EP0740194A1 - 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
- EP0740194A1 EP0740194A1 EP96106510A EP96106510A EP0740194A1 EP 0740194 A1 EP0740194 A1 EP 0740194A1 EP 96106510 A EP96106510 A EP 96106510A EP 96106510 A EP96106510 A EP 96106510A EP 0740194 A1 EP0740194 A1 EP 0740194A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver halide
- group
- contrast
- groups
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 30
- -1 Silver halide Chemical class 0.000 title claims description 56
- 229910052709 silver Inorganic materials 0.000 title claims description 33
- 239000004332 silver Substances 0.000 title claims description 33
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000839 emulsion Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 125000001302 tertiary amino group Chemical group 0.000 claims description 6
- 125000002560 nitrile group Chemical group 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 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
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 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
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 8
- 125000002648 azanetriyl group Chemical group *N(*)* 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 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
- 239000010410 layer Substances 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
- 239000000654 additive Substances 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 239000003795 chemical substances by application Substances 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
- 150000002429 hydrazines Chemical class 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 class 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
- 150000003254 radicals Chemical class 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
- 238000009792 diffusion process Methods 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
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- 238000002360 preparation method Methods 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 class [O-][N+](=O)C1=CC=C2NN=CC2=C1 WSGURAYTCUVDQL-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
- 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
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 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
- 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
- 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
- 230000005070 ripening Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 230000008313 sensitization Effects 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
- 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
- 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
- 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
- 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
- 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
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- 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
- 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
- 125000003277 amino 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
- 230000001588 bifunctional effect Effects 0.000 description 1
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- 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
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- 239000004202 carbamide Chemical class 0.000 description 1
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- 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
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- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical class CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
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- 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
- 238000001704 evaporation Methods 0.000 description 1
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- 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
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- 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
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect 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
- 125000005647 linker group Chemical group 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
- 229910000510 noble metal Inorganic materials 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
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 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
- 239000004848 polyfunctional curative Substances 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
- 239000010970 precious metal Substances 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
- 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
- 238000007363 ring formation reaction Methods 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 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
- 150000003512 tertiary amines Chemical group 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 for producing black and white negative images with ultra-high contrast and a method for producing a black and white negative image using such a material.
- halftone images In photomechanical reproduction, halftone images often have to be converted into halftone dot images.
- silver halide materials are used, which are used in special processes for ultra-partial contrast, i.e. H. developed to a maximum slope of the density curve of more than 10.
- H. ultra-partial contrast
- the lith process with low-sulfite, formaldehyde-containing hydroquinone developers is known. Development in the presence of hydrazine compounds has recently become of particular practical importance.
- EP-00 32 456-B1 claims a process in which a recording material is processed in the presence of a hydrazine compound with a hydroquinone-3-pyrazolidinone developer which contains a contrast-increasing amount of an amino compound.
- the known developers generally have a pH above 11. They are therefore not sufficiently stable in practice and have a highly corrosive effect on the components of the development machines.
- German Offenlegungsschrift DE-A-43 10 327 describes a process for producing negative images with ultra-partial contrast, in which the silver halide recording material is developed in the presence of compounds whose molecules have at least one quaternary nitrogen atom and at least one tertiary amine function.
- EP-04 73 342-A1 describes a photographic silver halide material that can be developed in a developer with a pH ⁇ 11 to ultra-partial contrast.
- the light-sensitive coating of this material contains a hydrazine compound of a certain formula and an amino or a quaternary onium compound and is adjusted to a pH of at least 5.9.
- the tertiary amino group is realized by a nitrogen atom which is bonded to two organic radicals with single bonds and to the nitrile group via a divalent linking group.
- the contrast-increasing compound falls under one of the general formulas (A), (B) or (C) given below: RR 1 N - X - (CN) n (A) NC - X - NR 2 - B - NR 2 - X - CN (B) RR 1 N - X - N (CH 2 CN) 2 (C)
- 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 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 preferably straight-chain, branched or cyclic alkylene groups with 1 to 20 carbon atoms, phenylene or aralkylene groups with 7 to 20 carbon atoms, or divalent chains from 1 to 20 methylene groups, in which, in addition to these, oxygen, sulfur, amino groups , Alkene or alkyne groups or also polyoxyalkylene groups, in particular polyoxyethylene or polyoxypropylene groups with 1 to 50 oxyalkyl units, can be incorporated.
- An ethylene or propylene group is particularly preferred.
- the groups mentioned can also be further 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 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 have at least one tertiary amino group in their molecule, they can be used both in the form of the free amine and in the form of a salt, i.e. of an adduct of an acid and the free amine can be prepared, handled and used.
- a preferred acid is hydrochloric acid.
- Contrast-increasing compounds according to the invention can be produced from easily accessible and inexpensive starting materials.
- the person skilled in the art can find suitable processes on the basis of the standard works on preparative organic chemistry, For example, the introduction of a cyanomethyl group using chloroacetonitrile, the alkylation of cyanides (Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 8 (1952), pages 290 ff.) and the dehydration of carboxamides (ibid., pages 330 ff.) .
- contrast-increasing compounds are: (C 2 H 5 ) 2 NC 3 H 6 ⁇ CN HCl 1 (i - C 3 H 7 ) 2 NC 2 H 4 ⁇ CN HCl 2 (C 4 H 9 ) 2 NC 2 H 4 ⁇ CN HCl 5 (C 4 H 9 ) 2 NC 3 H 6 ⁇ N (CH 2 CN) 2 7 (C 2 H 5 ) 2 NC 2 H 4 ⁇ O ⁇ C 2 H 4 ⁇ CN 9 (C 2 H 5 ) 2 NC 2 H 4 ⁇ S ⁇ C 2 H 4 ⁇ CN 10
- the recording material according to the invention contains a hydrazine compound.
- This hydrazine compound can be incorporated into one or more layers of the recording material in a manner known per se. These can be both layers which contain the light-sensitive silver halide and layers which are reactive with the former, i. H. which are arranged in such a way that substances can diffuse from one layer to the other if a concentration gradient is maintained by reactions.
- 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 (H)
- B is a ballast group
- G is an activating group
- L is one of the groups -CO- and -CO-CO-.
- Phenyl means a benzene ring to which B and the hydrazine group are attached, preferably in the para position.
- Preferred ballast groups are those that are not electron attractive, 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 above-mentioned alkyl groups as alkyl, and 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,
- the groups mentioned can in turn be substituted with conventional photographic ballast groups, as are known from incorporated diffusion-resistant couplers and other immobilized photographic additives.
- Such bailast groups typically contain at least 8 carbon atoms and can be selected from relatively inert aliphatic or aromatic groups such as alkyl, alkoxy, phenyl, alkylphenyl, phenoxy, alkylphenoxy, arylacyl, arylamido, alkylpyridinium-1-ylamido and similar groups.
- the alkyl and alkoxy groups preferably contain 1 to 20, the acylamino groups preferably 2 to 21 carbon atoms. However, up to 30 or more carbon atoms can be contained in these groups. Methoxyphenyl, tolyl, ballasted butyramidophenyl, butylsulfonamido and tolylsulfonamido are particularly preferred.
- the 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 that can form a silver complex or otherwise have 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), optionally substituted aralkyl (e.g. benzyl, o-hydroxybenzyl) and optionally substituted aryl (e.g.
- alkyl groups with electron-withdrawing substituents for example cationic groups with a quaternary nitrogen atom, such as pyridinium and imidazolium, being particularly preferred.
- 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 off with ring formation, as is the case e.g. in EP-B-02 53 665.
- OTS - is the anion of o-toluenesulfonic acid.
- the light-sensitive silver halides of the recording materials used according to the invention consist of silver chloride, silver bromide, silver chlorobromide, silver bromoiodide or silver chlorobromoiodide. They can be monodisperse or polydisperse, have a uniform composition, but also have grains with a core-shell structure, and can also be mixtures of grains of different composition and grain size distribution. They are made using a hydrophilic colloidal binder, preferably gelatin.
- the silver halide grains can be spherical, polyhedral or tabular in shape. Methods for producing suitable light-sensitive silver halide emulsions are known to the person skilled in the art and are summarized, for example, in Research Disclosure 365 044, chapters I to IV (September 1994).
- Preferred for the recording materials used according to the invention are silver halide emulsions which are produced by controlled double jet entry and have a cubic grain shape. Emulsions in which at least 80 percent by weight of the silver halide are present in cubic form are advantageous. Monodisperse emulsions, ie those in which the coefficient of variation (quotient of standard deviation and mean) of the grain size is less than 0.30, are particularly preferred. Under Grain size is understood to mean the edge length of a cube with the same volume as the real grain.
- the grain volume of the silver halide grains in the emulsions depends on the required sensitivity and can, for example, correspond to the cubic grains with an edge length of 0.1 to 0.7 ⁇ m. A preferred range is between 0.15 and 0.30 ⁇ m.
- Precious metal salts, especially salts of rhodium or iridium, can be present in the usual amounts in the emulsion preparation to control the photographic properties.
- the emulsions are preferably chemically sensitized. Suitable methods are sulfur, reduction and noble metal sensitization, which can also be used in combination. For the latter, for example, gold or iridium compounds can be used.
- the sensitization is preferably carried out in the presence of salts of organic thiosulfonic acids, such as p-toluenesulfonic acid.
- the emulsions can be spectrally sensitized with conventional sensitizing dyes, as described, for example, in Research Disclosure 365 044, Chapter V (September 1994).
- the emulsions can also contain conventional antifoggants.
- Substituted benzotriazole, 5-nitroindazole and 1-phenyl-5-mercaptotetrazole are preferred. These agents can be added at any time during the preparation of the emulsion or can be contained in an auxiliary layer of the photographic material.
- an iodide preferably an alkali iodide, can be added to the emulsion in an amount of about 0.5 to 5 mmol per mole of silver before or after chemical ripening.
- the emulsions can also contain known polymer dispersions which, for example, improve the dimensional stability of the photographic material. It deals usually 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 light-sensitive layers of the photographic materials can be hardened by adding a hardening agent.
- Hardening agents are mentioned, for example, in Research Disclosure 365 044, Chapter II B (September 1994). This hardening agent can be added to the emulsion or introduced via an auxiliary layer, for example an outer protective layer.
- 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 contain other additives which are known and customary for the production of certain properties. Such agents are listed, for example, in Research Disclosure 365 044 (September 1994) in chapters VI (brightener), IX A (coating aids), IX B (plasticizers and lubricants) and IX D (matting agents).
- the gelatin content of the emulsions is generally between 30 and 150 g per mol of silver; the range between 40 and 100 g per mol of silver is preferred.
- the invention also includes a process for the production of black and white negative photographic images, which is characterized in that a light-sensitive material described above is exposed imagewise, developed in an aqueous developer solution, fixed in a conventional manner, washed and dried.
- the developer solutions used according to the invention preferably contain 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 a pH of 9 to a maximum of 11 are particularly preferred. Such developer solutions are also stable in use and produce largely fog-free images.
- a dihydroxybenzene developer substance for example hydroquinone, pyrocatechol, methylhydroquinone or chlorohydroquinone
- an antioxidant preferably an alkali sulfite in a concentration of more than 0.3 mol per liter. Solutions with a pH of 9 to a maximum of 11 are particularly preferred. Such developer solutions are also stable in use and produce largely fog-free images.
- Developer solutions with a developer substance of the 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, can also be used. Developer solutions are also suitable which contain both developer substances of the dihydroxybenzene type and those of the ascorbic acid type.
- the developer solutions preferably contain known super-additive auxiliary developer substances, for example N-methyl-p-aminophenol or 1-phenylpyrazolidinone-3 or derivatives of these compounds.
- stabilizers from the groups of benzotriazoles and mercaptotetrazoles are also preferred.
- 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-nitrobenzetriazole, 5-benzoylaminobenztriazole, 1-hydroxymethylbenzyanotriazole, 6-.
- the contrast-enhancing compounds according to the invention can be added to the emulsion at any stage in the preparation. Due to their molecular structure, they can be both surface-active and interact with ionic polymers.
- the nitrile group gives the compounds hydrophilic properties.
- the hydrocarbon groups also present in the molecule have a 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 further hydrophilic groups, such as, for example, ethylene oxide groups, to match water solubility, interfacial activity and diffusibility of the compounds to the particular application.
- a further advantage of the compounds according to the invention is that they are decomposed into photographically inactive secondary products in the alkaline developer baths. They do not accumulate as a result of washing out in the developer, like other known contrast-increasing compounds incorporated in the recording material. Therefore, they do not affect the stability of developer activity, 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, in particular in the reproduction in the prepress for black-and-white and multi-color printing. It is explained in more detail by the following embodiment.
- 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 removing the Soluble salts by means of the flocking process were adjusted to a total gelatin content of 55 g per mol of silver and a chemical ripening with potassium thiotosylate, thiosulfate and gold salt was carried out.
- 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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Abstract
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 for producing black and white negative images with ultra-high contrast and a method for producing a black and white negative image using such a 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, halftone images often have to be converted into halftone dot images. For this purpose, silver halide materials are used, which are used in special processes for ultra-partial contrast, i.e. H. developed to a maximum slope of the density curve of more than 10. For example, the lith process with low-sulfite, formaldehyde-containing hydroquinone developers is known. Development in the presence of hydrazine compounds has recently become of particular practical importance.
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.This method often uses certain amino compounds to further increase the contrast. For example, EP-00 32 456-B1 claims a process in which a recording material is processed in the presence of a hydrazine compound with a hydroquinone-3-pyrazolidinone developer which contains a contrast-increasing amount of an amino compound.
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 containing a contrast-increasing amount of an amino compound 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 slight changes in concentration due to water evaporation during use, the solubility limit can easily be exceeded and the amino compound is eliminated. This can lead to uneven development and contamination of the recording materials and the Lead development machine. Because of their volatility in water vapor, the amino compounds which have been eliminated can also reach remote locations on the developing machine and cause undesirable impurities 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 containing known amino compounds, there is also a very unpleasant smell which is due to the high concentration required and the volatility of these compounds.
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 to formulate the developer concentrates which are customary as an economical commercial form. According to EP-A-02 03 521, salts of certain sulfonic or carboxylic acids can be used as solubilizers. However, the other problems addressed are not affected by such additives.
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 generally have a pH above 11. They are therefore not sufficiently stable in practice and 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.German Offenlegungsschrift DE-A-43 10 327 describes a process for producing negative images with ultra-partial contrast, in which the silver halide recording material is developed in the presence of compounds whose molecules have at least one quaternary nitrogen atom and at least one tertiary 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.EP-04 73 342-A1 describes a photographic silver halide material that can be developed in a developer with a pH <11 to ultra-partial contrast. The light-sensitive coating of this material contains a hydrazine compound of a certain formula and an amino or a quaternary onium compound and is adjusted to a pH of at least 5.9.
die Herstellung von Bildern mit ultrasteilem Kontrast auch bei relativ niedrigem Entwickler-pH und bei kurzer Entwicklungszeit ermöglichen.enable the production of images with ultra-high contrast even with a relatively low developer pH and with a short 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 realized by a nitrogen atom which is bonded to two organic radicals with single bonds and to the nitrile group via a divalent linking group.
In einer bevorzugten Ausführungsform der Erfindung fällt die kontraststeigernde Verbindung unter eine der nachstehend angegebenen allgemeinen Formeln (A), (B) oder (C):
RR1N - X - (CN)n (A)
NC - X - NR2 - B - NR2 - X - CN (B)
RR1N - X - N(CH2CN)2 (C)
In a preferred embodiment of the invention, the contrast-increasing compound falls under one of the general formulas (A), (B) or (C) given below:
RR 1 N - X - (CN) n (A)
NC - X - NR 2 - B - NR 2 - X - CN (B)
RR 1 N - X - N (CH 2 CN) 2 (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 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 preferably straight-chain, branched or cyclic alkylene groups with 1 to 20 carbon atoms, phenylene or aralkylene groups with 7 to 20 carbon atoms, or divalent chains from 1 to 20 methylene groups, in which, in addition to these, oxygen, sulfur, amino groups , Alkene or alkyne groups or also polyoxyalkylene groups, in particular polyoxyethylene or polyoxypropylene groups with 1 to 50 oxyalkyl units, can be incorporated. An ethylene or propylene group is particularly preferred. The groups mentioned can also be further 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:
―CH〈 ―CH2-CH〈 ―CH2-CH〈
―CH 〈―CH 2 -CH 〈―CH 2 -CH 〈
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 have at least one tertiary amino group in their molecule, they can be used both in the form of the free amine and in the form of a salt, i.e. of an adduct of an acid and the free amine can be prepared, 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 produced from easily accessible and inexpensive starting materials. The person skilled in the art can find suitable processes on the basis of the standard works on preparative organic chemistry, For example, the introduction of a cyanomethyl group using chloroacetonitrile, the alkylation of cyanides (Houben-Weyl, Methods of Organic Chemistry, 4th Edition, Volume 8 (1952), pages 290 ff.) and the dehydration of carboxamides (ibid., pages 330 ff.) . Further possibilities of the synthesis are the alkylation of the anion of a suitable CH-acidic 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 commercially available at low cost.
Beispiele für erfindungsgemäße kontraststeigernde Verbindungen sind:
(C2H5)2N-C3H6―CN HCl 1
(i- C3H7)2N-C2H4―CN HCl 2
(C4H9)2N-C2H4―CN HCl 5
(C4H9)2N-C3H6―N(CH2CN)2 7
(C2H5)2N-C2H4―O―C2H4―CN 9
(C2H5)2N-C2H4―S―C2H4―CN 10
(C 2 H 5 ) 2 NC 3 H 6 ―CN HCl 1
(i - C 3 H 7 ) 2 NC 2 H 4 ―CN HCl 2
(C 4 H 9 ) 2 NC 2 H 4 ―CN HCl 5
(C 4 H 9 ) 2 NC 3 H 6 ―N (CH 2 CN) 2 7
(C 2 H 5 ) 2 NC 2 H 4 ―O ― C 2 H 4 ―CN 9
(C 2 H 5 ) 2 NC 2 H 4 ―S ― C 2 H 4 ―CN 10
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 be incorporated into one or more layers of the recording material in a manner known per se. These can be both layers which contain the light-sensitive silver halide and layers which are reactive with the former, i. H. which are arranged in such a way that substances can diffuse from one layer to the other if a concentration gradient is maintained by reactions.
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:
B - Phenyl - NHNH - L - G (H)
Preferred hydrazine compounds are described by the general formula (H):
B - phenyl - NHNH - L - G (H)
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 and L is one of the groups -CO- and -CO-CO-. "Phenyl" means a benzene ring to which B and the hydrazine group are attached, 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 electron attractive, 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 above-mentioned alkyl groups as alkyl, and 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 Bailastgruppen 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 substituted with conventional photographic ballast groups, as are known from incorporated diffusion-resistant couplers and other immobilized photographic additives. Such bailast groups typically contain at least 8 carbon atoms and can be selected from relatively inert aliphatic or aromatic groups such as 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, including any ballast groups, preferably contain 1 to 20, the acylamino groups preferably 2 to 21 carbon atoms. However, up to 30 or more carbon atoms can be contained in these groups. Methoxyphenyl, tolyl, ballasted butyramidophenyl, butylsulfonamido and tolylsulfonamido are particularly preferred.
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.The 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 that can form a silver complex or otherwise have 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), optionally substituted aralkyl (e.g. benzyl, o-hydroxybenzyl) and optionally 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 a quaternary nitrogen atom, such as pyridinium and imidazolium, being 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 off with ring formation, as is the case e.g. in EP-B-02 53 665.
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 recording materials used according to the invention consist of silver chloride, silver bromide, silver chlorobromide, silver bromoiodide or silver chlorobromoiodide. They can be monodisperse or polydisperse, have a uniform composition, but also have grains with a core-shell structure, and can also be mixtures of grains of different composition and grain size distribution. They are made using a hydrophilic colloidal binder, preferably gelatin. The silver halide grains can be spherical, polyhedral or tabular in shape. Methods for producing suitable light-sensitive silver halide emulsions are known to the person skilled in the art and are summarized, for example, in Research Disclosure 365 044, chapters 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 the recording materials used according to the invention are silver halide emulsions which are produced by controlled double jet entry and have a cubic grain shape. Emulsions in which at least 80 percent by weight of the silver halide are present in cubic form are advantageous. Monodisperse emulsions, ie those in which the coefficient of variation (quotient of standard deviation and mean) of the grain size is less than 0.30, are particularly preferred. Under Grain size is understood to mean the edge length of a cube with the same volume as the real grain.
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, correspond to the cubic grains with an edge length of 0.1 to 0.7 μm. A preferred range is between 0.15 and 0.30 µm. Precious metal salts, especially salts of rhodium or iridium, can be present in the usual amounts in the emulsion preparation to control the photographic properties.
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 methods are sulfur, reduction and noble metal sensitization, which can also be used in combination. For the latter, for example, gold or iridium compounds can be used. The sensitization is preferably carried out in the presence of salts of organic thiosulfonic acids, such as p-toluenesulfonic acid.
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 spectrally sensitized with conventional sensitizing dyes, as described, for example, 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 contain conventional antifoggants. Substituted benzotriazole, 5-nitroindazole and 1-phenyl-5-mercaptotetrazole are preferred. These agents can be added at any time during the preparation of the emulsion or can be contained in an auxiliary layer of the photographic material. To improve the photographic properties, an iodide, preferably an alkali iodide, can be added to the emulsion in an amount of about 0.5 to 5 mmol per mole of silver before or after chemical ripening.
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. It deals usually 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 light-sensitive layers of the photographic materials can be hardened by adding a hardening agent. Hardening agents are mentioned, for example, in Research Disclosure 365 044, Chapter II B (September 1994). This hardening agent can be added to the emulsion or introduced via an auxiliary layer, for example an outer protective layer. 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 contain other additives which are known and customary for the production of certain properties. Such agents are listed, for example, in Research Disclosure 365 044 (September 1994) in chapters VI (brightener), IX A (coating aids), IX B (plasticizers and lubricants) and IX D (matting agents).
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 generally between 30 and 150 g per mol of silver; the range between 40 and 100 g per mol of silver is preferred.
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 process for the production of black and white negative photographic images, which is characterized in that a light-sensitive material described above is exposed imagewise, developed in an aqueous developer solution, fixed in a conventional manner, washed 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 preferably contain 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 a pH of 9 to a maximum of 11 are particularly preferred. Such developer solutions are also stable in use and produce largely fog-free images. Developer solutions with a developer substance of the 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, can also be used. Developer solutions are also suitable which contain both developer substances of the dihydroxybenzene type and those of the ascorbic acid type.
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 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.Developers containing stabilizers from the groups of benzotriazoles and mercaptotetrazoles are also preferred. 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-nitrobenzetriazole, 5-benzoylaminobenztriazole, 1-hydroxymethylbenzyanotriazole, 6-.
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 process according to the invention, the use of alkanolamines according to the prior art is either completely unnecessary or their amount can be reduced to a small fraction. As a result, the process works without annoying or harmful odor nuisance and corrosion by volatilizing amino compounds from the developer is 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 be added to the emulsion at any stage in the preparation. Due to their molecular structure, they can be both surface-active and interact with ionic polymers. The nitrile group gives the compounds hydrophilic properties. In contrast, the hydrocarbon groups also present in the molecule have a 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 further hydrophilic groups, such as, for example, ethylene oxide groups, to match water solubility, interfacial activity and diffusibility of the compounds to the particular 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.A further advantage of the compounds according to the invention is that they are decomposed into photographically inactive secondary products in the alkaline developer baths. They do not accumulate as a result of washing out in the developer, like other known contrast-increasing compounds incorporated in the recording material. Therefore, they do not affect the stability of developer activity, 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, in particular in the reproduction in the prepress for black-and-white and multi-color printing. It is explained in more detail by the following embodiment.
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 removing the Soluble salts by means of the flocking process were adjusted to a total gelatin content of 55 g per mol of silver and a chemical ripening with potassium thiotosylate, thiosulfate and gold salt was carried out. 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:
(C2H5)2N-CH2―CHOH―CH2OH V-1
(C 2 H 5 ) 2 N-CH 2 ―CHOH ― CH 2 OH V-1
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)
dadurch gekennzeichnet, daß
es in dieser oder in einer anderen mit ihr in reaktiver Beziehung stehenden Schicht mindestens eine kontraststeigernde Verbindung enthält, die in ihrem Molekül mindestens eine tertiäre Aminogruppe und mindestens eine Nitrilogruppe aufweist.Photosensitive silver halide recording material, in particular for the production of black and white negative images with ultra-partial contrast, with at least one photosensitive layer on at least one side of a support and optionally further layers on the same side of the support, which in the photosensitive or in a with this reactive layer contain at least one hydrazine compound
characterized in that
it contains at least one contrast-increasing compound in this or in another layer which is reactive with it and which has at least one tertiary amino group and at least one nitrile group in its molecule.
dadurch gekennzeichnet, daß die kontraststeigernde Verbindung unter eine der allgemeinen Formeln (A), (B) oder (C)
RR1N - X - (CN)n (A)
NC - X - NR2 - B - NR2 - X - CN (B)
RR1N - X - N(CH2CN)2 (C)
fällt, worin bedeuten
characterized in that the contrast-increasing compound has one of the general formulas (A), (B) or (C)
RR 1 N - X - (CN) n (A)
NC - X - NR 2 - B - NR 2 - X - CN (B)
RR 1 N - X - N (CH 2 CN) 2 (C)
falls in what mean
dadurch gekennzeichnet, daß
die Hydrazinverbindung die allgemeine Formel (H)
B - Phenyl - NHNH - L - G (H)
hat, wobei B eine Ballastgruppe, G eine aktivierende Gruppe und L gleich CO oder CO-CO ist.Silver halide light-sensitive material according to claim 1 or 2,
characterized in that
the hydrazine compound has the general formula (H)
B - phenyl - NHNH - L - G (H)
where B is a ballast group, G is an activating group and L is CO or CO-CO.
dadurch gekennzeichnet, daß
es die kontraststeigernde Verbindung in einer Menge von 0,05 bis 5 g je mol Silber enthält.Silver halide light-sensitive material according to any one of claims 1 to 3,
characterized in that
it contains the contrast-increasing compound in an amount of 0.05 to 5 g per mol of silver.
dadurch gekennzeichnet, daß
das Silberhalogenid der Emulsion zu mehr als 80 Gewichtsprozent aus kubischen Körnern besteht.Silver halide light-sensitive material according to any one of claims 1 to 4,
characterized in that
the silver halide of the emulsion consists of more than 80 percent by weight of cubic grains.
dadurch gekennzeichnet, daß
das Silberhalogenid der Emulsion eine mittlere Korngröße von 0,15 bis 0,30 µm aufweist.Silver halide light-sensitive material according to any one of claims 1 to 5,
characterized in that
the silver halide of the emulsion has an average grain size of 0.15 to 0.30 µm.
dadurch gekennzeichnet, daß
das Silberhalogenid der Emulsion monodispers ist.Silver halide light-sensitive material according to any one of claims 1 to 6,
characterized in that
the silver halide of the emulsion is monodisperse.
dadurch gekennzeichnet, daß
ein Aufzeichnungsmaterial nach einem der Ansprüche 1 bis 4 belichtet und in einem Entwickler mit einem pH zwischen 9 und 11 entwickelt wird.Process for producing a black and white negative image with ultra-partial contrast,
characterized in that
a recording material according to one of claims 1 to 4 is exposed and developed in a developer with a pH between 9 and 11.
dadurch gekennzeichnet, daß
der Entwickler mehr als 0,30 mol Sulfit je Liter enthält.A method according to claim 8,
characterized in that
the developer contains more than 0.30 mol of sulfite 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 true EP0740194A1 (en) | 1996-10-30 |
| EP0740194B1 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5229248A (en) * | 1990-08-16 | 1993-07-20 | Konica Corporation | Silver halide photographic light sensitive material |
| EP0618491A1 (en) * | 1993-03-30 | 1994-10-05 | Du Pont De Nemours (Deutschland) Gmbh | Method for generation of negative images having ultrahigh contrast |
Family Cites Families (6)
| 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 |
| US5283158A (en) * | 1991-10-31 | 1994-02-01 | Konica Corporation | Silver halide photographic light-sensitive material |
-
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
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5229248A (en) * | 1990-08-16 | 1993-07-20 | Konica Corporation | Silver halide photographic light sensitive material |
| EP0618491A1 (en) * | 1993-03-30 | 1994-10-05 | Du Pont De Nemours (Deutschland) Gmbh | Method for generation of negative images having ultrahigh contrast |
| DE4310327A1 (en) * | 1993-03-30 | 1994-10-06 | Du Pont Deutschland | Method of producing negative images with ultra-contrast contrast |
Also Published As
| Publication number | Publication date |
|---|---|
| US5663034A (en) | 1997-09-02 |
| EP0740194B1 (en) | 1998-04-01 |
| JP3668554B2 (en) | 2005-07-06 |
| DE59600132D1 (en) | 1998-05-07 |
| DE19515619A1 (en) | 1996-10-31 |
| JPH08334856A (en) | 1996-12-17 |
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