of the present invention basically contains (1) a photosensitive silver halide, (2) a reducing agent, (3) a dye-providing substance, and (4) a binder in the same layer, and further, if necessary. Accordingly, it is preferable to contain (5) an organic silver salt.
しかし、これらは必ずしも単一の感光層中に含有させる
必要はなく、例えば、感光層を2層に分け、前記
(1)、(2)、(4)、(5)の成分を一方側の感光
層に含有させ、この感光層に隣接する他方側の層に色素
供与物質(3)を含有せしめる等、相互に反応可能な状
態であれば2以上の感光層に分けて含有せしめてもよ
い。However, these do not necessarily have to be contained in a single photosensitive layer. For example, the photosensitive layer is divided into two layers, and the components (1), (2), (4), and (5) are contained on one side. It may be contained in two or more photosensitive layers as long as they can react with each other, such as being contained in the photosensitive layer and containing the dye-donor substance (3) in the layer on the other side adjacent to the photosensitive layer. .
また、感光層を例えば、高感度層と低感度層等の2層以
上に分割して設けてもよく、さらに他の感色性を異にす
る1または2以上の感光層を有してもよいし、またさら
に保護膜層、下塗層、バッキング層、中間層、或いはフ
ィルター層等各種の構成層を有していてもよい。In addition, the photosensitive layer may be divided into two or more layers such as a high-sensitivity layer and a low-sensitivity layer, and may have one or more photosensitive layers having different color sensitivities. Further, it may further have various constituent layers such as a protective film layer, an undercoat layer, a backing layer, an intermediate layer, or a filter layer.
熱現像感光層と同様、保護膜層、中間層、下塗層、バッ
キング層、その他の構成層についてもそれぞれの塗布液
を調製し、浸漬法、エアーナイフ法、カーテン塗布法ま
たは米国特許第3,681,294号に記載のホッパー塗布法等
の各種の塗布法により感光材料を作成することができ
る。Similar to the heat-developable photosensitive layer, a protective film layer, an intermediate layer, a subbing layer, a backing layer, each coating solution is prepared for other constituent layers, dipping method, air knife method, curtain coating method or U.S. Pat. The photosensitive material can be prepared by various coating methods such as the hopper coating method described in No.
更に必要ならば、米国特許第2,761,791号および英国特
許第837,095号に記載されている方法によって2層また
はそれ以上を同時に塗布することもできる。Furthermore, if desired, two or more layers can be coated simultaneously by the methods described in US Pat. No. 2,761,791 and British Patent No. 837,095.
本発明の熱現像感光材料の感光層に用いられる前記の成
分は、支持体上に塗布され、塗布の厚みは、乾燥後1〜
1,000μmが好ましく、より好ましくは3〜20μmであ
る。The above components used in the photosensitive layer of the photothermographic material of the present invention are coated on a support, and the thickness of coating is 1
The thickness is preferably 1,000 μm, more preferably 3 to 20 μm.
本発明の熱現像感光材料は、そのまま像様露光した後、
通常80℃〜200℃、好ましくは120℃〜170℃の温度範囲
で、1秒間〜180秒間、好ましくは1.5秒間〜120秒間加
熱されるだけで発色現像される。また、必要に応じて水
不透過性材料を密着せしめて現像してもよく、或いは露
光前に70℃〜180℃の温度範囲で予備加熱を施してもよ
い。The photothermographic material of the present invention is exposed imagewise as it is,
Usually, color development is carried out only by heating in the temperature range of 80 ° C. to 200 ° C., preferably 120 ° C. to 170 ° C. for 1 second to 180 seconds, preferably 1.5 seconds to 120 seconds. Further, if necessary, a water-impermeable material may be brought into close contact with the surface for development, or preheating may be carried out at a temperature range of 70 ° C. to 180 ° C. before exposure.
本発明の熱現像感光材料には、種々の露光手段を用いる
ことができる。潜像は可視光を含む輻射線の画像状露光
によって得られる。一般には通常のカラープリントに使
用される光源、例えばタングステンランプ、水銀灯、キ
セノンランプ、レーザー光線、CRT光線等を光源として
用うることができる。Various exposing means can be used for the photothermographic material of the present invention. The latent image is obtained by imagewise exposure to radiation containing visible light. Generally, a light source used for ordinary color printing, for example, a tungsten lamp, a mercury lamp, a xenon lamp, a laser beam, a CRT beam or the like can be used as the light source.
加熱手段は、通常の熱現像感光材料に適用し得る方法が
すべて利用でき、例えば加熱されたブロックないしプレ
ートに接触させたり、熱ローラーや熱ドラムに接触させ
たり、高温の雰囲気中を通過させたり、あるいは高周波
加熱を用いたり、さらには、本発明の感光材料中もしく
は熱転写用受像層(要素)中に導電性層を設け、通電や
強磁界によって生ずるジュール熱を利用することもでき
る。加熱パターンは特に制限されることはなく、あらか
じめ予熱(プレヒート)した後、再度加熱する方法をは
じめ、高温で短時間、あるいは低温で長時間、連続的に
上昇、下降あるいは繰りかえし、さらには不連続加熱も
可能ではあるが、簡便なパターンが好ましい。また露光
と加熱が同時に進行する方式であってもよい。As the heating means, all methods applicable to ordinary photothermographic materials can be used, for example, contact with a heated block or plate, contact with a heat roller or a heat drum, or passage through a high temperature atmosphere. Alternatively, high frequency heating may be used, or a conductive layer may be provided in the light-sensitive material of the present invention or in the image transfer layer (element) for thermal transfer, and Joule heat generated by energization or a strong magnetic field may be used. The heating pattern is not particularly limited, and it includes a method of preheating (preheating) in advance and then heating again, rising at a high temperature for a short time or at a low temperature for a long time, continuously rising, descending or repeating, and further discontinuous. Although heating is possible, a simple pattern is preferable. Further, it may be a system in which exposure and heating proceed simultaneously.
本発明の熱現像感光材料は、熱現像によって感光層に形
成された色素を受像層に転写してカラー画像を形成せし
める、いわゆる転写型の感光材料を包含し、また好まし
く適用することができる。The photothermographic material of the present invention includes a so-called transfer type photographic material in which a dye formed on the photographic layer by heat development is transferred to the image receiving layer to form a color image, and can be preferably applied.
熱現像受像層は、熱現像により放出乃至形成された色素
を受容する機能を有すればよく、色素拡散転写型感光材
料に用いられる媒染剤や特開昭57-207250号等に記載さ
れたガラス転移温度が40℃以上、250℃以下の耐熱性有
機高分子物質で形成されることが好ましい。The heat-developable image-receiving layer may have a function of receiving a dye released or formed by heat development, and may be a mordant used in a dye diffusion transfer type photosensitive material or a glass transition described in JP-A-57-207250. It is preferably formed of a heat resistant organic polymer substance having a temperature of 40 ° C. or higher and 250 ° C. or lower.
前記媒染剤の具体的な例としては、含窒素二級、三級ア
ミン類、含窒素複素環化合物、これらの四級カチオン性
化合物、米国特許第2,548,564号、同2,484,430号、同3,
148,061号、同3,756,814号に開示されているビニルピリ
ジンポリマーおよびビニルピリジニウムカチオンポリマ
ー、米国特許第2,675,316号に開示されているジアルキ
ルアミノ基を含むポリマー、米国特許第2,882,156号に
開示されているアミノグアニジン誘導体、特開昭54-137
333号に記載の共有結合性の反応性ポリマー、米国特許
第3,625,694号、同3,859,096号、英国特許第1,277,453
号、同2,011,012号に開示されているゼラチンなどと架
橋可能な媒染剤、米国特許第3,958,995号、同2,721,852
号、同2,798,063号に開示されている水性ゾル型媒染
剤、特開昭50-61228号に開示されている水不溶性媒染
剤、米国特許第3,788,855号、西独特許出願(OLS)第2,
843,320号、特開昭53-30328号、同52-155528号、同53-1
25号、同53-1024号、同54-74430号、同54-124726号、同
55-22766号、米国特許第3,642,482号、同3,488,706号、
同3,557,066号、同3,271,147号、同3,271,148号、特公
昭55-29418号、同56-36414号、同57-12139号、リサーチ
・ディスクロージャー12045(1974年)に開示されてい
る各種媒染剤をあげることができる。Specific examples of the mordant, nitrogen-containing secondary, tertiary amines, nitrogen-containing heterocyclic compounds, these quaternary cationic compounds, U.S. Patent Nos. 2,548,564, 2,484,430, 3,4,
Vinyl pyridine polymers and vinyl pyridinium cation polymers disclosed in 148,061 and 3,756,814, polymers containing dialkylamino groups disclosed in U.S. Pat.No. 2,675,316, aminoguanidine derivatives disclosed in U.S. Pat. , JP-A-54-137
Covalently bonded reactive polymers described in U.S. Pat. No. 3,625,694, U.S. Pat. No. 3,859,096, British Patent 1,277,453.
Nos. 2,011,012 and mordants capable of crosslinking with gelatin and the like, U.S. Patent Nos. 3,958,995 and 2,721,852
No. 2,798,063 aqueous sol type mordant disclosed in JP-A-50-61228, water-insoluble mordant disclosed in US Pat. No. 3,788,855, West German patent application (OLS) No. 2,
843, 320, JP-A-53-30328, 52-155528, 53-1
No. 25, No. 53-1024, No. 54-74430, No. 54-124726, No.
55-22766, U.S. Pat.Nos. 3,642,482, 3,488,706,
The various mordants disclosed in No. 3,557,066, No. 3,271,147, No. 3,271,148, Japanese Patent Publication Nos. 55-29418, 56-36414, 57-12139, Research Disclosure 12045 (1974) may be mentioned. it can.
特に有用な媒染剤はアンモニウム塩を含むポリマーで、
米国特許第3,709,690号に記載の四級アミノ基を含むポ
リマーである。アンモニウム塩を含むポリマーとして
は、例えばポリスチレン−コ−N,N,N−トリ−n−ヘキ
シル−N−ビニルベンジルアンモニウムクロライドで、
スチレンとビニルベンジルアンモニウムクロライドの比
率は、1:4〜4:1、好ましくは1:1である。Particularly useful mordants are polymers containing ammonium salts,
It is a polymer containing a quaternary amino group described in US Pat. No. 3,709,690. Examples of the polymer containing an ammonium salt include polystyrene-co-N, N, N-tri-n-hexyl-N-vinylbenzylammonium chloride,
The ratio of styrene to vinylbenzylammonium chloride is 1: 4 to 4: 1, preferably 1: 1.
典型的な色素拡散転写用の受像層はアンモニウム塩を含
むポリマーをゼラチンと混合して支持体上に塗布するこ
とにより得られる。A typical image receiving layer for dye diffusion transfer is obtained by mixing a polymer containing an ammonium salt with gelatin and coating the mixture on a support.
前記耐熱性有機高分子物質の例としては、分子量2,000
〜85,000のポリスチレン、炭素数4以下の置換基をもつ
ポリスチレン誘導体、ポリビニルシクロヘキサン、ポリ
ビニルベンゼン、ポリビニルピロリドン、ポリビニルカ
ルバゾル、ポリアリルベンゼン、ポリビニルアルコー
ル、ポリビニルホルマールおよびポリビニルブチラール
などのポリアセタール類、ポリ塩化ビニル、塩素化ポリ
エチレン、ポリ三塩化ふっ化エチレン、ポリアクリロニ
トリル、ポリ−N,N−ジメチルアクリルアミド、p−シ
アノフェニル基、ペンタクロロフェニル基および2,4−
ジクロロフェニル基をもつポリアクリレート、ポリアク
リルクロロアクリレート、ポリメチルメタクリレート、
ポリエチルメタクリレート、ポリプロピルメタクリレー
ト、ポリイソプロピルメタクリレート、ポリイソブチル
メタクリレート、ポリ−tert−ブチルメタクリレート、
ポリシクロヘキシルメタクリレート、ポリエチレングリ
コールジメタクリレート、ポリ−2−シアノ−エチルメ
タクリレート、ポリエチレンテレフタレートなどのポリ
エステル類、ポリスルホン、ビスフェノールAポリカー
ボネート等のポリカーボネート類、ポリアンヒドライ
ド、ポリアミド類並びにセルロースアセテート類等があ
げられる。また、Polymer Handbook 2nd ed.(J.Brandr
up,E.H.Immergut編)John Wiley&Sons出版、に記載さ
れているガラス転移温度40℃以上の合成ポリマーも有用
である。これらの高分子物質は、単独で用いられても、
また複数以上を組み合せて共重合体として用いてもよ
い。An example of the heat-resistant organic polymer substance has a molecular weight of 2,000.
~ 85,000 polystyrene, polystyrene derivatives having substituents with 4 or less carbon atoms, polyvinyl cyclohexane, polyvinyl benzene, polyvinyl pyrrolidone, polyvinyl carbazole, polyallyl benzene, polyvinyl alcohol, polyvinyl formal and polyvinyl butyral and other polyacetals, polyvinyl chloride , Chlorinated polyethylene, polytrifluoroethylene, polyacrylonitrile, poly-N, N-dimethylacrylamide, p-cyanophenyl group, pentachlorophenyl group and 2,4-
Polyacrylate with dichlorophenyl group, polyacrylchloroacrylate, polymethylmethacrylate,
Polyethylmethacrylate, polypropylmethacrylate, polyisopropylmethacrylate, polyisobutylmethacrylate, poly-tert-butylmethacrylate,
Examples thereof include polyesters such as polycyclohexyl methacrylate, polyethylene glycol dimethacrylate, poly-2-cyano-ethyl methacrylate and polyethylene terephthalate, polysulfones, polycarbonates such as bisphenol A polycarbonate, polyanhydrides, polyamides and cellulose acetates. Also, Polymer Handbook 2nd ed. (J. Brandr
Synthetic polymers having a glass transition temperature of 40 ° C. or higher described in John Wiley & Sons, published by up, EHImmergut) are also useful. These polymeric substances, even when used alone,
Further, a plurality of them may be combined and used as a copolymer.
特に有用なポリマーとしては、トリアセテート、ジアセ
テートなどのセルロースアセテート、ヘプタメチレンジ
アミンとテレフタル酸、フルオレンジプロピルアミンと
アジピン酸、ヘキサメチレンジアミンとジフェン酸、ヘ
キサメチレンジアミンとイソフタル酸などの組み合せに
よるポリアミド、ジエチレングリコールとジフェニルカ
ルボン酸、ビス−p−カルボキシフェノキシブタンとエ
チレングリコールなどの組み合せよるポリエステル、ポ
リエチレンテレフタレート、ポリカーボネート、塩化ビ
ニルがあげられる。これらのポリマーは改質されたもの
であってもよい。たとえば、シクロヘキサンジメタノー
ル、イソフタル酸、メトキシポリエチレン−グリコー
ル、1,2−ジカルボメトキシ−4−ベンゼンスルホン酸
などを改質剤として用いたポリエチレンテレフタレート
も有効である。これらのうち特に好ましくは、特願昭58
-97907号に記載のポリ塩化ビニルよりなる層及び特願昭
58-128600号に記載のポリカーボネートと可塑剤よりな
る層が挙げられる。Particularly useful polymers include cellulose acetates such as triacetate and diacetate, heptamethylenediamine and terephthalic acid, fluorenedipropylpropylamine and adipic acid, hexamethylenediamine and diphenic acid, and polyamides by a combination of hexamethylenediamine and isophthalic acid, Examples thereof include polyester, polyethylene terephthalate, polycarbonate, and vinyl chloride, which are combinations of diethylene glycol and diphenylcarboxylic acid, bis-p-carboxyphenoxybutane and ethylene glycol, and the like. These polymers may be modified. For example, polyethylene terephthalate using cyclohexanedimethanol, isophthalic acid, methoxypolyethylene glycol, 1,2-dicarbomethoxy-4-benzenesulfonic acid or the like as a modifier is also effective. Of these, Japanese Patent Application No. Sho 58 is particularly preferable.
-97907, layer made of polyvinyl chloride and Japanese Patent Application No.
A layer composed of the polycarbonate and the plasticizer described in 58-128600 can be mentioned.
上記のポリマーは適当な溶剤に溶かして支持体上に塗布
して受像層とするか、あるいは上記ポリマーより成るフ
ィルム状受像層を支持体にラミネートして用いられる
か、または支持体上に塗布することなく、上記ポリマー
より成る部材(例えばフィルム)単独で受像層を構成す
ること(受像層支持体兼用型)もできる。The above-mentioned polymer is dissolved in a suitable solvent and applied on a support to form an image-receiving layer, or a film-like image-receiving layer comprising the above-mentioned polymer is laminated on the support and used, or applied on the support. Alternatively, the member (for example, a film) made of the above polymer may be used alone to form the image receiving layer (also used as the image receiving layer support).
さらに受像層としては、透明支持体上の受像層の上にゼ
ラチン分散した二酸化チタン等を含む不透明化層(反射
性層)を設けて構成することもできる。この不透明化層
は、転写色画像を受像層の透明支持体側から見ることに
より反射型の色像が得られる。Further, the image receiving layer may be formed by providing an opaque layer (reflective layer) containing titanium dioxide dispersed in gelatin on the image receiving layer on a transparent support. With this opaque layer, a reflective color image can be obtained by viewing the transferred color image from the transparent support side of the image receiving layer.
[発明の具体的効果] 以上説明したように、本発明の熱現像感光材料はゼラチ
ン等との相溶性の優れた変性ポリビニルアルコール系重
合体を含有し、特に感光層のバインダーや必要に応じて
設けられる中間層、保護膜等に含有しているので、熱現
像性及び色素透過性が良好であり、転写型の場合には転
写ムラがなく、かつ製造時の塗布性にも優れている。[Specific effects of the invention] As described above, the photothermographic material of the present invention contains a modified polyvinyl alcohol-based polymer having excellent compatibility with gelatin and the like, and in particular, a binder of the photosensitive layer and, if necessary, Since it is contained in the provided intermediate layer, protective film, etc., it has good heat developability and dye permeability, and in the case of a transfer type, it has no transfer unevenness and is excellent in coatability during production.
感光層のバインダーを構成する、例えばゼラチンに変性
ポリビニルアルコール系重合体を含有した場合、特に熱
現像性及び色素透過性に優れ、さらにゼラチンとの相溶
性が良いため転写ムラも生じない。また、中間層を構成
する、例えばゼラチンに変性ポリビニルアルコール系重
合体を含有した場合には、特に色素透過性が良好であ
る。また保護膜を構成する、例えばゼラチンに変性ポリ
ビニルアルコール系重合体を含有した場合には、特に色
素透過性に優れ、さらにゼラチンとの相溶性が良いため
製造時に均一なべとつきの少ない膜を形成し、転写性も
良好である。When a modified polyvinyl alcohol-based polymer is contained in, for example, gelatin which constitutes the binder of the photosensitive layer, it is particularly excellent in heat developability and dye permeability and has good compatibility with gelatin, so that transfer unevenness does not occur. Further, when the modified polyvinyl alcohol-based polymer is contained in gelatin, which constitutes the intermediate layer, the dye permeability is particularly good. Further, when the protective film is formed, for example, when gelatin contains a modified polyvinyl alcohol-based polymer, it is particularly excellent in dye permeability and further has good compatibility with gelatin to form a uniform and non-sticky film during production. The transferability is also good.
[実施例] 以下、実施例により本発明をさらに具体的に説明する
が、本発明はこれらの態様に限定されない。[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these embodiments.
実施例−1 ベンゾトリアゾール銀22.7gにメチルアルコール400ml、
ポリビニルアルコール及び第1表に示した各種の水溶性
ポリマーそれぞれ8%水溶液500mlを加え、18時間ボー
ルミルにより分散した。次に、この分散液を攪拌しつつ
化学増感された沃臭化銀乳剤(沃化銀5モル%、乳剤1K
g中にゼラチン60g及び銀0.353モルを含む平均粒径0.05
μの立方体粒子)84mlを加えた。(ゼラチン約5.4g含
む) さらに3−アミノ−4−アリル−5−メルカプトトリア
ゾールの2%メタノール溶液9ml、アスコルビン酸8.9g
及び10%ゼラチン水溶液150mlを混合し、さらにD−キ
シリトール30gを加え、よく攪拌した。このようにして
調製した塗布液をバライタ紙上に塗布し、乾燥し、試料
1〜8を調製した。Example 1 22.7 g of benzotriazole silver and 400 ml of methyl alcohol,
Polyvinyl alcohol and each of the various water-soluble polymers shown in Table 1 were added with 500 ml of 8% aqueous solution and dispersed by a ball mill for 18 hours. Next, the silver iodobromide emulsion chemically sensitized while stirring this dispersion (5 mol% silver iodide, emulsion 1K)
An average particle size of 0.05 containing 60 g of gelatin and 0.353 mol of silver in 0.05 g
84 cubic particles). (Contains about 5.4 g of gelatin) 9 ml of 2% methanol solution of 3-amino-4-allyl-5-mercaptotriazole, 8.9 g of ascorbic acid
And 10 ml of 10% gelatin aqueous solution were mixed, 30 g of D-xylitol was further added, and the mixture was stirred well. The coating liquid thus prepared was applied onto baryta paper and dried to prepare samples 1 to 8.
次いで、それぞれの試料を130℃、20秒間ヒートブロッ
クで均一に加熱し、熱現像した。各試料の感度、最大濃
度(Dmax)、最小濃度(Dmin)を以下に示す。Then, each sample was uniformly heated in a heat block at 130 ° C. for 20 seconds and thermally developed. The sensitivity, maximum concentration (Dmax), and minimum concentration (Dmin) of each sample are shown below.
尚第1表に示した変性PVAは以下のようにして得られ
た。 The modified PVA shown in Table 1 was obtained as follows.
末端にメルカプト基を有するポリビニルアルコール(ケ
ン化度=98.7モル%、〔HS〕=1.46×10-5eq/g)100部
に蒸留水420部を加えて煮沸溶解した後、室温まで冷却
し、1N−H2SO4でpHを3.0に調製した。次いでアクリル酸
モノマー10部を加えて溶解し、チッ素置換した後70℃に
昇温して、蒸留水20部にK2S2O8 0.38部を溶解した開始
剤水溶液を添加して重合を開始した。3時間、70℃で攪
拌重合した後、室温まで冷却し、ポリビニルアルコール
−ポリアクリル酸ブロック共重合体水溶液を得た。pHを
5.5に調製し、濃度は17.3%であった。また20℃での粘
度は4500cpであった。このブロックの共重合体を変性PV
A(A)と表記する。After adding 420 parts of distilled water to 100 parts of polyvinyl alcohol having a mercapto group at the end (saponification degree = 98.7 mol%, [HS] = 1.46 × 10 −5 eq / g) and boiling to dissolve, cool to room temperature, pH was adjusted to 3.0 with 1N-H 2 SO 4. Then, 10 parts of acrylic acid monomer was added and dissolved, and after nitrogen substitution, the temperature was raised to 70 ° C., and an initiator aqueous solution in which 0.38 part of K 2 S 2 O 8 was dissolved in 20 parts of distilled water was added to carry out polymerization. Started. After stirring and polymerizing at 70 ° C. for 3 hours, the mixture was cooled to room temperature to obtain a polyvinyl alcohol-polyacrylic acid block copolymer aqueous solution. pH
Adjusted to 5.5, the concentration was 17.3%. The viscosity at 20 ° C was 4500 cp. Modified PV of this block copolymer
Notated as A (A).
以下同様の方法で変性PVA(B)〜(D)を調整した。
組成、濃度、pHを第2表にまとめて示す。The modified PVA (B) to (D) were prepared in the same manner as described below.
The composition, concentration and pH are summarized in Table 2.
第1表の結果から、本発明試料においては感度[本発明
試料6の感度を100とし相対感度(fog+0.1)を測定し
た。]及び最大濃度がともに高く、最小濃度は小さく、
本発明が熱現像性において良好な特性を有している事が
わかる。 From the results shown in Table 1, the sensitivity of the sample of the present invention [relative sensitivity (fog + 0.1) was measured by setting the sensitivity of sample 6 of the present invention to 100]. ] And the maximum density are both high, and the minimum density is low,
It can be seen that the present invention has good properties in heat developability.
実施例−2 ベンゾトリアゾール銀22.6gに1%ゼラチン水溶液400ml
を加え18時間ボールミルにより分散して、7.2%ゼラチ
ン水溶液を追加し、分散液を作製した。Example-2 400 ml of 1% gelatin aqueous solution to 22.6 g of benzotriazole silver
Was added and dispersed by a ball mill for 18 hours, and a 7.2% gelatin aqueous solution was added to prepare a dispersion liquid.
又同じベンゾトリアゾール銀22.6gにメタノール400ml、
8%ポリビニルアルコール(けん化度99.5%、粘度平均
重合度1750)水溶液500mlを加えボールミル分散し分散
液を作製した。それぞれに化学復感された沃臭化銀乳剤
(沃化銀4モル%、乳剤1kg中にゼラチン60g及び銀0.35
3モルを含む平均粒径0.1μmの立方体粒子)280mlを加
えた。The same benzotriazole silver 22.6g, methanol 400ml,
500 ml of an 8% polyvinyl alcohol (saponification degree 99.5%, viscosity average degree of polymerization 1750) aqueous solution was added, and ball mill dispersion was performed to prepare a dispersion liquid. Chemically resensitized silver iodobromide emulsions (4 mol% silver iodide, 60 g gelatin and 0.35 silver in 1 kg emulsion)
280 ml of cubic particles having an average particle size of 0.1 μm and containing 3 mol) were added.
さらにp−アミノ−N,N−ジエチルアニリン8.2g及びシ
アン色素形成カプラーとして下記カプラー(1)23.7g
をジ−n−ブチルフタレート10g酢酸エチル40mlに溶解
し5%アルカノールXC(デュポン社製、ジアルキルナフ
タレンスルホン酸ソーダ商品名)水溶液5ml及びゼラチ
ン5%水溶液100mlと混合し超音波分散したものを加え
た。さらに3−アミノ−4−アリル−5−メルカプトト
リアゾールの2%メタノール水溶液9ml、50gの3−メチ
ルペンタン−1,3,5−トリオール50gを加えてよく攪拌し
た。Further, 8.2 g of p-amino-N, N-diethylaniline and 23.7 g of the following coupler (1) as a cyan dye-forming coupler.
Was dissolved in 10 g of di-n-butyl phthalate and 40 ml of ethyl acetate, mixed with 5 ml of 5% alkanol XC (manufactured by DuPont, trade name of sodium dialkylnaphthalene sulfonate) and 100 ml of 5% gelatin aqueous solution, and ultrasonically dispersed. . Further, 9 ml of a 2% aqueous solution of 3-amino-4-allyl-5-mercaptotriazole in methanol and 50 g of 50 g of 3-methylpentane-1,3,5-triol were added and well stirred.
この様にして調製した塗布液をゼラチン下引(3μm乾
燥膜厚)をしたポリエチレンテレフタレートベース上に
塗布乾燥し試料9,10とした。又PVA(けん化度99.5%、
粘度平均重合度1750)を以下の様に他の水溶性ポリマー
に変えた試料11〜17を同様にして作製した。 The coating solution thus prepared was coated and dried on a polyethylene terephthalate base with gelatin subbing (3 μm dry film thickness) to obtain samples 9 and 10. Also PVA (saponification degree 99.5%,
Samples 11 to 17 in which the viscosity average degree of polymerization 1750) was changed to another water-soluble polymer as follows were prepared in the same manner.
試料No. 9ゼラチン 10 PVA117(クラレ製、けん化度98.5%、重合度1750) 11 PVA105(クラレ製、けん化度98.5%、重合度550) 12 PVA217(クラレ製、けん化度88.0%、重合度1700) 13 エスレックw−201(積水化学製、ブチラール化度1
1%、重合度650) 14 ポリビニルピロリドンk−30(東京化成製、重合度
40000) 15 変性PVA(A) 16 変性PVA(C) 17 変性PVA(D) 以上の試料はいずれも重量比でGel:水溶性ポリマー=2
2:40である。Sample No. 9 Gelatin 10 PVA117 (Kuraray, saponification degree 98.5%, degree of polymerization 1750) 11 PVA105 (Kuraray, saponification degree 98.5%, degree of polymerization 550) 12 PVA217 (Kuraray, saponification degree 88.0%, degree of polymerization 1700) 13 S-REC w-201 (manufactured by Sekisui Chemical, butyralization degree 1
1%, degree of polymerization 650) 14 Polyvinylpyrrolidone k-30 (Tokyo Kasei, degree of polymerization
40000) 15 Modified PVA (A) 16 Modified PVA (C) 17 Modified PVA (D) All of the above samples are Gel: Water-soluble polymer = 2 by weight ratio.
2:40.
又別に写真用バライタ紙にポリ塩化ビニルの5%テトラ
ヒドロフラン溶液を1m2あたりポリ塩化ビニルが1.20g
となる様に塗布し受像紙を作製した。Separately, on a photographic baryta paper, a 5% tetrahydrofuran solution of polyvinyl chloride was added to 1.20 g of polyvinyl chloride per 1 m 2.
To obtain an image-receiving paper.
試料9〜17をウェッジ露光した後受像紙と密着し150℃3
0秒間熱現像熱転写した。結果を第3表に示す。After exposing samples 9 to 17 with wedges, they were brought into close contact with the image receiving paper,
Thermal development and thermal transfer were carried out for 0 seconds. The results are shown in Table 3.
又これらの試料9〜17を28℃、相対湿度70%の条件下に
30分保存したところ、No.14の試料は特にベタつきがは
げしく、試料の重ね合わせが出来なかった。 In addition, these samples 9 to 17 under the conditions of 28 ℃, 70% relative humidity
After storing for 30 minutes, the sample No. 14 was particularly sticky and could not be overlaid.
第3表の結果から本発明は熱現像性、色素透過性及び転
写性において良好な特性を示していることがわかる。From the results shown in Table 3, it can be seen that the present invention exhibits favorable properties in heat developability, dye permeability and transferability.
実施例−3 実施例−2においてベンツトリアゾール銀をスルホベン
ツトリアゾール(Naの塩)銀32.8gに、又p−アミノ−
N,N−ジエチルアニリンをp−N,N−ジエチルアミノフェ
ニルスルファミン酸ソーダ17.3gに代えた他は実施例−
2と全く同様にして試料をつくり、同様に比較を行っ
た。結果を第4表に示す。Example-3 In Example-2, benztriazole silver was added to 32.8 g of sulfobenztriazole (Na salt) silver, and p-amino-
Example except that N, N-diethylaniline was replaced by 17.3 g of p-N, N-diethylaminophenylsulfamate sodium salt-
A sample was prepared in exactly the same manner as 2 and the same comparison was performed. The results are shown in Table 4.
実施例−2と同じ条件で全試料のベタつきをみたがNo.2
3は試料の重ね合わせが出来なかった。 No stickiness was observed in all samples under the same conditions as in Example-2.
No. 3 could not overlap the samples.
実施例−4 実施例−2と同じ9種の分散液を用いそれぞれに化学増
感された沃臭化銀乳剤(沃化銀4モル%、乳剤1kg中に
ゼラチン60g及び銀0.353モルを含む平均粒径0.1μmの
立方体粒子)280mlを加えた。Example-4 Silver iodobromide emulsions chemically sensitized using the same nine kinds of dispersions as in Example-2 (4 mol% of silver iodide, 60 g of gelatin and 0.353 mol of silver in 1 kg of emulsion) 280 ml of cubic particles having a particle size of 0.1 μm) were added.
さらに下記構造で表わされるマゼンタ色素供与物質
(1)53.7g、トリクレジルフォスフェート50g、酢酸エ
チル150mlを加え約60℃で加熱溶解させ均一な溶液とす
る。この溶液と5%アルカノールXC水溶液15ml及び5%
ゼラチン水溶液300mlと混合し超音波分散したものを加
えた。さらに下記化合物(1)の5%水溶液20ml及び下
記化合物(2)5.0gを加えてよく攪拌した。この様にし
て調製した塗布液をゼラチン下引(3μm膜厚)をした
ポリエチレンテレフタレートベース上に塗布乾燥し試料
27〜35とした。Further, 53.7 g of the magenta dye-donating substance (1) represented by the following structure, 50 g of tricresyl phosphate and 150 ml of ethyl acetate are added, and the mixture is heated and dissolved at about 60 ° C. to form a uniform solution. 15 ml of this solution and 5% alkanol XC aqueous solution and 5%
What was mixed with 300 ml of gelatin aqueous solution and ultrasonically dispersed was added. Further, 20 ml of a 5% aqueous solution of the following compound (1) and 5.0 g of the following compound (2) were added and well stirred. The coating solution thus prepared was coated on a polyethylene terephthalate base with a gelatin subbing (thickness of 3 μm) and dried to obtain a sample.
27 to 35.
化合物(2) H2N−SO2−N(CH3)2 又受像層としてポリ(アクリル酸メチル−コ−N,N,N−
トリメチル−N−ビニルベンジルアンモニウムクロライ
ド)(アクリル酸メチルとビニルベンジルアンモニウム
の比率は1:1)10gを200mlの水に溶解しゼラチン100gと
均一に混合した。この混合液を二酸化チタンを分散した
ポリエチレンテレフタレート上に90μのウェット膜厚で
均一に塗布した。この上にさらに以下の組成から成る2
層目の層を60μmのウェット膜厚となる様に均一に塗布
し乾燥させた。 Compound (2) H 2 N-SO 2 -N (CH 3 ) 2 or poly (methyl acrylate-co-N, N, N-) as an image receiving layer
10 g of trimethyl-N-vinylbenzylammonium chloride) (the ratio of methyl acrylate and vinylbenzylammonium was 1: 1) was dissolved in 200 ml of water and uniformly mixed with 100 g of gelatin. This mixed solution was uniformly applied on polyethylene terephthalate in which titanium dioxide was dispersed to a wet film thickness of 90 μm. On top of this, the following composition 2
The second layer was uniformly applied so as to have a wet film thickness of 60 μm and dried.
尿素 20g N−メチル尿素 20g 水 80ml グアニジニウムトリクロロ酢酸 4g ポリビニルアルコール(PVA117けん化度98%、平均重合
度1750)の10%水溶液 120ml エマルゲン908 5%水溶液 20ml ドデシルベンゼンスルホン酸ソーダ5%水溶液 5ml この試料を乾燥後受像材料として用いる。Urea 20g N-methylurea 20g Water 80ml Guanidinium trichloroacetic acid 4g Polyvinyl alcohol (PVA117 saponification degree 98%, average degree of polymerization 1750) 10% aqueous solution 120ml Emulgen 908 5% aqueous solution 20ml Sodium dodecylbenzenesulfonate 5% aqueous solution 5ml This After the sample is dried, it is used as an image receiving material.
上記感光材料No.27〜35をウェッジ露光後、受像材料と
重ね合わせ140℃で60秒間加熱した後受像材料を感光材
料からひきはがした。結果を第5表に示す。The above-mentioned light-sensitive materials No. 27 to 35 were exposed to wedges, then overlapped with the image-receiving material and heated at 140 ° C. for 60 seconds, and then the image-receiving material was peeled from the light-sensitive material. The results are shown in Table 5.
以上の様に本発明はDmaxの値が高い事がわかる。又実施
例1〜3と同じくNo.32の試料は特にベタつきがはげし
く試料の重ね合わせが出来なかった。 As described above, it can be seen that the present invention has a high Dmax value. As in Examples 1 to 3, the sample No. 32 was particularly sticky and could not be overlaid.
実施例−5 スルホベンツトリアゾール銀(Naの塩)32.8gにメタノ
ール400ml、8%ポリビニルピロリドン(K−30)水溶
液500mlを加え18時間ボールミルにより分散した。次に
この分散液を攪拌しつつ化学増感された沃臭化銀乳剤
(沃臭化銀4モル%、乳剤1kg中にゼラチン60g及び銀0.
353モルを含む平均粒径0.1μmの立方体粒子)280ml(G
el 17g)、さらにp−N,N−ジエチルアミノフェニルス
ルファミン酸ソーダ17.3gを加え、下記構造式で表わさ
れるカプラー(2)23.7gをn−ジオクチルフタレート1
0g、酢酸エチル60mlに溶解し、アルカノールB5%水溶液
5ml及びゼラチン5%水溶液100mlと混合し超音波分散し
たものを加えた。さらに3−アミノ−4−アリル−5−
メルカプトトリアゾールの2%メタノール溶液9ml、50g
の3−メチルペンタン−1,3,5−トリオール50gを加えて
よく攪拌した。この様にして調製した塗布液をゼラチン
下引(3g/m2の付量)をしたポリエチレンテレフタレー
トベース上に銀量が1g/m2になる様に塗布乾燥した。次
いでこの上に以下の組成から成る保護膜を乾燥時3g/m2
の塗布量となる様に塗布し試料No.36〜43を作製した。Example-5 To 32.8 g of silver sulfobenztriazole (Na salt), 400 ml of methanol and 500 ml of an 8% polyvinylpyrrolidone (K-30) aqueous solution were added and dispersed by a ball mill for 18 hours. Next, this dispersion was chemically sensitized while stirring the emulsion (4 mol% of silver iodobromide, 60 g of gelatin and 0.
280 ml of cubic particles with an average particle size of 0.1 μm containing 353 mol (G
el 17g), and p-N, N-diethylaminophenylsulfamate sodium salt 17.3g were added, and coupler (2) 23.7g represented by the following structural formula was added to n-dioctyl phthalate 1
0g, dissolved in 60 ml of ethyl acetate, alkanol B 5% aqueous solution
5 ml and 100 ml of 5% gelatin aqueous solution, mixed and ultrasonically dispersed, were added. Furthermore, 3-amino-4-allyl-5-
2% methanol solution of mercaptotriazole 9ml, 50g
50 g of 3-methylpentane-1,3,5-triol was added and stirred well. The coating solution thus prepared was coated and dried on a polyethylene terephthalate base having a gelatin subbing (coating amount of 3 g / m 2 ) so that the amount of silver was 1 g / m 2 . Then, a protective film having the following composition was dried on it at 3 g / m 2
Sample Nos. 36 to 43 were prepared by coating so that the coating amount becomes.
No.36は通常の感光材料と同じゼラチン保護膜、No.37〜
39は代表的な合成水溶性ポリマーを単独で保護膜として
用いたもの、又No.40〜43はゼラチンとこれらの代表的
水溶性ポリマーの混合物を保護膜として用いたものであ
る。No.37〜39はゼラチンを含まない塗布液であるので
塗布後にやや膜が流れ不均一になっており、これに対し
No.36,40,41,42及び43は均一に塗布されていた。 No.36 is the same gelatin protective film as normal photosensitive materials, No.37-
No. 39 uses a typical synthetic water-soluble polymer alone as a protective film, and Nos. 40 to 43 use gelatin and a mixture of these typical water-soluble polymers as a protective film. Nos. 37 to 39 are coating liquids that do not contain gelatin, so the film flows slightly after coating and becomes non-uniform.
Nos. 36, 40, 41, 42 and 43 were evenly applied.
又、写真用バライタ紙上にポリ塩化ビニル(n=1,10
0、和光純薬社製)をテトラヒドロフラン溶液として塗
布しポリ塩化ビニル層の乾燥膜厚が10μとなる様に受像
層をつくった。In addition, polyvinyl chloride (n = 1,10
0, manufactured by Wako Pure Chemical Industries, Ltd.) was applied as a tetrahydrofuran solution to form an image receiving layer so that the dry film thickness of the polyvinyl chloride layer would be 10 μm.
上記試料No.36〜43をそれぞれウェッジ露光後受像要素
と重ね150℃で30秒間均一に加熱し、剥離した。結果を
第6表に示す。Each of Sample Nos. 36 to 43 described above was overlapped with the image receiving element after wedge exposure, and uniformly heated at 150 ° C. for 30 seconds to be peeled off. The results are shown in Table 6.
又28℃、相対湿度70%の条件下に保存した時の感材表面
のベトつきを、○余りベトつかない、△ややベトつく、
×かなりベトついて感材を重ねられないにより評価し
た。以上の結果より本発明試料は塗布性にすぐれ、色素
の透過性にすぐれ、表面のベトつきも少く保護膜として
良好な性質を示す事がわかる。 Also, the stickiness of the surface of the photosensitive material when stored under conditions of 28 ° C. and 70% relative humidity is: ○ not very sticky, △ slightly sticky,
× It was evaluated as being extremely sticky and the photosensitive material could not be overlaid. From the above results, it is understood that the sample of the present invention has excellent coatability, excellent dye permeability, little surface tackiness, and good properties as a protective film.
実施例−6 実施例−5のカプラーの代りに下記構造式であらわされ
るカプラー(3)23.7g及びジ−オクチルフタレート10g
を用い、熱溶剤として50gの3−メチルペンタン−1,3,5
−トリオチルを用いたものをE、これに代えてD−キシ
リナールを用いたものをF、N,N′−ジメチルウレアを
用いたものをG、1,5−ペンタンジオールを用いたもの
をHとした。Example-6 Instead of the coupler of Example-5, 23.7 g of a coupler (3) represented by the following structural formula and 10 g of di-octyl phthalate were used.
50 g of 3-methylpentane-1,3,5 as a hot solvent
-The one using triotyl is E, the one using D-xylinal in place of it is F, the one using N, N'-dimethylurea is G, the one using 1,5-pentanediol is H. did.
この上にこの感光層と同じ組成比のバインダー及び熱溶
剤を塗布したものを試料E−1、F−1、G−1、H−
1とした。又、ポリビニルピロリドンの代りに変性PVA
(A)と(B)を用いたものをそれぞれE−2、E−
3、F−2、F−3、G−2、G−3、H−2、H−3
とした(バインダー塗布量3g/m2)。E−1、F−1、
G−1、H−1は28℃、70%相対湿度下で保存した状態
での膜のベトつきがひどくほとんど重ね合せの出来ない
程度であった。F−2〜H−2、F−3〜H−3はベト
つきがなく良好であった。これらの試料をそれぞれ露光
後、受像層と合わせ、実施例−5と同様に熱現像した。
結果を第7表に示す。 Samples E-1, F-1, G-1, and H- were prepared by applying a binder and a thermal solvent having the same composition ratio as that of the photosensitive layer on the sample.
It was set to 1. Also, modified PVA instead of polyvinylpyrrolidone
Those using (A) and (B) are E-2 and E-, respectively.
3, F-2, F-3, G-2, G-3, H-2, H-3
(Binder coating amount 3 g / m 2 ). E-1, F-1,
G-1 and H-1 were so sticky that they could not be superposed on each other when stored at 28 ° C. and 70% relative humidity. F-2 to H-2 and F-3 to H-3 were good without stickiness. After exposure of each of these samples, they were combined with the image-receiving layer and subjected to heat development in the same manner as in Example-5.
The results are shown in Table 7.
第 7 表 試料No. Dmax 備 考 E−1 1.68 比 較 F−1 1.28 〃 G−1 1.70 〃 H−1 1.60 〃 E−2 1.70 本発明 F−2 1.31 〃 G−2 1.68 〃 H−2 1.65 〃 E−3 1.65 〃 F−3 1.25 〃 G−3 1.66 〃 H−3 1.60 〃 試料E−1、F−1、G−1、H−1は濃度がでてはい
るが熱現像時の膜のこわれ(つぶれ)が大きく転写ムラ
が認められた。Table 7 Sample No. Dmax Remarks E-1 1.68 Comparison F-1 1.28 〃 G-1 1.70 〃 H-1 1.60 〃 E-2 1.70 Present invention F-2 1.31 〃 G-2 1.68 〃 H-2 1.65 〃 E-3 1.65 〃 F-3 1.25 〃 G-3 1.66 〃 H-3 1.60 〃 Samples E-1, F-1, G-1, and H-1 have high density but are films at the time of heat development Scratch (crush) was large and uneven transfer was observed.
保護膜組成 E−1,2,3 Gel/ポリマー/3−メチルペンタン−1,3,5−
トリオール =22/40/50 F−1,2,3 Gel/ポリマー/D−キシリトール =22/40/50 G−1,2,3 Gel/ポリマー/N,N′−ジメチルウレア =
〃 H−1,2,3 Gel/ポリマー/1,5−ペンタンジオール =
〃 本発明は保護膜として変性PVAを用いる事により色素透
過性のよい、熱溶剤を変化させても余りベトつかない良
好な感光材料が得られる事がわかる。Protective film composition E-1,2,3 Gel / Polymer / 3-methylpentane-1,3,5-
Triol = 22/40/50 F-1,2,3 Gel / Polymer / D-xylitol = 22/40/50 G-1,2,3 Gel / Polymer / N, N'-dimethylurea =
〃 H-1,2,3 Gel / Polymer / 1,5-Pentanediol =
It can be seen that in the present invention, by using the modified PVA as the protective film, it is possible to obtain a good light-sensitive material having good dye permeability and being less sticky even when the thermal solvent is changed.
実施例−7 赤感性ハロゲン化銀乳剤(ヨウ化銀含有率4モル%、粒
径0.1μmの化学熟成済のヨウ臭化銀乳剤に3,3′−ジ−
(γ−スルホプロピル)−9−メチルチアジカルボシア
ニンナトリウム塩を銀1モルあたり600mg添加したも
の)を銀に換算して0.2g分、ポリ(4−ビニルピロリド
ン)水溶液中において4−スルホベンツトリアゾールと
硝酸銀を等モル反応させてpH6.0としたものを銀に換算
して0.2g分、3−メチルペンタン−1,3,5−トリオール
を1.6g、4−ジエチルアミノ−2−メチルフェニルスル
ファミン酸ソーダ0.4g、色素供与物質として2−アセト
アミド−4−(1−カルボキシ−トリデシルオキシ)−
5−メチル−6−クロルフェノール0.52g及び3−アミ
ノ−4−アリル−5−メルカプト−1,2,4−トリアゾー
ル6mg、その他に追加ゼラチン、界面活性剤及びゼラチ
ン硬化剤を加えた塗布液を写真用下引加工を施した厚さ
100μmの透明ポリエチレンテレフタレートフィルム上
に塗布した。銀、ゼラチン及びポリ(4−ビニルピロリ
ドン)の塗布量はそれぞれ1.2g/m2、1.25g/m2及び2.9g/
m2であった。次いで中間層として以下にあげたポリマー
から成る中間層を設けた。Example-7 Red-sensitive silver halide emulsion (silver iodide content 4 mol%, chemically ripened silver iodobromide emulsion having a grain size of 0.1 μm was added to 3,3′-di-
0.2 g of (γ-sulfopropyl) -9-methylthiadicarbocyanine sodium salt added at 600 mg per mol of silver) was converted to silver in an aqueous poly (4-vinylpyrrolidone) solution. 0.2g of 3-methylpentane-1,3,5-triol, 1.6g of 4-diethylamino-2-methylphenylsulfamine was calculated by converting equimolar amounts of triazole and silver nitrate to pH 6.0 and converting to silver. 0.4 g of acid soda, 2-acetamido-4- (1-carboxy-tridecyloxy)-
A coating solution containing 0.52 g of 5-methyl-6-chlorophenol and 6 mg of 3-amino-4-allyl-5-mercapto-1,2,4-triazole, and additional gelatin, a surfactant and a gelatin hardener. Photographed thickness
It was coated on a 100 μm transparent polyethylene terephthalate film. The coating amount of silver, gelatin and poly (4-vinylpyrrolidone) is 1.2 g / m 2 , 1.25 g / m 2 and 2.9 g / m 2 , respectively.
It was m 2 . Then, an intermediate layer made of the following polymers was provided as an intermediate layer.
中間層の付量はバインダーtotalで1g/m2であり、3−メ
チルペンタン−1,3,5−トリオール0.7g/m2含むものであ
る。さらにこの上に前記赤感性ハロゲン化銀乳剤を緑感
性ハロゲン化銀乳剤(沃化銀含有率4モル%、平均粒径
0.125μm、立方体粒子の化学熟成済のヨウ臭化銀乳剤
に3,3′−カルボキシエチル−1,5′−ジクロル−オキサ
カルボシアニンを銀1モルあたり500mg添加したもの)
に代え、色素供与物質としてα−ベンゾイル−α−〔1
−フェニル−2−[4−{2−オクタデセニル−3−カ
ルボキシプロパン−アミド}ベンジル]−1,2,4−トリ
アゾリジン−3,5−ジオン−4−イル−〕−2−クロル
アセトアニリド0.65gに代えた以外は同様な塗布液を同
様にこの上に塗布し、それぞれの試料を中間層No.1〜7
に対応して44〜50とした。それぞれの試料を用い赤色光
で露光後実施例5で作製した受像紙と重ねた後熱現像及
び熱転写した。結果を第8表に示す。 The coating amount of the intermediate layer was 1 g / m 2 in total of the binder and contained 0.7 g / m 2 of 3-methylpentane-1,3,5-triol. Furthermore, the red-sensitive silver halide emulsion was further coated thereon with a green-sensitive silver halide emulsion (silver iodide content 4 mol%, average grain size).
0.125 μm, cubic grains of chemically ripened silver iodobromide emulsion with 3,3′-carboxyethyl-1,5′-dichloro-oxacarbocyanine added at 500 mg per silver mole)
In place of α-benzoyl-α- [1
-Phenyl-2- [4- {2-octadecenyl-3-carboxypropane-amido} benzyl] -1,2,4-triazolidine-3,5-dione-4-yl-]-2-chloroacetanilide to 0.65 g The same coating liquid was applied on this in the same manner except that it was replaced, and each sample was applied to the intermediate layers No. 1 to 7.
It corresponds to 44 to 50. Each sample was exposed to red light, and after overlapping with the image-receiving paper prepared in Example 5, heat development and heat transfer were performed. The results are shown in Table 8.
試料No.44は極端に色素の透過性が悪く、また試料No.4
5,46,48は転写ムラがみられた。これに対し、本発明試
料は転写濃度が高く、かつ転写ムラも生じない。 Sample No.44 has extremely poor dye permeability, and Sample No.4
5,46,48 had uneven transfer. In contrast, the sample of the present invention has a high transfer density and does not cause transfer unevenness.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岩垣 賢 東京都日野市さくら町1番地 小西六写真 工業株式会社内 (72)発明者 佐藤 寿昭 岡山県倉敷市酒津1621番地 株式会社クラ レ内 (72)発明者 山内 淳之介 岡山県倉敷市酒津1621番地 株式会社クラ レ内 (72)発明者 岡谷 卓司 岡山県倉敷市酒津1621番地 株式会社クラ レ内 (56)参考文献 特開 昭59−178456(JP,A) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Ken Iwagaki 1 Sakura-cho, Hino-shi, Tokyo Konishi Roku Photo Industrial Co., Ltd. (72) Toshiaki Sato 1621 Sakata, Kurashiki-shi, Okayama Kuraray Co., Ltd. (72) ) Inventor Junnosuke Yamauchi 1621 Sakurazu, Kurashiki City, Okayama Prefecture Kuraray Co., Ltd. (72) Inventor Takuji Okaya 1621 Sakata Tsu, Kurashiki City, Okayama Prefecture (56) Reference JP-A-59-178456 (JP, Sho A)
Claims (1)
を含有する感光層を有する熱現像感光材料において、該
感光材料が、ポリビニルアルコール系重合体を一成分と
しイオン性基を有する重合体を他成分とする水溶性又は
水分散性のブロック共重合体を含有する層を有し、前記
イオン性基を有する重合体に対する前記ポリビニルアル
コール系重合体の重量比率が0.2以上50以下であること
を特徴とする熱現像感光材料。1. A photothermographic material having a photosensitive layer containing at least silver halide grains on a support, wherein the photosensitive material comprises a polymer containing a polyvinyl alcohol polymer as a component and having an ionic group. Having a layer containing a water-soluble or water-dispersible block copolymer as another component, the weight ratio of the polyvinyl alcohol polymer to the polymer having the ionic group is 0.2 or more and 50 or less. Characterized photothermographic material.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60019399A JPH0690487B2 (en) | 1985-02-04 | 1985-02-04 | Photothermographic material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60019399A JPH0690487B2 (en) | 1985-02-04 | 1985-02-04 | Photothermographic material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS61193142A JPS61193142A (en) | 1986-08-27 |
JPH0690487B2 true JPH0690487B2 (en) | 1994-11-14 |
Family
ID=11998193
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60019399A Expired - Fee Related JPH0690487B2 (en) | 1985-02-04 | 1985-02-04 | Photothermographic material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0690487B2 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0840906B1 (en) * | 1995-07-18 | 2001-10-24 | Agfa-Gevaert N.V. | Process for producing a photothermographic recording material |
US6074814A (en) * | 1996-07-24 | 2000-06-13 | Agfa-Gevaert | Photothermographic material comprising an infra-red sensitizer |
EP0821271B1 (en) * | 1996-07-24 | 2006-04-19 | Agfa-Gevaert | Process for preparing an Infra-red photothermographic material comprising a spectral sensitizer and a stilbene derivative supersensitizer and image recording method |
EP0821270A1 (en) * | 1996-07-24 | 1998-01-28 | Agfa-Gevaert N.V. | Photothermographic material comprising an infra-red sensitizer |
EP0903624B1 (en) * | 1997-09-17 | 2003-05-14 | Agfa-Gevaert | Binders for thermographic materials |
DE69814544T2 (en) * | 1997-09-17 | 2004-03-18 | Agfa-Gevaert | Binder for thermographic materials |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59178456A (en) * | 1983-03-30 | 1984-10-09 | Fuji Photo Film Co Ltd | Color image forming method |
JPS61156252A (en) * | 1984-12-28 | 1986-07-15 | Fuji Photo Film Co Ltd | Photographic element |
-
1985
- 1985-02-04 JP JP60019399A patent/JPH0690487B2/en not_active Expired - Fee Related
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JPS61193142A (en) | 1986-08-27 |
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