EP0740194B1 - Silver halide containing material for making negative images having ultrahigh contrast - Google Patents
Silver halide containing material for making negative images having ultrahigh contrast Download PDFInfo
- Publication number
- EP0740194B1 EP0740194B1 EP96106510A EP96106510A EP0740194B1 EP 0740194 B1 EP0740194 B1 EP 0740194B1 EP 96106510 A EP96106510 A EP 96106510A EP 96106510 A EP96106510 A EP 96106510A EP 0740194 B1 EP0740194 B1 EP 0740194B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver halide
- group
- light sensitive
- recording material
- material according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- -1 Silver halide Chemical class 0.000 title claims description 59
- 229910052709 silver Inorganic materials 0.000 title claims description 38
- 239000004332 silver Substances 0.000 title claims description 38
- 239000000463 material Substances 0.000 title claims description 33
- 239000000839 emulsion Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 10
- 125000001302 tertiary amino group Chemical group 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims 3
- 125000005647 linker group Chemical group 0.000 claims 2
- 239000000758 substrate Substances 0.000 claims 2
- 125000002648 azanetriyl group Chemical group *N(*)* 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 9
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 8
- 150000002429 hydrazines Chemical class 0.000 description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000002560 nitrile group Chemical group 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 3
- WSGURAYTCUVDQL-UHFFFAOYSA-N 5-nitro-1h-indazole Chemical compound [O-][N+](=O)C1=CC=C2NN=CC2=C1 WSGURAYTCUVDQL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 235000010323 ascorbic acid Nutrition 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 125000006353 oxyethylene group Chemical group 0.000 description 2
- 125000003386 piperidinyl group Chemical group 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 2
- LGBPWIAXPVUTMY-JLAZNSOCSA-N (2r)-3,4-dihydroxy-2-[(1s)-1-hydroxyethyl]-2h-furan-5-one Chemical compound C[C@H](O)[C@H]1OC(=O)C(O)=C1O LGBPWIAXPVUTMY-JLAZNSOCSA-N 0.000 description 1
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical class C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 description 1
- QPTIWFZSPZVBEW-UHFFFAOYSA-N 1-(4-chlorophenyl)-2h-tetrazole-5-thione Chemical compound SC1=NN=NN1C1=CC=C(Cl)C=C1 QPTIWFZSPZVBEW-UHFFFAOYSA-N 0.000 description 1
- MOXZSKYLLSPATM-UHFFFAOYSA-N 1-(4-hydroxyphenyl)-2h-tetrazole-5-thione Chemical compound C1=CC(O)=CC=C1N1C(=S)N=NN1 MOXZSKYLLSPATM-UHFFFAOYSA-N 0.000 description 1
- UFYPTOJTJONMJG-UHFFFAOYSA-N 1-cyclohexyl-2h-tetrazole-5-thione Chemical compound S=C1N=NNN1C1CCCCC1 UFYPTOJTJONMJG-UHFFFAOYSA-N 0.000 description 1
- QUFRGNOIJAGRFY-UHFFFAOYSA-N 1-naphthalen-1-yl-2h-tetrazole-5-thione Chemical compound S=C1N=NNN1C1=CC=CC2=CC=CC=C12 QUFRGNOIJAGRFY-UHFFFAOYSA-N 0.000 description 1
- CLIDMUTWHLMPMN-UHFFFAOYSA-O 1h-imidazol-3-ium-3-carboxamide Chemical class NC(=O)[NH+]1C=CN=C1 CLIDMUTWHLMPMN-UHFFFAOYSA-O 0.000 description 1
- JAAIPIWKKXCNOC-UHFFFAOYSA-N 1h-tetrazol-1-ium-5-thiolate Chemical class SC1=NN=NN1 JAAIPIWKKXCNOC-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- 125000006290 2-hydroxybenzyl group Chemical group [H]OC1=C(C([H])=C([H])C([H])=C1[H])C([H])([H])* 0.000 description 1
- RSEBUVRVKCANEP-UHFFFAOYSA-N 2-pyrroline Chemical compound C1CC=CN1 RSEBUVRVKCANEP-UHFFFAOYSA-N 0.000 description 1
- OEBMOZBCDOBXAN-UHFFFAOYSA-N 2h-benzotriazole-5-carbonitrile Chemical compound C1=C(C#N)C=CC2=NNN=C21 OEBMOZBCDOBXAN-UHFFFAOYSA-N 0.000 description 1
- QBNQNDKOKMBUJW-UHFFFAOYSA-N 4,6-dichloro-2H-triazin-5-one Chemical group ClC1=C(C(=NN=N1)Cl)O QBNQNDKOKMBUJW-UHFFFAOYSA-N 0.000 description 1
- DSVIHYOAKPVFEH-UHFFFAOYSA-N 4-(hydroxymethyl)-4-methyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(CO)CN1C1=CC=CC=C1 DSVIHYOAKPVFEH-UHFFFAOYSA-N 0.000 description 1
- ZFIQGRISGKSVAG-UHFFFAOYSA-N 4-methylaminophenol Chemical compound CNC1=CC=C(O)C=C1 ZFIQGRISGKSVAG-UHFFFAOYSA-N 0.000 description 1
- CCGXXRSRPCOKDL-UHFFFAOYSA-N 5,6-dichloro-1h-triazin-4-one;sodium Chemical compound [Na].ClC=1NN=NC(=O)C=1Cl CCGXXRSRPCOKDL-UHFFFAOYSA-N 0.000 description 1
- BQCIJWPKDPZNHD-UHFFFAOYSA-N 5-bromo-2h-benzotriazole Chemical compound C1=C(Br)C=CC2=NNN=C21 BQCIJWPKDPZNHD-UHFFFAOYSA-N 0.000 description 1
- PZBQVZFITSVHAW-UHFFFAOYSA-N 5-chloro-2h-benzotriazole Chemical compound C1=C(Cl)C=CC2=NNN=C21 PZBQVZFITSVHAW-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- AOCDQWRMYHJTMY-UHFFFAOYSA-N 5-nitro-2h-benzotriazole Chemical compound C1=C([N+](=O)[O-])C=CC2=NNN=C21 AOCDQWRMYHJTMY-UHFFFAOYSA-N 0.000 description 1
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RENMDAKOXSCIGH-UHFFFAOYSA-N Chloroacetonitrile Chemical compound ClCC#N RENMDAKOXSCIGH-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-MVHIGOERSA-N D-ascorbic acid Chemical compound OC[C@@H](O)[C@@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-MVHIGOERSA-N 0.000 description 1
- QZKRHPLGUJDVAR-UHFFFAOYSA-K EDTA trisodium salt Chemical compound [Na+].[Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O QZKRHPLGUJDVAR-UHFFFAOYSA-K 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- WYNCHZVNFNFDNH-UHFFFAOYSA-N Oxazolidine Chemical compound C1COCN1 WYNCHZVNFNFDNH-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 229920004892 Triton X-102 Polymers 0.000 description 1
- 125000002252 acyl group Chemical class 0.000 description 1
- 125000004423 acyloxy group Chemical class 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000002355 alkine group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical class 0.000 description 1
- 125000004849 alkoxymethyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 125000004644 alkyl sulfinyl group Chemical class 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000004397 aminosulfonyl group Chemical class NS(=O)(=O)* 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000005251 aryl acyl group Chemical group 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical class 0.000 description 1
- 125000005135 aryl sulfinyl group Chemical class 0.000 description 1
- 125000005421 aryl sulfonamido group Chemical group 0.000 description 1
- 125000004391 aryl sulfonyl group Chemical class 0.000 description 1
- 125000005110 aryl thio group Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- VJEIIJANCJRLFJ-UHFFFAOYSA-N azecane Chemical group C1CCCCNCCCC1 VJEIIJANCJRLFJ-UHFFFAOYSA-N 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical group C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- WDEFENNKTPQVSJ-UHFFFAOYSA-N benzene-1,4-diol;pyrazolidin-3-one Chemical compound O=C1CCNN1.OC1=CC=C(O)C=C1 WDEFENNKTPQVSJ-UHFFFAOYSA-N 0.000 description 1
- MXJIHEXYGRXHGP-UHFFFAOYSA-N benzotriazol-1-ylmethanol Chemical compound C1=CC=C2N(CO)N=NC2=C1 MXJIHEXYGRXHGP-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000004202 carbamide Chemical class 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 125000003917 carbamoyl group Chemical class [H]N([H])C(*)=O 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical class [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical class CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical class C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- AEOCXXJPGCBFJA-UHFFFAOYSA-N ethionamide Chemical compound CCC1=CC(C(N)=S)=CC=N1 AEOCXXJPGCBFJA-UHFFFAOYSA-N 0.000 description 1
- BQINTNNSPWSRCD-UHFFFAOYSA-N ethyl n-amino-n-(carbamoylamino)carbamate Chemical class CCOC(=O)N(N)NC(N)=O BQINTNNSPWSRCD-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 229910052741 iridium Chemical class 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical class [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002504 iridium compounds Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- HRDXJKGNWSUIBT-UHFFFAOYSA-N methoxybenzene Chemical group [CH2]OC1=CC=CC=C1 HRDXJKGNWSUIBT-UHFFFAOYSA-N 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- VLLXDIQVPMMHCN-UHFFFAOYSA-N n-(2h-benzotriazol-5-yl)benzamide Chemical compound C1=CC2=NNN=C2C=C1NC(=O)C1=CC=CC=C1 VLLXDIQVPMMHCN-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 150000004010 onium ions Chemical group 0.000 description 1
- SFJGCXYXEFWEBK-UHFFFAOYSA-N oxazepine Chemical compound O1C=CC=CC=N1 SFJGCXYXEFWEBK-UHFFFAOYSA-N 0.000 description 1
- 125000005429 oxyalkyl group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- RUDNWZFWWJFUSF-UHFFFAOYSA-M potassium;(4-methylphenyl)-oxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].CC1=CC=C(S([O-])(=O)=S)C=C1 RUDNWZFWWJFUSF-UHFFFAOYSA-M 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- UGZVCHWAXABBHR-UHFFFAOYSA-O pyridin-1-ium-1-carboxamide Chemical class NC(=O)[N+]1=CC=CC=C1 UGZVCHWAXABBHR-UHFFFAOYSA-O 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- ZVJHJDDKYZXRJI-UHFFFAOYSA-N pyrroline Natural products C1CC=NC1 ZVJHJDDKYZXRJI-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003283 rhodium Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical class [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 125000000020 sulfo group Chemical class O=S(=O)([*])O[H] 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000080 wetting agent 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
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/067—Additives for high contrast images, other than hydrazine compounds
-
- 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
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
-
- 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
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/061—Hydrazine compounds
-
- 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
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
- G03C2001/03541—Cubic grains
-
- 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
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
- G03C2001/0357—Monodisperse emulsion
-
- 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
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
- G03C2001/03594—Size of the grains
-
- 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
- G03C2200/00—Details
- G03C2200/44—Details pH value
-
- 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/30—Developers
Definitions
- the invention relates to a silver halide photographic material to create black and white Negative images with ultra-partial contrast and a method for Using a black and white negative image of such material.
- Halftone images can be converted into halftone dot images.
- silver halide materials which one in special methods for ultra-partial contrast, d. H. to a maximum gradient of the density curve of more than 10, developed.
- the lith process is also known, for example Low-sulfite, formaldehyde-containing hydroquinone developers. Development has recently become of particular practical importance in the presence of hydrazine compounds.
- EP-A-02 03 521 can be salts of certain sulfonic or carboxylic acids as Solubilizers are used. The remaining However, problems addressed are caused by such additions unaffected.
- the known developers usually have a pH above 11. Therefore, they are not sufficiently stable and in practice have a highly corrosive effect on the components of the development machines.
- German patent application DE-A-43 10 327 there is a Process for the generation of negative images with ultra-partial Contrast described in which the development of the Silver halide recording material in the presence of Connections are made whose molecules have at least one quaternary nitrogen atom and at least one tertiary Have amine function.
- EP-04 73 342-A1 there is a photographic Silver halide material described in a developer with a pH ⁇ 11 to be developed to ultra-partial contrast can.
- the light sensitive coating of this material contains a hydrazine compound of a certain formula as well an amino or a quaternary onium compound and is on set a pH of at least 5.9.
- EP 04 22 677 describes the use of tertiary Amino compounds with at least three oxyethylene units in the Molecule as a development accelerator in developer solutions, which also work in the presence of hydrazine compounds.
- EP 05 39 998 claims silver halide materials, which besides Hydrazine compounds or thioether compounds with tertiary Amino group included.
- the invention has for its object a silver halide recording material to propose that for generating Negative images with ultra-partial contrast at short Processing time with a stable, odorless and not Corrosive developer suitable and from those mentioned above Disadvantages is free, as well as a process for the production of Black and white negative images with ultra-partial contrast specify.
- the tertiary amino group is replaced by a nitrogen atom realized, which with single bonds to two organic Remnants as well as via a divalent connecting group to the Nitri group is bound.
- the contrast-increasing compound falls under one of the general formulas (A), (B) or (C) given below: RR 1 N - X - (CN) n NC - X - NR 2 - B - NR 2 - X - CN RR 1 N - X - N (CH 2 CN) 2
- the radicals R and R 1 may be the same or different and each may be a straight-chain or branched alkyl group having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl.
- Each of the groups R and R 1 can also be a benzyl group.
- the groups R and R 1 and also the heterocyclic rings corresponding to these groups can be further substituted, preferably with hydroxyl, alkoxy, alkylthio or alkylamino groups, where the alkyl can have 1 to 6 carbon atoms. Examples of such substituents are methoxy, ethoxy, propoxy, butoxy, ethylamino, dimethylamino, butylthio.
- R or R 1 can also connect to the connecting group X with their free end to form a ring which includes the nitrogen atom of the tertiary amino group.
- a ring can be, for example, a piperidine ring or a morpholine ring.
- the divalent connecting groups X and B are preferred straight-chain, branched or cyclic alkylene groups with 1 up to 20 carbon atoms, phenylene or aralkylene groups with 7 to 20 carbon atoms, or divalent chains from 1 to 20 methylene groups, in addition to these also oxygen, Sulfur, amino groups, alkene or alkyne groups or also Polyoxyalkylene groups, especially polyoxyethylene or Polyoxypropylene groups with 1 to 50 oxyalkyl units can be installed. An ethylene or Propylene group.
- the groups mentioned can also continue be substituted, for example with alkyl, hydroxyl and further tertiary amino groups.
- the connecting group X can also be trivalent and thus connect the tertiary amino group with two nitrile groups.
- the groups mentioned in the previous paragraph are suitable if they contain a further free valence instead of a hydrogen atom. Examples include:
- the radical R 2 in the general formula (B) denotes a saturated or unsaturated alkyl group, preferably having 1 to 12 carbon atoms, an aryl group, preferably having 6 to 14 carbon atoms or an aralkyl group, preferably having 7 to 15 carbon atoms. These groups can in turn be substituted, for example with hydroxyl, amino, alkylamino and alkoxy groups, the alkyl preferably having 1 to 6 carbon atoms. If it is an alkyl group, it can also be attached to a carbon atom of group B with its end facing away from the nitrogen, forming a ring. Such a ring can be, for example, a piperidine, pyrrolidine or hexahydroazepine ring.
- the two radicals R 2 can also form together with B or with parts of B and with the two nitrogen atoms one or two saturated rings, preferably with 5 or 6 members, for example pyrrolidine or piperidine rings.
- n is either 1 or 2.
- contrast-increasing compounds according to the invention in have at least one tertiary amino group in their molecule, They can be in the form of the free amine as well as in the form a salt, i.e. an adduct of an acid and that free amine, produced, handled and used.
- a preferred acid is hydrochloric acid.
- Contrast-increasing compounds according to the invention can be from easily accessible and inexpensive raw materials produce.
- the person skilled in the art can use the Find standard works on preparative organic chemistry, for example the introduction of a cyanomethyl group Chloroacetonitrile, the alkylation of cyanides (Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 8 (1952), Pages 290 ff.) And the drainage of carboxamides (ibid., pages 330 ff.).
- Other possibilities of synthesis are the alkylation of the anion of a suitable CH-azide Compound such as malononitrile with aminohalogen alkanes and the conversion of ketones with cyanides to cyanohydrins.
- Several of the compounds of the invention are also reasonably priced in stores.
- contrast-increasing compounds are: (C 2 H 5 ) 2 NC 3 H 6 ⁇ CN HCl (i - C 3 H 7 ) 2 NC 2 H 4 ⁇ CN HCl (C 4 H 9 ) 2 NC 2 H 4 ⁇ CN HCl (C 4 H 9 ) 2 NC 3 H 6 ⁇ N (CH 2 CN) 2 (C 2 H 5 ) 2 NC 2 H 4 ⁇ O ⁇ C 2 H 4 ⁇ CN (C 2 H 5 ) 2 NC 2 H 4 ⁇ S ⁇ C 2 H 4 ⁇ CN
- the recording material according to the invention contains a Hydrazine compound.
- This hydrazine compound can in itself known way either in one or more layers of Recording material can be incorporated.
- This can be both Layers which are the photosensitive silver halide contain, as well as layers with the former in reactive connection, d. H. which are arranged so that Can diffuse substances from one layer to the other, if a concentration gradient through reactions is maintained.
- Suitable hydrazine compounds are described, for example, in Research Disclosure 235 010 (November 1983), DE-27 25 743-A1, EP-00 32 456-B1, EP-01 26 000-A2, EP-01 38 200-A2, EP-02 03 521-A2, EP-02 17 310-A2, EP- 02 53 665-A2, EP-03 24 391-A2, EP-03 24 426-A2, EP-03 26 443-A2, EP-03 56 898-A2, EP-04 73 342-A1, EP-05 01 546-A1, EP-04 81 565-A, EP-05 98 315-A1, EP-04 44 506.
- Preferred hydrazine compounds are described by the general formula (H): B - phenyl - NHNH - L - G
- B is a ballast group
- G is an activating group Group
- L one of the groups -CO- and -CO-CO-.
- Phenyl means a benzene ring on the B and the hydrazine group are bound, preferably in the para position.
- Preferred ballast groups are those that are not are electron-attracting, for example straight or branched alkyl groups (e.g. methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl, n-hexyl, n-octyl, t-octyl, n-decyl, n-dodecyl and similar groups), also alkoxy groups, which contain one of the alkyl groups mentioned above as alkyl, as well as acylamino groups, such as acetylamino, propanoylamino, Butanoylamino, octanoylamino, benzoylamino, alkyl and Arylsulfonamido and similar groups.
- alkyl groups e.g. methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl,
- Ballast groups typically contain at least 8 Carbon atoms and can be made of relatively inert aliphatic or aromatic groups are selected, for example alkyl, alkoxy, phenyl, alkylphenyl, phenoxy, Alkylphenoxy, arylacyl, arylamido, alkylpyridinium-1-ylamido and similar groups.
- the alkyl and alkoxy groups include any Ballast groups preferably 1 to 20, the acylamino groups preferably 2 to 21 carbon atoms. But it can be up to Contain 30 or more carbon atoms in these groups be. Methoxyphenyl, tolyl, ballasted butyramidophenyl, butylsulfonamido and Toluylsulfonamido.
- Preferred hydrazine compounds include those whose Ballast group still contains an adsorption promoting group. Such groups promote the adsorption of the molecule on the Surface of the silver halide crystals and are in themselves known. They typically contain at least one sulfur or Nitrogen atom which can form a silver complex or otherwise has an affinity for the silver halide surface. Preferred examples are thiourea, thiuronium, heterocyclic thioamide and triazole groups.
- G is preferably hydrogen, optionally substituted alkyl (e.g. methyl, hydroxymethyl, monofluoromethyl, pyridinomethyl, Phenoxymethyl, alkoxymethyl such as methoxymethyl), if appropriate substituted aralkyl (e.g. benzyl, o-hydroxybenzyl) and possibly substituted aryl (e.g. phenyl, 3,5-dichlorophenyl, o-methanesulfonamidophenyl, 4-methanesulfonylmethyl, 2-hydroxymethylphenyl), alkyl groups with electron-withdrawing substituents, for example cationic groups with quaternary nitrogen atom, such as Pyridinium and Imidazolium, are particularly preferred.
- alkyl e.g. methyl, hydroxymethyl, monofluoromethyl, pyridinomethyl, Phenoxymethyl, alkoxymethyl such as methoxymethyl
- substituted aralkyl e.g. benzyl
- G can also be further substituted, e.g. B. with alkyl, Aralkyl, alkenyl, alkynyl, alkoxy, aryl, substituted amino, Ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkyl or Arylthio, alkyl- or arylsulfonyl, alkyl- or arylsulfinyl, Hydroxy, halogen, cyan, sulfo, aryloxycarbonyl, acyl, Alkoxycarbonyl, acyloxy, carbamide, sulfonamide, carboxyl, Phosphamide, diacylamino, imide.
- G can also be chosen so that the L-G part of the molecule is separated to form a ring, as is e.g. in EP-B-02 53 665 is described.
- OTS - is the anion of o-toluenesulfonic acid.
- the light-sensitive silver halides of the invention recording materials used consist of Silver chloride, silver bromide, silver chlorobromide, Silver bromoiodide or silver chlorobromoiodide.
- the silver halide grains can be spherical, polyhedral or tabular to have. Methods of making suitable photosensitive Silver halide emulsions are known to the person skilled in the art and for example in Research Disclosure 365 044, Chapter I to IV (September 1994).
- Recording materials are silver halide emulsions that be produced by controlled double jet inlet and have a cubic grain shape. Emulsions are advantageous in which at least 80 percent by weight of the silver halide are available in cubic form. Are particularly preferred monodisperse emulsions, i.e. H. those where the Coefficient of variation (quotient of standard deviation and Mean) the grain size is less than 0.30. Under Grain size becomes the edge length of one with the real grain volume equal cube understood.
- the grain volume of the silver halide grains in the emulsions depends on the required sensitivity and can for example the cubic grain from 0.1 to 0.7 ⁇ m Edge length. A preferred range is between 0.15 and 0.30 ⁇ m.
- the emulsions are preferably chemically sensitized. Suitable processes are the sulfur, the reduction and the precious metal sensitization, also in combination can be applied. For the latter, for example Gold or iridium compounds can be used.
- the Sensitization is preferred in the presence of salts organic thiosulfonic acids, such as p-toluenesulfonic acid, carried out.
- the emulsions can be mixed with usual Sensitizing dyes are spectrally sensitized, such as in Research Disclosure 365 044, Chapter V (September 1994).
- the emulsions can also be conventional antifoggants contain.
- Substituted benzotriazole are preferred, 5-nitroindazole and 1-phenyl-5-mercaptotetrazole. This means can be used at any time during emulsion production be added or in an auxiliary layer of the photographic material may be included.
- the photographic properties can before or the emulsion after chemical ripening an iodide, preferably a Alkali iodide, in an amount of about 0.5 to 5 mmol per mole Silver can be added.
- the emulsions can also contain known polymer dispersions which, for example, improve the dimensional stability of the photographic material. These are generally latices of hydrophobic polymers in an aqueous matrix. Examples of suitable polymer dispersions are mentioned in Research Disclosure 176 043, Chapter IX B (December 1978). Polymers of esters of acrylic and methacrylic acid are preferred, particularly preferably of C 1 to C 6 esters. The particle size of these polymer latices is preferably between 20 and 100 nm.
- the photosensitive layers of the photographic Materials can be hardened by adding a hardening agent be.
- hardeners are in research Disclosure 365 044, Chapter II B (September 1994). This hardener can be added to the emulsion or via a Auxiliary layer, for example an outer protective layer, be introduced.
- Suitable hardeners are, for example Aldehydes, such as formaldehyde or glutaraldehyde, vinyl sulfones, s-triazines, aziridines, carbodiimides, carbamoylpyridinium compounds, mono- and bifunctional carbamoylimidazolium compounds.
- a preferred curing agent is Hydroxydichlorotriazine.
- the photographic material can be further additives for the Generation of certain properties are known and common, contain. Such funds are, for example, in research Disclosure 365 044 (September 1994) in Chapter VI (Brightener), IX A (coating aid), IX B (Plasticizers and lubricants) and IX D (matting agents) listed.
- the gelatin content of the emulsions is in general between 30 and 150 g per mole of silver; the is preferred Range between 40 and 100 g per mol of silver.
- the invention also includes a method for the production black and white negative photographic images, which is characterized by having a preliminary described light-sensitive material exposed imagewise in an aqueous developer solution developed, fixed in the usual way, watered and dried.
- the developer solutions used according to the invention contain preferably a dihydroxybenzene developer substance, for example hydroquinone, pyrocatechol, methylhydroquinone or chlorohydroquinone, and an antioxidant, preferably an alkali sulfite in a concentration of more than 0.3 mol per liter. Solutions with are particularly preferred pH values from 9 to a maximum of 11. Such developer solutions are also durable in use and largely result fog-free images.
- Ascorbic acid type for example L-ascorbic acid, D-ascorbic acid, L-erythroascorbic acid, 6-deoxy-L-ascorbic acid, Imino-L-erythroascorbic acid or Sugar derivatives of these acids.
- Developer solutions that both developer substances from Dihydroxybenzene type as well as those of the ascorbic acid type contain.
- the developer solutions preferably contain known solutions super-additive auxiliary developer substances, for example N-methyl-p-aminophenol or 1-phenylpyrazolidinone-3 or derivatives of these compounds.
- developers that consist of stabilizers contain the groups of benzotriazoles and mercaptotetrazoles.
- Such stabilizers are, for example 1-phenyl-5-mercaptotetrazole, 1- (4-hydroxyphenyl) -5-mercaptotetrazole, 1- (1-naphthyl) -5-mercaptotetrazole, 1-cyclohexyl-5-mercaptotetrazole, 1- (4-chlorophenyl) -5- mercaptotetrazole, 1- (3-capramidophenyl) -5-mercaptotetrazole, benzotriazole, 5-chlorobenzotriazole, 5-bromobenzotriazole, 5-methylbenztriazole, 5-nitrobenztriazole, 5-benzoylaminobenztriazole, 1-hydroxymethylbenztriazole, 6-cyanobenztriazole.
- the contrast-enhancing compounds according to the invention can added to the emulsion at every stage of manufacture will. Because of their molecular structure, they can both be surface active as well as with ionic polymers Interaction.
- the nitrile group gives the Compounds hydrophilic properties. In contrast, in Molecule also present hydrocarbon groups hydrophobic and diffusion-inhibiting effect. It is therefore possible by selecting the number of nitrile groups, the number and type of hydrocarbon groups and possibly other hydrophilic groups such as ethylene oxide groups Water solubility, interfacial activity and Diffusibility of the connections on the respective To coordinate the application.
- the compounds according to the invention are in the alkaline developer baths too photographically inactive secondary products are decomposed. she therefore do not enrich themselves - like other well-known in Recording material incorporated contrast-enhancing Connections - as a result of washing out in the developer. Therefore they affect the stability of developer activity not even if they are only slightly diffusion inhibited (ballasted).
- the invention can be used to produce black and white Negative images with ultra-partial contrast, especially in the Reproduction in prepress for the black and white and Multi-color printing. It is through the following Embodiment explained in more detail.
- a cubic silver chlorobromide emulsion (80 mole percent chloride) was produced by pAg-controlled two-jet inlet in the presence of a rhodium salt, the grains of which had an edge length of 0.21 ⁇ m. After the soluble salts had been removed by means of the flocking process, the total gelatin content was 55 g per mol of silver and chemical ripening was carried out using potassium thiotosylate, thiosulfate and gold salt.
- potassium iodide (1.6 mmol / mol Ag), phenyl mercaptotetrazole, 5-nitroindazole, a polyethylene latex, a sensitizer for the green spectral range, two coating aids (Triton® X-102, Triton® X-200; manufacturer: Rohm & Haas ), 0.12 mmol of 1-pyridiniumacetyl-2- (4-benzyloxyphenyl) hydrazine bromide (compound H-9) per mol of silver and 0.10 mmol of dichlorohydroxytriazine sodium salt per g of gelatin were added.
- Camera films were produced by applying the emulsion together with overcasts containing gelatin, matting agent, wetting agent (Triton® X-200) and additives according to Table 1.
- the silver application was 4.2 g / m 2
- the pouring application 0.9 g gelatin per m 2 .
- Sample strips of the recording materials obtained were exposed to white light through an original from a density gradient wedge, which was partially underlaid with a contact grid.
- the strips were developed, fixed, washed and dried in a developing machine (Dürr Graphica) at 36 ° C.
- the development time was 28 s.
- a commercially available fixing bath was used.
- the developer had the following composition: water 500 g Sodium bisulfite 50 g KOH 27 g EDTA trisodium salt 3.7 g Hydroquinone 25 g Potassium bromide 4 g Benzotriazole 0.3 g Phenyl mercaptotetrazole 0.05 g 4-hydroxymethyl-4-methyl-1-phenylpyrazolidinone 1 g Boric acid 3 g Sodium hydroxide 24 g Diethylene glycol 40 g Water to 1 liter, pH to 10.5 at 22 ° C.
- the rating 10 means optimal sharpness of the points, 4 - 5 is only of limited use and corresponds to the sharpness of a Rapid Access film without contrast enhancement, 1 - 3 is unusable.
- Table 1 attempt additive Dmin Dmax S G1 G2 PQ Verb.
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Description
Die Erfindung betrifft ein photographisches Silberhalogenid-Aufzeichnungsmaterial zur Erzeugung von schwarz-weißen Negativbildern mit ultrasteilem Kontrast und ein Verfahren zur Herstellung eines Schwarz-Weiß-Negativbildes unter Verwendung eines solchen Materials.The invention relates to a silver halide photographic material to create black and white Negative images with ultra-partial contrast and a method for Using a black and white negative image of such material.
Bei der photomechanischen Reproduktion müssen häufig Halbtonbilder in Rasterpunktbilder umgewandelt werden. Hierzu verwendet man Silberhalogenidmaterialien, die man in besonderen Verfahren zu ultrasteilem Kontrast, d. h. zu einer maximalen Steigung der Schwärzungskurve von mehr als 10, entwickelt. Bekannt sind beispielsweise das Lithverfahren mit sulfitarmen, formaldehydhaltigen Hydrochinonentwicklern. Besondere praktische Bedeutung hat neuerdings die Entwicklung in Gegenwart von Hydrazinverbindungen.In photomechanical reproduction, often Halftone images can be converted into halftone dot images. For this one uses silver halide materials which one in special methods for ultra-partial contrast, d. H. to a maximum gradient of the density curve of more than 10, developed. The lith process is also known, for example Low-sulfite, formaldehyde-containing hydroquinone developers. Development has recently become of particular practical importance in the presence of hydrazine compounds.
Bei diesem Verfahren werden häufig gewisse Aminoverbindungen zur weiteren Steigerung des Kontrastes angewendet. So wird in der EP-00 32 456-B1 ein Verfahren beansprucht, bei dem man ein Aufzeichnungsmaterial in Gegenwart einer Hydrazinverbindung mit einem Hydrochinon-3-Pyrazolidinon-Entwickler verarbeitet, der eine kontraststeigernde Menge einer Aminoverbindung enthält.Certain amino compounds are often used in this process applied to further increase the contrast. So in EP-00 32 456-B1 claims a method in which one Recording material in the presence of a hydrazine compound processed with a hydroquinone-3-pyrazolidinone developer, which is a contrast increasing amount of an amino compound contains.
Entwickler, die eine kontraststeigernde Menge einer Aminoverbindung enthalten, sind nicht frei von Nachteilen. Die erforderliche Konzentration der Aminoverbindung ist beträchtlich und liegt häufig in der Nähe der Löslichkeitsgrenze. Infolge der Temperaturerhöhung oder von geringen Konzentrationsänderungen durch Wasserverdunstung während des Gebrauchs kann die Löslichkeitsgrenze leicht überschritten werden und die Aminoverbindung scheidet sich aus. Dies kann zu ungleichmäßiger Entwicklung und zur Verunreinigung der Aufzeichnungsmaterialien und der Entwicklungsmaschine führen. Wegen ihrer wasserdampfflüchtigkeit können die ausgeschiedenen Aminoverbindungen auch an entfernte Stellen der Entwicklungsmaschine gelangen und unerwünschte Verunreinigungen sowie Korrosion hervorrufen.Developers who have a contrast increasing amount of one Containing amino compounds are not free from disadvantages. The required concentration of the amino compound is considerable and is often close to the Solubility limit. As a result of the temperature increase or of low concentration changes due to water evaporation during use the solubility limit can be easily exceeded and the amino compound separates out. This can lead to uneven development and Contamination of the recording materials and the Lead development machine. Because of their water vapor volatility the excreted amino compounds can also get to remote parts of the processor and cause unwanted contamination and corrosion.
Bei der Verwendung von Entwicklern, welche bekannte Aminoverbindungen enthalten, tritt ein auch sehr unangenehmer Geruch auf, der auf die hohe erforderliche Konzentration und die Flüchtigkeit dieser Verbindungen zurückzuführen ist.When using developers who are known Containing amino compounds occurs also very uncomfortable Smell based on the high concentration and required the volatility of these connections is due.
Da die Aminoverbindungen nur begrenzt löslich sind ist es schwierig, die als wirtschaftliche Handelsform üblichen Entwicklerkonzentrate zu formulieren. Nach der EP-A-02 03 521 können zwar Salze gewisser Sulfo- oder Carbonsäuren als Lösungsvermittler eingesetzt werden. Die übrigen angesprochenen Probleme werden jedoch durch solche Zusätze nicht beeinflußt.Since the amino compounds are only soluble to a limited extent, it is difficult, the usual as an economic form of trading Formulate developer concentrates. According to EP-A-02 03 521 can be salts of certain sulfonic or carboxylic acids as Solubilizers are used. The remaining However, problems addressed are caused by such additions unaffected.
Die bekannten Entwickler haben in der Regel einen pH über 11. Daher sind sie für die Praxis nicht hinreichend stabil und wirken stark korrosiv auf die Bauteile der Entwicklungsmaschinen.The known developers usually have a pH above 11. Therefore, they are not sufficiently stable and in practice have a highly corrosive effect on the components of the development machines.
In der deutschen Offenlegungsschrift DE-A-43 10 327 ist ein Verfahren zur Erzeugung von Negativbildern mit ultrasteilem Kontrast beschrieben, bei dem die Entwicklung des Silberhalogenid-Aufzeichnungsmaterials in Gegenwart von Verbindungen erfolgt, deren Moleküle mindestens ein quaternäres Stickstoffatom und mindestens eine tertiäre Aminfunktion aufweisen.In the German patent application DE-A-43 10 327 there is a Process for the generation of negative images with ultra-partial Contrast described in which the development of the Silver halide recording material in the presence of Connections are made whose molecules have at least one quaternary nitrogen atom and at least one tertiary Have amine function.
In der EP-04 73 342-A1 ist ein photographisches Silberhalogenidmaterial beschrieben, das in einem Entwickler mit einem pH < 11 zu ultrasteilem Kontrast entwickelt werden kann. Die lichtempfindliche Beschichtung dieses Material enthält eine Hydrazinverbindung einer bestimmten Formel sowie eine Amino- oder eine quaternäre Oniumverbindung und ist auf einen pH von mindestens 5,9 eingestellt. In EP-04 73 342-A1 there is a photographic Silver halide material described in a developer with a pH <11 to be developed to ultra-partial contrast can. The light sensitive coating of this material contains a hydrazine compound of a certain formula as well an amino or a quaternary onium compound and is on set a pH of at least 5.9.
US 4,975,354 schlägt vor, den Silberhalogenidmaterialien neben Hydrazinverbindungen noch bestimmte sekundäre oder tertiäre Aminoverbindungen, die außerdem mindestens drei Oxyethylenenheiten in ihrem Molekül enthalten, als Kontrastverstärker ("booster") zu inkorporieren.US 4,975,354 suggests the silver halide materials alongside Hydrazine compounds still certain secondary or tertiary Amino compounds that also have at least three Oxyethylene units contained in their molecule as Incorporating contrast enhancers ("boosters").
EP 04 22 677 beschreibt die Anwendung von tertiären Aminoverbindungen mit mindestens drei Oxyethyleneinheiten im Molekül als Entwicklungsbeschleuniger in Entwicklerlösungen, die auch in Gegenwart von Hydrazinverbindungen wirken.EP 04 22 677 describes the use of tertiary Amino compounds with at least three oxyethylene units in the Molecule as a development accelerator in developer solutions, which also work in the presence of hydrazine compounds.
EP 05 39 998 beansprucht Silberhalogenidmaterialien, die neben Hydrazinverbindungen noch Thioetherverbindungen mit tertiärer Aminogruppe enthalten.EP 05 39 998 claims silver halide materials, which besides Hydrazine compounds or thioether compounds with tertiary Amino group included.
Die Erfindung stellt sich die Aufgabe, ein Silberhalogenid-Aufzeichnungsmaterial vorzuschlagen, das zum Erzeugen von Negativbildern mit ultrasteilem Kontrast bei kurzer Verarbeitungszeit mit einem stabilen, geruchfreien und nicht korrosiven Entwickler geeignet und von den oben erwähnten Nachteilen frei ist, sowie ein Verfahren zur Herstellung von Schwarz-Weiß-Negativbildern mit ultrasteilem Kontrast anzugeben.The invention has for its object a silver halide recording material to propose that for generating Negative images with ultra-partial contrast at short Processing time with a stable, odorless and not Corrosive developer suitable and from those mentioned above Disadvantages is free, as well as a process for the production of Black and white negative images with ultra-partial contrast specify.
Diese Aufgaben werden gelöst durch ein Silberhalogenid-Aufzeichnungsmaterial nach dem Hauptanspruch und durch ein Verfahren nach Anspruch 8.These objects are achieved by a silver halide recording material according to the main claim and by a The method of claim 8.
Es wurde nämlich überraschenderweise gefunden, daß Verbindungen, die in ihrem Molekül mindestens eine Nitrilogruppe sowie mindestens eine tertiäre Aminogruppe enthalten, wenn sie gemeinsam mit Hydrazinverbindungen in Silberhalogenid-Aufzeichnungsmaterialien inkorporiert werden, die Herstellung von Bildern mit ultrasteilem Kontrast auch bei relativ niedrigem Entwickler-pH und bei kurzer Entwicklungszeit ermöglichen.Surprisingly, it was found that Compounds that have at least one in their molecule Nitri group and at least one tertiary amino group included when in together with hydrazine compounds Silver halide recording materials are incorporated, the production of images with ultra-partial contrast relatively low developer pH and a short one Enable development time.
Die tertiäre Aminogruppe wird durch ein Stickstoffatom realisiert, welches mit Einfachbindungen an zwei organische Reste sowie über eine zweiwertige verbindende Gruppe an die Nitrilogruppe gebunden ist.The tertiary amino group is replaced by a nitrogen atom realized, which with single bonds to two organic Remnants as well as via a divalent connecting group to the Nitri group is bound.
In einer bevorzugten Ausführungsform der Erfindung fällt die
kontraststeigernde Verbindung unter eine der nachstehend
angegebenen allgemeinen Formeln (A), (B) oder (C):
Die Reste R und R1 können gleich oder verschieden sein und je eine geradkettige oder verzweigte Alkylgruppe mit 1 bis 6 Kohlenstoffatomen sein, beispielsweise Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, n-Hexyl. Sie können auch unter Einschluß des Stickstoffatoms und ggf. eines weiteren Stickstoffatoms, eines Sauerstoffatoms oder einer Carbonylgruppe einen heterozyklischen Ring mit 5 bis 12 Gliedern bilden, beispielsweise einen Piperidin-, Pyrrolidin-, Pyrrolin-, Oxazolidin-, Imidazolin-, Morpholin-, Pyrazan-, Azepin-, Oxazepin- oder Azacyclodecanring. Jede der Gruppen R und R1 kann auch eine Benzylgruppe sein. Die Gruppen R und R1 und auch die diesen Gruppen entsprechenden heterozyklischen Ringe können weiter substituiert sein, bevorzugt mit Hydroxyl-, Alkoxy-, Alkylthio- oder Alkylaminogruppen, wobei das Alkyl 1 bis 6 Kohlenstoffatome aufweisen kann. Beispiele solcher Substituenten sind Methoxy, Ethoxy, Propoxy, Butoxy, Ethylamino, Dimethylamino, Butylthio.The radicals R and R 1 may be the same or different and each may be a straight-chain or branched alkyl group having 1 to 6 carbon atoms, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-hexyl. You can also form a heterocyclic ring with 5 to 12 members, including for example a piperidine, pyrrolidine, pyrroline, oxazolidine, imidazoline, morpholine, pyrazane, including the nitrogen atom and optionally another nitrogen atom, an oxygen atom or a carbonyl group -, azepine, oxazepine or azacyclodecane ring. Each of the groups R and R 1 can also be a benzyl group. The groups R and R 1 and also the heterocyclic rings corresponding to these groups can be further substituted, preferably with hydroxyl, alkoxy, alkylthio or alkylamino groups, where the alkyl can have 1 to 6 carbon atoms. Examples of such substituents are methoxy, ethoxy, propoxy, butoxy, ethylamino, dimethylamino, butylthio.
R oder R1 können auch mit ihrem freien Ende unter Bildung eines Ringes, der das Stickstoffatom der tertiären Aminogruppe einschließt, an die verbindende Gruppe X anknüpfen. Ein solcher Ring kann beispielsweise ein Piperidinring oder ein Morpholinring sein.R or R 1 can also connect to the connecting group X with their free end to form a ring which includes the nitrogen atom of the tertiary amino group. Such a ring can be, for example, a piperidine ring or a morpholine ring.
Die zweiwertigen verbindenden Gruppen X und B sind bevorzugt gradkettige, verzweigte oder cyclische Alkylengruppen mit 1 bis 20 Kohlenstoffatomen, Phenylen- oder Aralkylengruppen mit 7 bis 20 Kohlenstoffatomen, oder zweiwertige Ketten aus 1 bis 20 Methylengruppen, in die neben diesen auch Sauerstoff, Schwefel, Aminogruppen, Alken- oder Alkingruppen oder auch Polyoxyalkylengruppen, insbesondere Polyoxyethylen oder Polyoxypropylengruppen mit 1 bis 50 Oxyalkyleinheiten eingebaut sein können. Besonders bevorzugt ist eine Ethylen- oder Propylengruppe. Die genannten Gruppen können auch weiter substituiert sein, beispielsweise mit Alkyl-, Hydroxyl- und weitern tertiären Aminogruppen.The divalent connecting groups X and B are preferred straight-chain, branched or cyclic alkylene groups with 1 up to 20 carbon atoms, phenylene or aralkylene groups with 7 to 20 carbon atoms, or divalent chains from 1 to 20 methylene groups, in addition to these also oxygen, Sulfur, amino groups, alkene or alkyne groups or also Polyoxyalkylene groups, especially polyoxyethylene or Polyoxypropylene groups with 1 to 50 oxyalkyl units can be installed. An ethylene or Propylene group. The groups mentioned can also continue be substituted, for example with alkyl, hydroxyl and further tertiary amino groups.
Die verbindende Gruppe X kann auch dreiwertig sein und so die
tertiäre Aminogruppe mit zwei Nitrilogruppen verbinden.
Geeignet sind die im vorstehenden Absatz genannten Gruppen,
wenn in ihnen eine weitere freie Valenz anstelle eines
Wasserstoffatoms vorhanden ist. Als Beispiele seien genannt:
Der Rest R2 in der allgemeinen Formel (B) bedeutet eine gesättigte oder ungesättigte Alkylgruppe, bevorzugt mit 1 bis 12 Kohlenstoffatomen, eine Arylgruppe, bevorzugt mit 6 bis 14 Kohlenstoffatomen oder eine Aralkylgruppe, bevorzugt mit 7 bis 15 Kohlenstoffatomen. Diese Gruppen können ihrerseits substituiert sein, beispielsweise mit Hydroxyl-, Amino-, Alkylamino- und Alkoxygruppen, wobei hierin das Alkyl vorzugsweise 1 bis 6 Kohlenstoffatome aufweist. Wenn es sich um eine Alkylgruppe handelt, dann kann diese auch mit ihrem vom Stickstoff abgewandten Ende unter Bildung eines Ringes an ein Kohlenstoffatom der Gruppe B gebunden sein. Ein solcher Ring kann beispielsweise ein Piperidin-, Pyrrolidin- oder Hexahydroazepinring sein. Die beiden Reste R2 können auch gemeinsam mit B oder mit Teilen von B und mit den beiden Stickstoffatomen einen oder zwei gesättigte Ringe, vorzugsweise mit 5 oder 6 Gliedern, bilden, zum Beispiel Pyrrolidin- oder Piperidinringe.The radical R 2 in the general formula (B) denotes a saturated or unsaturated alkyl group, preferably having 1 to 12 carbon atoms, an aryl group, preferably having 6 to 14 carbon atoms or an aralkyl group, preferably having 7 to 15 carbon atoms. These groups can in turn be substituted, for example with hydroxyl, amino, alkylamino and alkoxy groups, the alkyl preferably having 1 to 6 carbon atoms. If it is an alkyl group, it can also be attached to a carbon atom of group B with its end facing away from the nitrogen, forming a ring. Such a ring can be, for example, a piperidine, pyrrolidine or hexahydroazepine ring. The two radicals R 2 can also form together with B or with parts of B and with the two nitrogen atoms one or two saturated rings, preferably with 5 or 6 members, for example pyrrolidine or piperidine rings.
In der allgemeinen Formel (A) ist n entweder 1 oder 2.In the general formula (A), n is either 1 or 2.
Da die erfindungsgemäßen kontraststeigernden Verbindungen in ihrem Molekül mindestens eine tertiäre Aminogruppe aufweisen, können sie sowohl in Form des freien Amins als auch in Form eines Salzes, d.h. eines Addukts aus einer Säure und dem freien Amin, hergestellt, gehandhabt und verwendet werden. Eine bevorzugte Säure ist Salzsäure.Since the contrast-increasing compounds according to the invention in have at least one tertiary amino group in their molecule, They can be in the form of the free amine as well as in the form a salt, i.e. an adduct of an acid and that free amine, produced, handled and used. A preferred acid is hydrochloric acid.
Erfindungsgemäße kontraststeigernde Verbindungen lassen sich aus leicht zugänglichen und kostengünstigen Ausgangsstoffen herstellen. Geeignete Verfahren kann der Fachmann anhand der Standardwerke zur präparativen organischen Chemie auffinden, beispielsweise die Einführung einer Cyanomethylgruppe mittels Chloracetonitril, die Alkylierung von Cyaniden (Houben-Weyl, Methoden der organischen Chemie, 4. Auflage, Band 8 (1952), Seiten 290 ff.) und die Entwässerung von Carbonsäureamiden (ebenda, Seiten 330 ff.). Weitere Möglichkeiten der Synthese sind die Alkylierung des Anions einer geeigneten CH-aziden Verbindung, wie Malonsäuredinitril, mit Aminohalogenalkanen und die Umsetzung von Ketonen mit Cyaniden zu Cyanhydrinen. Mehrere der erfindungsgemäßen Verbindungen sind auch preisgünstig im Handel erhältlich.Contrast-increasing compounds according to the invention can be from easily accessible and inexpensive raw materials produce. The person skilled in the art can use the Find standard works on preparative organic chemistry, for example the introduction of a cyanomethyl group Chloroacetonitrile, the alkylation of cyanides (Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 8 (1952), Pages 290 ff.) And the drainage of carboxamides (ibid., pages 330 ff.). Other possibilities of synthesis are the alkylation of the anion of a suitable CH-azide Compound such as malononitrile with aminohalogen alkanes and the conversion of ketones with cyanides to cyanohydrins. Several of the compounds of the invention are also reasonably priced in stores.
Beispiele für erfindungsgemäße kontraststeigernde Verbindungen
sind:
Das erfindungsgemäße Aufzeichnungsmaterial enthält eine Hydrazinverbindung. Diese Hydrazinverbindung kann in an sich bekannter Weise entweder in eine oder mehrere Schichten des Aufzeichnungsmaterials inkorporiert werden. Dies können sowohl Schichten sein, welche das lichtempfindliche Silberhalogenid enthalten, als auch Schichten, die mit den erstgenannten in reaktiver Verbindung stehen, d. h. die so angeordnet sind, daß Stoffe von einer in die andere Schicht diffundieren können, wenn durch Reaktionen ein Konzentrationsgefälle aufrechterhalten wird.The recording material according to the invention contains a Hydrazine compound. This hydrazine compound can in itself known way either in one or more layers of Recording material can be incorporated. This can be both Layers which are the photosensitive silver halide contain, as well as layers with the former in reactive connection, d. H. which are arranged so that Can diffuse substances from one layer to the other, if a concentration gradient through reactions is maintained.
Geeignete Hydrazinverbindungen sind beispielsweise beschrieben
in Research Disclosure 235 010 (November 1983),
DE-27 25 743-A1, EP-00 32 456-B1, EP-01 26 000-A2,
EP-01 38 200-A2, EP-02 03 521-A2, EP-02 17 310-A2,
EP-02 53 665-A2, EP-03 24 391-A2, EP-03 24 426-A2,
EP-03 26 443-A2, EP-03 56 898-A2, EP-04 73 342-A1,
EP-05 01 546-A1, EP-04 81 565-A , EP-05 98 315-A1,
EP-04 44 506.Suitable hydrazine compounds are described, for example, in Research Disclosure 235 010 (November 1983),
DE-27 25 743-A1, EP-00 32 456-B1, EP-01 26 000-A2, EP-01 38 200-A2, EP-02 03 521-A2, EP-02 17 310-A2, EP- 02 53 665-A2, EP-03 24 391-A2, EP-03 24 426-A2, EP-03 26 443-A2, EP-03 56 898-A2, EP-04 73 342-A1, EP-05 01 546-A1, EP-04 81 565-A, EP-05 98 315-A1, EP-04 44 506.
Bevorzugte Hydrazinverbindungen sind durch die allgemeine
Formel (H) beschrieben:
Hierin bedeuten B eine Ballastgruppe, G eine aktivierende Gruppe und L eine der Gruppen -CO- und -CO-CO-. "Phenyl" bedeutet einen Benzolring, an den B und die Hydrazingruppe gebunden sind, und zwar bevorzugt in Para-Stellung.Here B is a ballast group, G is an activating group Group and L one of the groups -CO- and -CO-CO-. "Phenyl" means a benzene ring on the B and the hydrazine group are bound, preferably in the para position.
Bevorzugte Ballastgruppen sind jene, die nicht elektronenanziehend sind, beispielsweise gerade oder verzweigte Alkylgruppen, (z. B. Methyl, Ethyl, n-Propyl, Isopropyl, n-Butyl, Isobutyl, n-Hexyl, n-Octyl, t-Octyl, n-Decyl, n-Dodecyl und ähnliche Gruppen), auch Alkoxygruppen, die als Alkyl eine der oben genannten Alkylgruppen enthalten, sowie Acylaminogruppen, wie Acetylamino, Propanoylamino, Butanoylamino, Octanoylamino, Benzoylamino, Alkyl- und Arylsulfonamido- und ähnliche Gruppen.Preferred ballast groups are those that are not are electron-attracting, for example straight or branched alkyl groups (e.g. methyl, ethyl, n-propyl, Isopropyl, n-butyl, isobutyl, n-hexyl, n-octyl, t-octyl, n-decyl, n-dodecyl and similar groups), also alkoxy groups, which contain one of the alkyl groups mentioned above as alkyl, as well as acylamino groups, such as acetylamino, propanoylamino, Butanoylamino, octanoylamino, benzoylamino, alkyl and Arylsulfonamido and similar groups.
Die genannten Gruppen können ihrerseits mit herkömmlichen photographischen Ballastgruppen substituiert sein, wie sie von inkorporierten diffusionsfesten Kupplern und anderen immobilisierten photographischen Zusätzen bekannt sind. Solche Ballastgruppen enthalten typischerweise mindestens 8 Kohlenstoffatome und können aus relativ reaktionsträgen aliphatischen oder aromatischen Gruppen ausgewählt werden, beispielsweise Alkyl, Alkoxy, Phenyl, Alkylphenyl, Phenoxy, Alkylphenoxy, Arylacyl, Arylamido, Alkylpyridinium-1-ylamido und ähnlichen Gruppen.The groups mentioned can in turn be used with conventional photographic ballast groups as substituted by incorporated diffusion-proof couplers and others immobilized photographic additives are known. Such Ballast groups typically contain at least 8 Carbon atoms and can be made of relatively inert aliphatic or aromatic groups are selected, for example alkyl, alkoxy, phenyl, alkylphenyl, phenoxy, Alkylphenoxy, arylacyl, arylamido, alkylpyridinium-1-ylamido and similar groups.
Die Alkyl- und Alkoxygruppen enthalten einschließlich etwaiger Ballastgruppen vorzugsweise 1 bis 20, die Acylaminogruppen vorzugsweise 2 bis 21 Kohlenstoffatome. Es können aber bis zu 30 oder mehr Kohlenstoffatome in diesen Gruppen enthalten sein. Besonders bevorzugt sind Methoxyphenyl, Tolyl, ballastiertes Butyramidophenyl, Butylsulfonamido und Toluylsulfonamido.The alkyl and alkoxy groups include any Ballast groups preferably 1 to 20, the acylamino groups preferably 2 to 21 carbon atoms. But it can be up to Contain 30 or more carbon atoms in these groups be. Methoxyphenyl, tolyl, ballasted butyramidophenyl, butylsulfonamido and Toluylsulfonamido.
Zu den bevorzugten Hydrazinverbindungen gehören jene, deren Ballastgruppe noch eine adsorptionsfördernde Gruppe enthält. Solche Gruppen fördern die Adsorption des Moleküls an der Oberfläche der Silberhalogenidkristalle und sind an sich bekannt. Sie enthalten typischerweise wenigstens ein Schwefel- oder Stickstoffatom, das einen Silberkomplex bilden kann oder sonst eine Affinität zur Silberhalogenidoberfläche hat. Bevorzugte Beispiele sind Thioharnstoff-, Thiuronium-, heterozyklische Thioamid- und Triazolgruppen.Preferred hydrazine compounds include those whose Ballast group still contains an adsorption promoting group. Such groups promote the adsorption of the molecule on the Surface of the silver halide crystals and are in themselves known. They typically contain at least one sulfur or Nitrogen atom which can form a silver complex or otherwise has an affinity for the silver halide surface. Preferred examples are thiourea, thiuronium, heterocyclic thioamide and triazole groups.
G ist vorzugsweise Wasserstoff, ggf. substituiertes Alkyl (z.B. Methyl, Hydroxymethyl, Monofluormethyl, Pyridinomethyl, Phenoxymethyl, Alkoxymethyl wie Methoxymethyl), ggf. substituiertes Aralkyl (z.B. Benzyl, o-Hydroxybenzyl) und ggf. substituiertes Aryl (z.B. Phenyl, 3,5-Dichlorphenyl, o-Methansulfonamidophenyl, 4-Methansulfonylmethyl, 2-Hydroxymethylphenyl), wobei Alkylgruppen mit elektronenanziehenden Substituenten, beispielsweise kationischen Gruppen mit quaternärem Stickstoffatom, wie Pyridinium und Imidazolium, besonders bevorzugt sind.G is preferably hydrogen, optionally substituted alkyl (e.g. methyl, hydroxymethyl, monofluoromethyl, pyridinomethyl, Phenoxymethyl, alkoxymethyl such as methoxymethyl), if appropriate substituted aralkyl (e.g. benzyl, o-hydroxybenzyl) and possibly substituted aryl (e.g. phenyl, 3,5-dichlorophenyl, o-methanesulfonamidophenyl, 4-methanesulfonylmethyl, 2-hydroxymethylphenyl), alkyl groups with electron-withdrawing substituents, for example cationic groups with quaternary nitrogen atom, such as Pyridinium and Imidazolium, are particularly preferred.
G kann auch weiter substituiert sein, z. B. mit Alkyl, Aralkyl, Alkenyl, Alkinyl, Alkoxy, Aryl, substituiertem Amino, Ureido, Urethan, Aryloxy, Sulfamoyl, Carbamoyl, Alkyl- oder Arylthio, Alkyl- oder Arylsulfonyl, Alkyl- oder Arylsulfinyl, Hydroxy, Halogen, Cyan, Sulfo, Aryloxycarbonyl, Acyl, Alkoxycarbonyl, Acyloxy, Carbamid, Sulfonamid, Carboxyl, Phosphamid, Diacylamino, Imid.G can also be further substituted, e.g. B. with alkyl, Aralkyl, alkenyl, alkynyl, alkoxy, aryl, substituted amino, Ureido, urethane, aryloxy, sulfamoyl, carbamoyl, alkyl or Arylthio, alkyl- or arylsulfonyl, alkyl- or arylsulfinyl, Hydroxy, halogen, cyan, sulfo, aryloxycarbonyl, acyl, Alkoxycarbonyl, acyloxy, carbamide, sulfonamide, carboxyl, Phosphamide, diacylamino, imide.
G kann auch so gewählt werden, daß das L-G-Teil des Moleküls unter Ringbildung abgetrennt wird, wie dies z.B. in EP-B-02 53 665 beschrieben ist.G can also be chosen so that the L-G part of the molecule is separated to form a ring, as is e.g. in EP-B-02 53 665 is described.
Beispiele geeigneter Hydrazinverbindungen sind
OTS- ist das Anion der o-Toluolsulfonsäure.OTS - is the anion of o-toluenesulfonic acid.
Die lichtempfindlichen Silberhalogenide der erfindungsgemäß verwendeten Aufzeichnungsmaterialien bestehen aus Silberchlorid, Silberbromid, Silberchlorobromid, Silberbromoiodid oder Silberchlorobromoiodid. Sie können monodispers oder polydispers sein, eine einheitliche Zusammensetzung haben, aber auch Körner mit Kern-Schale-Aufbau aufweisen, sowie auch Gemische von Körnern verschiedener Zusammensetzung und Korngrößenverteilung sein. Sie werden unter Verwendung eines hydrophilen kolloidalen Bindemittels, bevorzugt Gelatine, hergestellt. Die Silberhalogenidkörner können sphärische, polyedrische oder tafelförmige Gestalt haben. Methoden zur Herstellung geeigneter lichtempfindlicher Silberhalogenidemulsionen sind dem Fachmann bekannt und beispielsweise in der Research Disclosure 365 044, Kapitel I bis IV (September 1994) zusammengefaßt.The light-sensitive silver halides of the invention recording materials used consist of Silver chloride, silver bromide, silver chlorobromide, Silver bromoiodide or silver chlorobromoiodide. You can be monodisperse or polydisperse, a uniform Have composition, but also grains with core-shell structure have, as well as mixtures of grains of different Composition and grain size distribution. you will be using a hydrophilic colloidal binder, preferably gelatin. The silver halide grains can be spherical, polyhedral or tabular to have. Methods of making suitable photosensitive Silver halide emulsions are known to the person skilled in the art and for example in Research Disclosure 365 044, Chapter I to IV (September 1994).
Bevorzugt für die erfindungsgemäß verwendeten Aufzeichnungsmaterialien werden Silberhalogenidemulsionen, die durch kontrollierten Doppelstrahleinlauf hergestellt werden und eine kubische Kornform haben. Vorteilhaft sind Emulsionen, bei denen mindestens 80 Gewichtsprozent des Silberhalogenids in kubischer Form vorliegen. Besonders bevorzugt sind monodisperse Emulsionen, d. h. solche, bei denen der Variationskoeffizient (Quotient aus Standardabweichung und Mittelwert) der Korngröße kleiner als 0,30 ist. Unter Korngröße wird die Kantenlänge eines mit dem wirklichen Korn volumengleichen Würfels verstanden.Preferred for those used according to the invention Recording materials are silver halide emulsions that be produced by controlled double jet inlet and have a cubic grain shape. Emulsions are advantageous in which at least 80 percent by weight of the silver halide are available in cubic form. Are particularly preferred monodisperse emulsions, i.e. H. those where the Coefficient of variation (quotient of standard deviation and Mean) the grain size is less than 0.30. Under Grain size becomes the edge length of one with the real grain volume equal cube understood.
Das Kornvolumen der Silberhalogenidkörner in den Emulsionen richtet sich nach der erforderlichen Empfindlichkeit und kann beispielsweise dem kubischer Körner von 0,1 bis 0,7 µm Kantenlänge entsprechen. Ein bevorzugter Bereich liegt zwischen 0,15 und 0,30 µm. Bei der Emulsionsherstellung können Edelmetallsalze, besonders Salze von Rhodium oder Iridium, zur Steuerung der photographischen Eigenschaften in den üblichen Mengen anwesend sein.The grain volume of the silver halide grains in the emulsions depends on the required sensitivity and can for example the cubic grain from 0.1 to 0.7 µm Edge length. A preferred range is between 0.15 and 0.30 µm. When making emulsions Precious metal salts, especially salts of rhodium or iridium, for Control of photographic properties in the usual Be present in large quantities.
Die Emulsionen werden bevorzugt chemisch sensibilisiert. Geeignete Verfahren sind die Schwefel-, die Reduktions- und die Edelmetallsensibilisierung, die auch in Kombination angewendet werden können. Für letztere können beispielsweise Gold- oder Iridiumverbindungen benutzt werden. Die Sensibilisierung wird bevorzugt in Gegenwart von Salzen organischer Thiosulfonsäuren, wie der p-Toluolthiosulfonsäure, durchgeführt.The emulsions are preferably chemically sensitized. Suitable processes are the sulfur, the reduction and the precious metal sensitization, also in combination can be applied. For the latter, for example Gold or iridium compounds can be used. The Sensitization is preferred in the presence of salts organic thiosulfonic acids, such as p-toluenesulfonic acid, carried out.
Die Emulsionen können mit üblichen Sensibilisierungsfarbstoffen spektral sensibilisiert werden, wie beispielsweise in Research Disclosure 365 044, Kapitel V (September 1994), beschrieben.The emulsions can be mixed with usual Sensitizing dyes are spectrally sensitized, such as in Research Disclosure 365 044, Chapter V (September 1994).
Die Emulsionen können auch übliche Antischleiermittel enthalten. Bevorzugt sind ggf. substituiertes Benztriazol, 5-Nitroindazol und 1-Phenyl-5-mercaptotetrazol. Diese Mittel können zu jedem Zeitpunkt bei der Emulsionsherstellung zugesetzt werden oder in einer Hilfsschicht des photographischen Materials enthalten sein. Zur Verbesserung der photographischen Eigenschaften kann der Emulsion vor oder nach der chemischen Reifung ein Jodid, vorzugsweise ein Alkalijodid, in einer Menge von etwa 0,5 bis 5 mmol je Mol Silber zugesetzt werden.The emulsions can also be conventional antifoggants contain. Substituted benzotriazole are preferred, 5-nitroindazole and 1-phenyl-5-mercaptotetrazole. This means can be used at any time during emulsion production be added or in an auxiliary layer of the photographic material may be included. For improvement the photographic properties can before or the emulsion after chemical ripening an iodide, preferably a Alkali iodide, in an amount of about 0.5 to 5 mmol per mole Silver can be added.
Die Emulsionen können auch bekannte Polymerdispersionen enthalten, durch die beispielsweise die Dimensionsstabilität des photographischen Materials verbessert wird. Es handelt sich dabei in der Regel um Latices hydrophober Polymere in wäßriger Matrix. Beispiele für geeignete Polymerdispersionen sind in der Research Disclosure 176 043, Kapitel IX B (Dezember 1978) genannt. Bevorzugt werden Polymere von Estern der Acryl- und der Methacrylsäure, besonders bevorzugt von C1- bis C6-Estern. Die Teilchengröße dieser Polymerlatices liegt bevorzugt zwischen 20 und 100 nm.The emulsions can also contain known polymer dispersions which, for example, improve the dimensional stability of the photographic material. These are generally latices of hydrophobic polymers in an aqueous matrix. Examples of suitable polymer dispersions are mentioned in Research Disclosure 176 043, Chapter IX B (December 1978). Polymers of esters of acrylic and methacrylic acid are preferred, particularly preferably of C 1 to C 6 esters. The particle size of these polymer latices is preferably between 20 and 100 nm.
Die lichtempfindlichen Schichten der photographischen Materialien können durch Zusatz eines Härtungsmittels gehärtet sein. Härtungsmittel sind beispielsweise in der Research Disclosure 365 044, Kapitel II B (September 1994) genannt. Dieses Härtemittel kann der Emulsion zugesetzt oder über eine Hilfsschicht beispielsweise eine äußere Schutzschicht, eingebracht werden. Geeignete Härtemittel sind beispielsweise Aldehyde, wie Formaldehyd oder Glutaraldehyd, Vinylsulfone, s-Triazine, Aziridine, Carbodiimide, Carbamoylpyridiniumverbindungen, mono- und bifunktionelle Carbamoylimidazoliumverbindungen. Ein bevorzugtes Härtungsmittel ist Hydroxydichlorotriazin.The photosensitive layers of the photographic Materials can be hardened by adding a hardening agent be. For example, hardeners are in research Disclosure 365 044, Chapter II B (September 1994). This hardener can be added to the emulsion or via a Auxiliary layer, for example an outer protective layer, be introduced. Suitable hardeners are, for example Aldehydes, such as formaldehyde or glutaraldehyde, vinyl sulfones, s-triazines, aziridines, carbodiimides, carbamoylpyridinium compounds, mono- and bifunctional carbamoylimidazolium compounds. A preferred curing agent is Hydroxydichlorotriazine.
Das photographische Material kann weitere Zusätze, die für die Erzeugung bestimmter Eigenschaften bekannt und üblich sind, enthalten. Solche Mittel sind zum Beispiel in der Research Disclosure 365 044 (September 1994) in den Kapiteln VI (Aufheller), IX A (Beschichtungshilfsmittel), IX B (Weichmacher und Gleitmittel) und IX D (Mattierungsmittel) aufgeführt.The photographic material can be further additives for the Generation of certain properties are known and common, contain. Such funds are, for example, in research Disclosure 365 044 (September 1994) in Chapter VI (Brightener), IX A (coating aid), IX B (Plasticizers and lubricants) and IX D (matting agents) listed.
Der Gelatinegehalt der Emulsionen liegt im allgemeinen zwischen 30 und 150 g je mol Silber; bevorzugt wird der Bereich zwischen 40 und 100 g je mol Silber.The gelatin content of the emulsions is in general between 30 and 150 g per mole of silver; the is preferred Range between 40 and 100 g per mol of silver.
Zur Erfindung gehört auch ein Verfahren für die Herstellung schwarz-weißer negativer photographischer Bilder, welches dadurch gekennzeichnet ist, daß man ein vorgehend beschriebenes lichtempfindliches Aufzeichnungsmaterial bildmäßig belichtet, in einer wäßrigen Entwicklerlösung entwickelt, in üblicher Weise fixiert, wässert und trocknet. The invention also includes a method for the production black and white negative photographic images, which is characterized by having a preliminary described light-sensitive material exposed imagewise in an aqueous developer solution developed, fixed in the usual way, watered and dried.
Die erfindungsgemäß verwendeten Entwicklerlösungen enthalten bevorzugt eine Dihydroxybenzol-Entwicklersubstanz, beispielsweise Hydrochinon, Brenzkatechin, Methylhydrochinon oder Chlorhydrochinon, und ein Oxydationsschutzmittel, bevorzugt ein Alkalisulfit in einer Konzentration von mehr als 0,3 mol je Liter. Besonders bevorzugt werden Lösungen mit pH-Werten von 9 bis höchstens 11. Solche Entwicklerlösungen sind auch im Gebrauch gut haltbar und ergeben weitgehend schleierfreie Bilder. Ebenfalls verwendbar sind Entwicklerlösungen mit einer Entwicklersubstanz vom Ascorbinsäuretyp, beispielsweise L-Ascorbinsäure, D-Ascorbinsäure, L-Erythroascorbinsäure, 6-Desoxy-L-ascorbinsäure, Imino-L-erythroascorbinsäure oder Zuckerderivate dieser Säuren. Geeignet sind auch Entwicklerlösungen, die sowohl Entwicklersubstanzen vom Dihydroxybenzol-Typ als auch solche vom Ascorbinsäuretyp enthalten.The developer solutions used according to the invention contain preferably a dihydroxybenzene developer substance, for example hydroquinone, pyrocatechol, methylhydroquinone or chlorohydroquinone, and an antioxidant, preferably an alkali sulfite in a concentration of more than 0.3 mol per liter. Solutions with are particularly preferred pH values from 9 to a maximum of 11. Such developer solutions are also durable in use and largely result fog-free images. Are also usable Developer solutions with a developer substance from Ascorbic acid type, for example L-ascorbic acid, D-ascorbic acid, L-erythroascorbic acid, 6-deoxy-L-ascorbic acid, Imino-L-erythroascorbic acid or Sugar derivatives of these acids. Are also suitable Developer solutions that both developer substances from Dihydroxybenzene type as well as those of the ascorbic acid type contain.
Bevorzugt enthalten die Entwicklerlösungen bekannte superadditiv wirkende Hilfsentwicklersubstanzen, beispielsweise N-Methyl-p-aminophenol oder 1-Phenylpyrazolidinon-3 oder Derivate dieser Verbindungen.The developer solutions preferably contain known solutions super-additive auxiliary developer substances, for example N-methyl-p-aminophenol or 1-phenylpyrazolidinone-3 or derivatives of these compounds.
Ebenfalls bevorzugt sind Entwickler, die Stabilisatoren aus den Gruppen der Benztriazole und Mercaptotetrazole enthalten. Solche Stabilisatoren sind beispielsweise 1-Phenyl-5-mercaptotetrazol, 1-(4-Hydroxyphenyl)-5-mercaptotetrazol, 1-(1-Naphthyl)-5-mercaptotetrazol, 1-Cyclohexyl-5-mercaptotetrazol, 1-(4-Chlorphenyl)-5-mercaptotetrazol, 1-(3-Capramidophenyl)-5-mercaptotetrazol, Benztriazol, 5-Chlorbenztriazol, 5-Brombenztriazol, 5-Methylbenztriazol, 5-Nitrobenztriazol, 5-Benzoylaminobenztriazol, 1-Hydroxymethylbenztriazol, 6-Cyanobenztriazol.Also preferred are developers that consist of stabilizers contain the groups of benzotriazoles and mercaptotetrazoles. Such stabilizers are, for example 1-phenyl-5-mercaptotetrazole, 1- (4-hydroxyphenyl) -5-mercaptotetrazole, 1- (1-naphthyl) -5-mercaptotetrazole, 1-cyclohexyl-5-mercaptotetrazole, 1- (4-chlorophenyl) -5- mercaptotetrazole, 1- (3-capramidophenyl) -5-mercaptotetrazole, benzotriazole, 5-chlorobenzotriazole, 5-bromobenzotriazole, 5-methylbenztriazole, 5-nitrobenztriazole, 5-benzoylaminobenztriazole, 1-hydroxymethylbenztriazole, 6-cyanobenztriazole.
Bei dem erfindungsgemäßen Verfahren ist die Verwendung von Alkanolaminen nach dem Stand der Technik entweder völlig entbehrlich oder ihre Menge kann auf einen geringen Bruchteil vermindert werden. Dadurch arbeitet das Verfahren ohne störende oder schädliche Geruchsbelästigung und die Korrosion durch aus dem Entwickler sich verflüchtigende Aminoverbindungen wird vermieden.In the method according to the invention, the use of State of the art alkanolamines either completely dispensable or their amount can be a small fraction can be reduced. As a result, the process works without annoying or harmful smell and the corrosion by evaporating from the developer Amino compounds are avoided.
Die erfindungsgemäßen kontraststeigernden Verbindungen können der Emulsion in jedem Stadium der Herstellung zugesetzt werden. Aufgrund ihrer Molekülstruktur können sie sowohl oberflächenaktiv sein als auch mit ionischen Polymeren in Wechselwirkung treten. Die Nitrilgruppe verleiht den Verbindungen hydrophile Eigenschaften. Dagegen haben die im Molekül ebenfalls vorhandenen Kohlenwasserstoffgruppen eine hydrophobe und diffusionshemmende Wirkung. Es ist daher möglich, durch Auswahl der Zahl der Nitrilgruppen, der Zahl und Art der Kohlenwasserstoffgruppen und ggf. weiterer hydrophiler Gruppen, wie beispielsweise Ethylenoxidgruppen, Wasserlöslichkeit, Grenzflächenaktivität und Diffusionsfähigkeit der Verbindungen auf den jeweiligen Anwendungszweck abzustimmen.The contrast-enhancing compounds according to the invention can added to the emulsion at every stage of manufacture will. Because of their molecular structure, they can both be surface active as well as with ionic polymers Interaction. The nitrile group gives the Compounds hydrophilic properties. In contrast, in Molecule also present hydrocarbon groups hydrophobic and diffusion-inhibiting effect. It is therefore possible by selecting the number of nitrile groups, the number and type of hydrocarbon groups and possibly other hydrophilic groups such as ethylene oxide groups Water solubility, interfacial activity and Diffusibility of the connections on the respective To coordinate the application.
Vorteilhaft bei den erfindungsgemäßen Verbindungen ist weiterhin, daß sie in den alkalischen Entwicklerbädern zu photographisch inaktiven Folgeprodukten zersetzt werden. Sie reichern sich daher nicht - wie andere bekannte im Aufzeichnungsmaterial inkorporierte kontraststeigernde Verbindungen - infolge Auswaschens im Entwickler an. Daher beeinträchtigen sie die Stabilität der Entwickleraktivität nicht, selbst wenn sie nur in geringem Maße diffusionsgehemmt (ballastiert) sind.It is advantageous for the compounds according to the invention further that they are in the alkaline developer baths too photographically inactive secondary products are decomposed. she therefore do not enrich themselves - like other well-known in Recording material incorporated contrast-enhancing Connections - as a result of washing out in the developer. Therefore they affect the stability of developer activity not even if they are only slightly diffusion inhibited (ballasted).
Die Erfindung kann zur Erzeugung von schwarz-weißen Negativbildern mit ultrasteilem Kontrast, insbesondere bei der Reproduktion in der Druckvorstufe für den Schwarz-Weiß- und Mehrfarbdruck, angewendet werden. Sie wird durch das folgende Ausführungsbeispiel näher erläutert.The invention can be used to produce black and white Negative images with ultra-partial contrast, especially in the Reproduction in prepress for the black and white and Multi-color printing. It is through the following Embodiment explained in more detail.
Durch pAg-geregelten Zweistrahleinlauf in Gegenwart eines Rhodiumsalzes wurde eine kubische Silberchlorobromidemulsion (80 Molprozent Chlorid) hergestellt, deren Körner eine Kantenlänge von 0,21 µm hatten. Nach der Entfernung der löslichen Salze mittels des Flockverfahrens wurde auf einen Gesamtgelatinegehalt von 55 g je mol Silber eingestellt und eine chemische Reifung mit Kaliumthiotosylat, Thiosulfat und Goldsalz durchgeführt. Danach wurden noch Kaliumiodid (1,6 mmol/mol Ag), Phenylmercaptotetrazol, 5-Nitroindazol, ein Polyethylenlatex, ein Sensibilisator für den grünen Spektralbereich, zwei Beschichtungshilfsmittel (Triton® X-102, Triton® X-200; Hersteller: Rohm & Haas), 0,12 mmol 1-Pyridiniumacetyl-2-(4-benzyloxyphenyl)hydrazinbromid (Verbindung H-9) je mol Silber und 0,10 mmol Dichlorohydroxytriazin-Natriumsalz je g Gelatine zugesetzt. Durch Auftragen der Emulsion zusammen mit Übergüssen, die Gelatine, Mattierungsmittel, Netzmittel (Triton® X-200) und Zusätze nach Tabelle 1 enthielten, wurden Kamerafilme hergestellt. Der Silberauftrag betrug 4,2 g/m2, der Übergußauftrag 0,9 g Gelatine je m2.A cubic silver chlorobromide emulsion (80 mole percent chloride) was produced by pAg-controlled two-jet inlet in the presence of a rhodium salt, the grains of which had an edge length of 0.21 μm. After the soluble salts had been removed by means of the flocking process, the total gelatin content was 55 g per mol of silver and chemical ripening was carried out using potassium thiotosylate, thiosulfate and gold salt. Then potassium iodide (1.6 mmol / mol Ag), phenyl mercaptotetrazole, 5-nitroindazole, a polyethylene latex, a sensitizer for the green spectral range, two coating aids (Triton® X-102, Triton® X-200; manufacturer: Rohm & Haas ), 0.12 mmol of 1-pyridiniumacetyl-2- (4-benzyloxyphenyl) hydrazine bromide (compound H-9) per mol of silver and 0.10 mmol of dichlorohydroxytriazine sodium salt per g of gelatin were added. Camera films were produced by applying the emulsion together with overcasts containing gelatin, matting agent, wetting agent (Triton® X-200) and additives according to Table 1. The silver application was 4.2 g / m 2 , the pouring application 0.9 g gelatin per m 2 .
Als Vergleichsverbindungen wurden verwendet:
Probestreifen der erhaltenen Aufzeichnungsmaterialien wurden
durch eine Vorlage aus einem Dichteverlaufskeil, der teilweise
mit einem Kontaktraster unterlegt war, mit Weißlicht
belichtet. Die Streifen wurden in einer Entwicklungsmaschine
(Dürr Graphica) bei 36 °C entwickelt, fixiert, gewässert und
getrocknet. Die Entwicklungszeit betrug 28 s. Es wurde ein
handelsübliches Fixierbad verwendet. Der Entwickler hatte
folgende Zusammensetzung:
Die verarbeiteten Streifen wurden nach folgenden Kriterien
ausgewertet: Minimaldichte Dmin, Maximaldichte Dmax,
Empfindlichkeit S als Dichte des Vorlagen-Verlaufskeils an der
Stelle, die im Rasterbild den Tonwert 50% ergab, Fußgradation
G1 zwischen den Dichtewerten D = 0,1 und 0,4 im Halbtonbild,
Hauptgradation G2 zwischen D = 1,0 und 2,5 sowie eine visuelle
Bewertung der Punktqualität PQ der Rasterpunkte. Die Bewertung
10 bedeutet optimale Schärfe der Punkte, 4 - 5 ist nur bedingt
brauchbar und entspricht der Schärfe eines Rapid Access Films
ohne Kontrastverstärkung, 1 - 3 ist unbrauchbar. Die
Ergebnisse sind in Tabelle 1 zusammengefaßt.
Claims (9)
- Light sensitive silver halide recording material, in particular for preparing black-and-white negative images having ultrahigh contrast, comprising at least one light sensitive layer on at least one side of a substrate and optionally other layers on the same side of the substrate, which contain in the light sensitive layer or in a layer being reactively related to to this layer at least one hydrazine compound,
characterized in that
it contains in this layer or in a layer reactively related to it at least one contrast enhancing compound which has in its molecule at least one tertiary amino group and at least one nitrilo group. - Light sensitive silver halide recording material according to claim 1,
characterized in that
the contrast enhancing compound falls under one of the general formulae (A), (B) or (C)- R, R1
- equal or different each an optionally substituted alkyl group having 1 to 6 carbon atoms or an optionally substituted benzyl group, or R and R1 form a five- or six-membered ring together with the nitrogen atom and optionally with an additional oxygen atom,
- R2
- a saturated or unsaturated alkyl group or an aryl group, these groups can be further substituted, also one alkyl group may be bound with its end away from the nitrogen atom to a carbon atom of group B, thus forming a ring,
- X
- a divalent or trivalent linking group,
- B
- a divalent linking group,
- n
- 1 or 2.
- Light sensitive silver halide recording material according to claim 1 or 2,
characterized in that
the hydrazine compound has the general formula (H) - Light sensitive silver halide recording material according to one of claims 1 to 3,
characterized in that
it contains the contrast enhancing compound in an amount from 0,05 to 5 g per mole of silver. - Light sensitive silver halide recording material according to one of claims 1 to 4,
characterized in that
more than 80 weight percent of the emulsion silver halide consist of cubic grains. - Light sensitive silver halide recording material according to one of claims 1 to 5,
characterized in that
the emulsion silver halide has an average grain size of 0,15 to 0,30 µm. - Light sensitive silver halide recording material according to one of claims 1 to 6,
characterized in that
the emulsion silver halide is monodisperse. - Method for producing a black-and-white negative image having ultrahigh contrast,
characterized in that
a recording material according to one of claims 1 to 4 is exposed and developed in a dedveloper having a pH between 9 and 11. - Method according to claim 8,
characterized in that
the developer contains more than 0,30 mole sulphite per liter.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19515619A DE19515619A1 (en) | 1995-04-28 | 1995-04-28 | Silver halide recording material for producing negative images with ultra-contrast contrast |
| DE19515619 | 1995-04-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0740194A1 EP0740194A1 (en) | 1996-10-30 |
| EP0740194B1 true EP0740194B1 (en) | 1998-04-01 |
Family
ID=7760576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP96106510A Expired - Lifetime EP0740194B1 (en) | 1995-04-28 | 1996-04-25 | Silver halide containing material for making negative images having ultrahigh contrast |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5663034A (en) |
| EP (1) | EP0740194B1 (en) |
| JP (1) | JP3668554B2 (en) |
| DE (2) | DE19515619A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19618196A1 (en) * | 1996-05-07 | 1997-11-13 | Du Pont Deutschland | Silver halide recording material with improved storage stability to produce negative images with ultra-contrast contrast |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4269929A (en) * | 1980-01-14 | 1981-05-26 | Eastman Kodak Company | High contrast development of photographic elements |
| JPS61267759A (en) * | 1985-05-22 | 1986-11-27 | Fuji Photo Film Co Ltd | Formation of negative image |
| JPH0736076B2 (en) * | 1986-03-24 | 1995-04-19 | 富士写真フイルム株式会社 | Silver halide photographic light-sensitive material and image forming method using the same |
| US4975354A (en) * | 1988-10-11 | 1990-12-04 | Eastman Kodak Company | Photographic element comprising an ethyleneoxy-substituted amino compound and process adapted to provide high constrast development |
| JP2704453B2 (en) * | 1989-10-13 | 1998-01-26 | 富士写真フイルム株式会社 | Silver halide photosensitive material |
| US5229248A (en) * | 1990-08-16 | 1993-07-20 | Konica Corporation | Silver halide photographic light sensitive material |
| US5283158A (en) * | 1991-10-31 | 1994-02-01 | Konica Corporation | Silver halide photographic light-sensitive material |
| DE4310327A1 (en) * | 1993-03-30 | 1994-10-06 | Du Pont Deutschland | Method of producing negative images with ultra-contrast contrast |
-
1995
- 1995-04-28 DE DE19515619A patent/DE19515619A1/en not_active Withdrawn
-
1996
- 1996-04-16 US US08/632,859 patent/US5663034A/en not_active Expired - Fee Related
- 1996-04-25 EP EP96106510A patent/EP0740194B1/en not_active Expired - Lifetime
- 1996-04-25 DE DE59600132T patent/DE59600132D1/en not_active Expired - Fee Related
- 1996-04-26 JP JP14059296A patent/JP3668554B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US5663034A (en) | 1997-09-02 |
| DE19515619A1 (en) | 1996-10-31 |
| JP3668554B2 (en) | 2005-07-06 |
| DE59600132D1 (en) | 1998-05-07 |
| JPH08334856A (en) | 1996-12-17 |
| EP0740194A1 (en) | 1996-10-30 |
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