JPH0153768B2 - - Google Patents
Info
- Publication number
- JPH0153768B2 JPH0153768B2 JP14182282A JP14182282A JPH0153768B2 JP H0153768 B2 JPH0153768 B2 JP H0153768B2 JP 14182282 A JP14182282 A JP 14182282A JP 14182282 A JP14182282 A JP 14182282A JP H0153768 B2 JPH0153768 B2 JP H0153768B2
- Authority
- JP
- Japan
- Prior art keywords
- photosensitive
- silver halide
- curing agent
- formula
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000003795 chemical substances by application Substances 0.000 claims description 54
- 229910052709 silver Inorganic materials 0.000 claims description 53
- 239000004332 silver Substances 0.000 claims description 53
- 230000009467 reduction Effects 0.000 claims description 46
- -1 silver halide Chemical class 0.000 claims description 43
- 229920000642 polymer Polymers 0.000 claims description 41
- 239000000839 emulsion Substances 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 25
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 15
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical group C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims description 11
- 239000010410 layer Substances 0.000 description 80
- 238000001723 curing Methods 0.000 description 70
- 108010010803 Gelatin Proteins 0.000 description 25
- 239000008273 gelatin Substances 0.000 description 25
- 229920000159 gelatin Polymers 0.000 description 25
- 235000019322 gelatine Nutrition 0.000 description 25
- 235000011852 gelatine desserts Nutrition 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000003786 synthesis reaction Methods 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 239000004816 latex Substances 0.000 description 13
- 229920000126 latex Polymers 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000003860 storage Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 229920001515 polyalkylene glycol Polymers 0.000 description 8
- 239000000975 dye Substances 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000000084 colloidal system Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000005457 ice water Substances 0.000 description 6
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000001235 sensitizing effect Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 4
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 235000010980 cellulose Nutrition 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000006224 matting agent Substances 0.000 description 4
- 238000011946 reduction process Methods 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000000732 arylene group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 150000002763 monocarboxylic acids Chemical class 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- KXSNTZCQKNKBOW-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl 3-(2-chloroethylsulfonyl)propanoate Chemical compound ClCCS(=O)(=O)CCC(=O)OCCOC(=O)C=C KXSNTZCQKNKBOW-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229960003237 betaine Drugs 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000000269 nucleophilic effect Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229940047670 sodium acrylate Drugs 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- AZGINNVTHJQMPB-UHFFFAOYSA-M sodium;2-methylpropane-1-sulfonate;prop-2-enamide Chemical compound [Na+].NC(=O)C=C.CC(C)CS([O-])(=O)=O AZGINNVTHJQMPB-UHFFFAOYSA-M 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- QKUGKZFASYQCGO-SREVYHEPSA-N (z)-4-oxo-4-phenylmethoxybut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)OCC1=CC=CC=C1 QKUGKZFASYQCGO-SREVYHEPSA-N 0.000 description 1
- FYADHXFMURLYQI-UHFFFAOYSA-N 1,2,4-triazine Chemical group C1=CN=NC=N1 FYADHXFMURLYQI-UHFFFAOYSA-N 0.000 description 1
- RIEQDAWNHLUKFR-UHFFFAOYSA-N 1,3-bis(2-chloroethylsulfonyl)propan-2-ol Chemical compound ClCCS(=O)(=O)CC(O)CS(=O)(=O)CCCl RIEQDAWNHLUKFR-UHFFFAOYSA-N 0.000 description 1
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 1
- YMCRLEQKPXEVBW-UHFFFAOYSA-N 1-(2-chloroethylsulfonyl)-3-[2-(1-ethenylcyclohexa-2,4-dien-1-yl)sulfonylethylsulfonyl]propan-2-ol Chemical compound ClCCS(=O)(=O)CC(O)CS(=O)(=O)CCS(=O)(=O)C1(C=C)CC=CC=C1 YMCRLEQKPXEVBW-UHFFFAOYSA-N 0.000 description 1
- FPQUEAOPHRFJGH-UHFFFAOYSA-M 1-(3-phenylprop-1-enyl)pyridin-1-ium;chloride Chemical compound [Cl-].C=1C=CC=CC=1CC=C[N+]1=CC=CC=C1 FPQUEAOPHRFJGH-UHFFFAOYSA-M 0.000 description 1
- BDHGFCVQWMDIQX-UHFFFAOYSA-N 1-ethenyl-2-methylimidazole Chemical compound CC1=NC=CN1C=C BDHGFCVQWMDIQX-UHFFFAOYSA-N 0.000 description 1
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 description 1
- CMCIZAQXXZNGMF-UHFFFAOYSA-N 2-(2-chloroethylsulfonyl)-n-ethenyl-2-methyl-3-phenylpropanamide Chemical compound C=CNC(=O)C(S(=O)(=O)CCCl)(C)CC1=CC=CC=C1 CMCIZAQXXZNGMF-UHFFFAOYSA-N 0.000 description 1
- LWQOYLJQWUQFEG-UHFFFAOYSA-N 2-(2-chloroethylsulfonyl)propanoyl chloride Chemical compound ClC(=O)C(C)S(=O)(=O)CCCl LWQOYLJQWUQFEG-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- HTXNENZCPGIVLC-UHFFFAOYSA-N 2-(aminomethyl)-5-(2-chloroethylsulfonyl)-1-phenylpent-1-en-3-one Chemical compound ClCCS(=O)(=O)CCC(=O)C(=CC1=CC=CC=C1)CN HTXNENZCPGIVLC-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- VHCSBTPOPKFYIU-UHFFFAOYSA-N 2-chloroethanesulfonyl chloride Chemical compound ClCCS(Cl)(=O)=O VHCSBTPOPKFYIU-UHFFFAOYSA-N 0.000 description 1
- GPOGMJLHWQHEGF-UHFFFAOYSA-N 2-chloroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCl GPOGMJLHWQHEGF-UHFFFAOYSA-N 0.000 description 1
- AEPWOCLBLLCOGZ-UHFFFAOYSA-N 2-cyanoethyl prop-2-enoate Chemical compound C=CC(=O)OCCC#N AEPWOCLBLLCOGZ-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- IXPWKHNDQICVPZ-UHFFFAOYSA-N 2-methylhex-1-en-3-yne Chemical compound CCC#CC(C)=C IXPWKHNDQICVPZ-UHFFFAOYSA-N 0.000 description 1
- AUZRCMMVHXRSGT-UHFFFAOYSA-N 2-methylpropane-1-sulfonic acid;prop-2-enamide Chemical compound NC(=O)C=C.CC(C)CS(O)(=O)=O AUZRCMMVHXRSGT-UHFFFAOYSA-N 0.000 description 1
- VAPQAGMSICPBKJ-UHFFFAOYSA-N 2-nitroacridine Chemical compound C1=CC=CC2=CC3=CC([N+](=O)[O-])=CC=C3N=C21 VAPQAGMSICPBKJ-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- WTVWEUNNNOTJTQ-UHFFFAOYSA-N 3-(2-chloroethylsulfonyl)-n-[(prop-2-enoylamino)methyl]propanamide Chemical compound ClCCS(=O)(=O)CCC(=O)NCNC(=O)C=C WTVWEUNNNOTJTQ-UHFFFAOYSA-N 0.000 description 1
- KAKDHLJJBBJUHT-UHFFFAOYSA-N 3-(2-chloroethylsulfonyl)propanoyl chloride Chemical compound ClCCS(=O)(=O)CCC(Cl)=O KAKDHLJJBBJUHT-UHFFFAOYSA-N 0.000 description 1
- HTWRFCRQSLVESJ-UHFFFAOYSA-N 3-(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCOC(=O)C(C)=C HTWRFCRQSLVESJ-UHFFFAOYSA-N 0.000 description 1
- IWTYTFSSTWXZFU-UHFFFAOYSA-N 3-chloroprop-1-enylbenzene Chemical compound ClCC=CC1=CC=CC=C1 IWTYTFSSTWXZFU-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- PXDAXYDMZCYZNH-UHFFFAOYSA-N 3-methyl-2h-1,3-benzothiazole Chemical compound C1=CC=C2N(C)CSC2=C1 PXDAXYDMZCYZNH-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- LUHCBWDNSKIADE-UHFFFAOYSA-M 4-methylbenzenesulfonate;triethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.CC[N+](CC)(CC)CCOC(=O)C(C)=C LUHCBWDNSKIADE-UHFFFAOYSA-M 0.000 description 1
- INVVMIXYILXINW-UHFFFAOYSA-N 5-methyl-1h-[1,2,4]triazolo[1,5-a]pyrimidin-7-one Chemical compound CC1=CC(=O)N2NC=NC2=N1 INVVMIXYILXINW-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- IHCWZTAESJPNFN-UHFFFAOYSA-N C(CC)(=O)O.CN(C(CC)NC(C=C)=O)C Chemical compound C(CC)(=O)O.CN(C(CC)NC(C=C)=O)C IHCWZTAESJPNFN-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- JNRYNQZLNRPUOW-UHFFFAOYSA-M Cl[Ag][Cl][Br][Ag] Chemical compound Cl[Ag][Cl][Br][Ag] JNRYNQZLNRPUOW-UHFFFAOYSA-M 0.000 description 1
- 241001269524 Dura Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical class O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-ISLYRVAYSA-N V-65 Substances CC(C)CC(C)(C#N)\N=N\C(C)(C#N)CC(C)C WYGWHHGCAGTUCH-ISLYRVAYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- VSCHDHXACOLPFZ-UHFFFAOYSA-N acetic acid N-[1-(dimethylamino)propyl]-2-methylprop-2-enamide Chemical compound CC(O)=O.CCC(NC(=O)C(C)=C)N(C)C VSCHDHXACOLPFZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002877 alkyl aryl group Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- GDCXBZMWKSBSJG-UHFFFAOYSA-N azane;4-methylbenzenesulfonic acid Chemical compound [NH4+].CC1=CC=C(S([O-])(=O)=O)C=C1 GDCXBZMWKSBSJG-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000006367 bivalent amino carbonyl group Chemical group [H]N([*:1])C([*:2])=O 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- VZDYWEUILIUIDF-UHFFFAOYSA-J cerium(4+);disulfate Chemical compound [Ce+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VZDYWEUILIUIDF-UHFFFAOYSA-J 0.000 description 1
- 229910000355 cerium(IV) sulfate Inorganic materials 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N cinnamyl alcohol Chemical compound OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- ZSKAXRGRRXCFGC-UHFFFAOYSA-M diethyl-methyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.CC[N+](C)(CC)CCOC(=O)C(C)=C ZSKAXRGRRXCFGC-UHFFFAOYSA-M 0.000 description 1
- ZWWQRMFIZFPUAA-UHFFFAOYSA-N dimethyl 2-methylidenebutanedioate Chemical compound COC(=O)CC(=C)C(=O)OC ZWWQRMFIZFPUAA-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- FPMVYJWETQRZBU-UHFFFAOYSA-N ethenyl benzenesulfinate;potassium Chemical compound [K].C=COS(=O)C1=CC=CC=C1 FPMVYJWETQRZBU-UHFFFAOYSA-N 0.000 description 1
- PWHMFVALYNYYMZ-UHFFFAOYSA-N ethenyl phenylmethanesulfonate;sodium Chemical compound [Na].C=COS(=O)(=O)CC1=CC=CC=C1 PWHMFVALYNYYMZ-UHFFFAOYSA-N 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 229940076131 gold trichloride Drugs 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- FBPFZTCFMRRESA-UHFFFAOYSA-N hexane-1,2,3,4,5,6-hexol Chemical class OCC(O)C(O)C(O)C(O)CO FBPFZTCFMRRESA-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- BVWUEIUNONATML-UHFFFAOYSA-N n-benzylethenamine Chemical compound C=CNCC1=CC=CC=C1 BVWUEIUNONATML-UHFFFAOYSA-N 0.000 description 1
- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- HVAMZGADVCBITI-UHFFFAOYSA-M pent-4-enoate Chemical compound [O-]C(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-M 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003378 silver Chemical class 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
- 229940045105 silver iodide Drugs 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- XESUCHPMWXMNRV-UHFFFAOYSA-M sodium;2-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1C=C XESUCHPMWXMNRV-UHFFFAOYSA-M 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten 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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
Description
本発明は製版用ハロゲン化銀写真感光材料及び
これを用いて行なう減力処理方法に関するもので
ある。さらに詳しくは硬化剤の新しい組合せ使用
により、減力処理適性が著しく改良され、且つ、
写真性能、硬膜進行性、後硬膜性、及び硬化度の
保存湿度依存性が改良された製版用ハロゲン化銀
写真感光材料（以下製版用感材という）及びこれ
を用いて行なう減力処理方法に関するものであ
る。
製版用感材は、印刷工業等の分野に於て濃淡画
像を網点画像に変換したり、線画像を撮影するな
どを写真製版工程に用いる感材である。
通常これらの製版用感材を用いて印刷用原板を
得るにあたつては、印刷特性に適合した画像の微
妙な調子再現や芸術的な表現を満足させる為に、
該製版用感材に対して減力処理と呼ばれる処理を
施して網点面積を減少させたり線画の巾を拡大又
は縮少させるなど画像を部分的に又は全面的に微
修正する工程を経ることが多い。
この為、製版用感材に於ては減力処理適性を有
しているか否かが極めて重要な性能の１つとな
る。
露光・現像処理を経て網点画像又は線画像を形
成した製版用感材を減力処理するには、該網点又
は線画像を形成している金属銀を減力液と接触さ
せる方法が用いられている。減力液としては多く
のものが知られており、たとえば、ミース著ザ・
セオリー・オブ・ザ・フオトグラフイツク・プロ
セス（Mees，The Theory of the
Photographic Process）第738〜739頁（1954年、
Macmillan社刊行）には過マンガン酸塩、第２
鉄塩、第２セリウム塩、赤血塩、重クロム酸塩、
過硫酸塩などの減力成分を用いた減力液が記載さ
れている。
ところが、減力処理とは結局、銀画像を酸化
し、溶解することであるから、網点画像を減力処
理する場合、減力処理により網点面積を減少せし
めると、それと併行して網点の黒化濃度の減少が
生ずる。従つて減力処理により修正可能な範囲は
網点面積の減少時に発生する網点１個当りの黒化
濃度の減少の度合によつて制限されることにな
る。換言すれば、網点画像の修正可能な範囲のメ
ジヤーは、網点１個当りの黒化濃度を一定値以下
に保つて網点面積をいくら減少せしめ得たかによ
つて表わすことが出来る。
本明細書に於ては、減力処理により写真製版工
程で必要とされるぎりぎりの値にまで網点の黒化
濃度が減少した時に、網点面積が処理前の網点面
積に対してどの位減少したかを「減力巾」なる用
語で表わすことにする。この減力巾が広いほど減
力処理適性が高くなることはいうまでもない。
減力処理適性を向上させる技術としては、例え
ば特開昭52―68419号公報に記載された減力処理
時にメルカプト化合物を含む減力法が知られてい
るが、特殊な減力液となり、減力速度が一般に使
われている減力液と異なつて使いにくくなる。ま
た乳剤膜を軟膜にして、カバーリングパワーを上
げて濃度を上げれば、減力巾を広くし、減力処理
適性を改善することができるが、この方法では必
要な膜強度が得られない。
減力巾を広くして減力処理適性を改善する技術
の中で最も有効な方法は画像を形成する銀量を多
くすることである。何故なら、前述したように減
力処理とは減力液により銀画像を酸化し、溶解す
ることであるから、一般に銀画像を形成している
銀の単位面積当りの量が多ければ多い程減力処理
により画像を修正できる範囲は広くなるからであ
る。従つて製版用感材に用いるハロゲン化銀の単
位面積当りの塗布量を多くすれば減力巾は広くな
るのであるが、周知の如く銀は極めて高価かつ貴
重なものであるから、いたずらに塗布銀量を多く
することは製版用感材のコストの点からも省資源
的見地からも好ましくない。
以上のことから、減力巾を広くするには、現像
銀の溶解速度が乳剤層に対して垂直方向と水平方
向で異なるような技術が必要である。即ち現像銀
の溶解速度の異方性の大きい方が好ましい。この
考えを実現させるため、本発明者らは種々の方策
を検討した。その結果非感光性上部層の硬化度と
ハロゲン銀乳剤層の硬化度を独立にコントロール
することのできる硬化技術（塗布層別硬化技術）
を応用し、非感光性上部層の硬化度を大きくする
ことにより減力巾が広くなり、減力処理適性が著
しく改善されることを見い出した（特願昭56―
140669号）。
上記の塗布層別硬化技術の中では、非感光性上
部層に非拡散性の高分子硬化剤を添加する一方、
該層又は他の層に拡散性の低分子硬化剤を用いる
手法が最も効果的であるが、併用する拡散性の低
分子硬化剤の種類によつては減力液の組成を変え
た場合の減力巾と減力時間の変化が大きくなると
いう望ましくない現象が発生することがある。
一方、写真感光材料の構成層の硬化の度合はし
ばしば写真特性に重大な影響を与えるので、通常
写真感光材料は塗布後の硬化反応が終了し、写真
特性が安定するまでストツクされ、その後に初め
て出荷される。従つて硬化反応の進行が早い程ス
トツク期間が短縮されるので貯蔵コストが低くな
り好ましくない。また上記の硬化反応の進行が周
囲の温湿度（特に湿度）に影響を受けにくいほ
ど、ストツク期間中の温湿度管理が容易になる。
ところが高分子硬化剤の硬化反応速度は一般に
遅いので、前記の塗布層別硬化技術を用いた製版
用感材においてはストツク期間が長くなるし、ま
たその硬化反応の進行がストツク期間中の温湿度
の影響を受けやすいという問題があつた。
従つて本発明の目的は第１に減力巾が大きく、
かつ減力液の組成の相違に依存する減力性能の変
動が少ない製版用感材を提供することにある。
本発明の目的は第２に硬化反応の進行が早く、
かつ周囲の温湿度に対する依存性が少ない硬化技
術を施した製版用感材を提供することにある。
本発明の目的は第３に、組成の異なる減力液を
用いても略同一の優れた減力を行なうことができ
る減力処理方法を提供することにある。
本発明の目的は、支持体上に少なくとも１層の
感光性ハロゲン化銀乳剤層及び該乳剤層の上部に
少なくとも１層の非感光性上部層を有して成る製
版用感材に於て、非感光性上部層の少なくとも１
層の融解時間が感光性ハロゲン化銀乳剤層の融解
時間よりも大きくなるように、高分子硬化剤と活
性ビニル基を有する低分子硬化剤とを併用して硬
化した製版用感材とこの製版用感材を露光・現像
処理したあと減力処理する減力処理方法によつて
達成された。
本発明における非感光性上部層は、感光性ハロ
ゲン化銀乳剤層の上部全面にわたつて設けられる
本質的に親水性コロイドからなる層である。かか
る非感光性上部層は１層のみでもよく、場合によ
つては２層又はそれ以上設けられても良い。また
本発明における感光性ハロゲン化銀乳剤層は感光
性ハロゲン化銀粒子が親水性コロイド中に分散さ
れて成る層であり、かかる感光性ハロゲン化銀乳
剤層は１層のみでもよく、場合によつては２層以
上設けられても良い。
本発明において、非感光性上部層の少なくとも
１層の融解時間が感光性ハロゲン化銀乳剤層の融
解時間よりも大きいということは、該非感光性上
部層が乳剤層よりもより強く硬化されていること
を意味する。
硬化した層の硬化度を評価する方法としては、
当業界では、硬化層をある溶液で膨潤させた時の
膨潤度、あるいは、荷重をかけた針状のスタイラ
スを用いて引掻き、傷の生ずる荷重であらわす引
掻強度などがよく知られているが、本発明の目的
の評価のためには、硬化膜をある一定温度に保つ
た溶液中に漬け、膜が融解しはじめるまでの時間
すなわち融解時間（melting time：MT）を用い
て評価するのが最も有効である。融解時間の測定
には、75℃に保つた0.2NNaOH溶液中に行うの
が最もよい（但し必ずしもこれに限るわけではな
い）。
本発明の製版用感材は高分子硬化剤と活性ビニ
ル基を有する低分子硬化剤を併用して、非感光上
部層の少なくとも１層が感光性ハロゲン化銀乳剤
層よりも大きな融解時間を持つように硬化されて
いる。高分子硬化剤は高分子であるが故に耐拡散
性を持つので、非感光性上部層の少なくとも１層
に添加するとその層のみが選択的に硬化される。
その他の層は活性ビニル基を有する低分子硬化剤
で硬化される。活性ビニル基を有する低分子硬化
剤には拡散性を持つものが多いので、この硬化剤
は非感光性上部層又は感光性ハロゲン化銀乳剤層
のいずれに添加してもよい。この場合、活性ビニ
ル基を有する低分子硬化剤は上記高分子硬化剤が
添加された非感光性上部層にも拡散するが、該層
は両硬化剤により硬化されるので感光性ハロゲン
化銀乳剤層よりも強く硬化されることになる。
高分子硬化剤と活性ビニル基を持つ低分子硬化
剤の使用量を一義的に規定するのは困難であつ
て、各層の融解時間を測定して試行錯誤法で決定
されるものである。
本発明の目的に対しては非感光性上部層の融解
時間が感光性ハロゲン化銀の融解時間よりも前述
の測定法で好ましくは50秒以上特に100秒以上大
きくなるように硬化剤の使用量を設定するのが好
ましい。
本発明に使用される高分子硬化剤は特開昭56―
66841号、英国特許第1322971号、英国特許第
3671256号、等の特許、及びD.M.Burness J.
Pouradier“The Theory of the Photographic
Process”4th ed.（T.H.James ed.）、
Macmillan、New York，1977.pp84，やG.A.
Campbell，L.R.Hamilton，I.S.Ponticello，
“Polymeric Amine and Ammonium Salts”
（E.J.Goethals ed.）Pergamon Press，New
York1979，pp321〜332，などの成書でよく知ら
れているゼラチンと反応する官能基を有するポリ
マーである。特に分子量が１万以上の高分子硬化
剤が好ましい。
この高分子硬化剤としては次に示す一般式
（）、（）及び（）のものが好ましく、特に
一般式（）のものが好ましい。
式中Ａはその右に示したモノマー単位と共重合
可能なエチレン性不飽和モノマーを表わす。
また式中R1は水素原子または１から６個の炭
素原子を有する低級アルキル基を表わす。Ｑは―
CO2―，
The present invention relates to a silver halide photographic light-sensitive material for plate making and a reduction processing method using the same. More specifically, the use of a new combination of curing agents significantly improves the suitability for reducing force, and
A silver halide photographic light-sensitive material for plate making (hereinafter referred to as a sensitive material for plate making) with improved photographic performance, hardening progress, post-hardening property, and storage humidity dependence of degree of curing, and a reduction treatment performed using the same. It is about the method. A photosensitive material for platemaking is a photosensitive material that is used in photolithographic processes, such as converting a gray scale image into a halftone image or photographing a line image, in fields such as the printing industry. Normally, when obtaining printing plates using these plate-making photosensitive materials, in order to satisfy the delicate tone reproduction of images and artistic expressions that match the printing characteristics,
A process called force reduction processing is applied to the photosensitive material for plate making to partially or completely modify the image, such as reducing the halftone dot area or enlarging or reducing the width of the line drawing. There are many. For this reason, one of the extremely important performances of photosensitive materials for plate making is whether or not they have suitability for pressure reduction processing. In order to reduce the pressure of a photosensitive material for plate making on which a halftone image or line image has been formed through exposure and development processing, a method is used in which the metallic silver forming the halftone dots or line image is brought into contact with a reduction liquid. It is being Many types of reducing fluids are known, such as the one written by Mies.
Mees, The Theory of the Photographic Process
Photographic Process) pp. 738-739 (1954,
(published by Macmillan) includes permanganate,
iron salts, ceric salts, red blood salts, dichromates,
Reducing fluids using reducing components such as persulfates have been described. However, since the reduction process ultimately involves oxidizing and dissolving the silver image, when applying the reduction process to the halftone dot image, when the area of the halftone dot is reduced by the reduction process, the halftone dot area is reduced at the same time. A decrease in the blackening density occurs. Therefore, the range that can be corrected by power reduction processing is limited by the degree of reduction in blackening density per halftone dot that occurs when the halftone dot area is reduced. In other words, the measure of the correctable range of the halftone dot image can be expressed by how much the halftone dot area can be reduced while keeping the blackening density per halftone dot below a certain value. In this specification, when the blackening density of a halftone dot is reduced to the minimum value required in the photolithography process by force reduction processing, the halftone dot area is compared to the halftone dot area before processing. We will use the term ``reduction width'' to express the amount of force reduction. It goes without saying that the wider the force reduction range, the higher the suitability for force reduction processing. As a technique for improving suitability for force reduction processing, for example, a reduction method that includes a mercapto compound during force reduction processing is known, as described in Japanese Patent Application Laid-open No. 52-68419. The force speed is different from commonly used reducing fluids, making it difficult to use. Furthermore, if the emulsion film is made into a soft film and the covering power is increased to increase the density, the reduction width can be widened and the suitability for reduction processing can be improved, but this method does not provide the necessary film strength. Among the techniques for widening the reduction width and improving suitability for reduction processing, the most effective method is to increase the amount of silver used to form an image. This is because, as mentioned above, the reduction process involves oxidizing and dissolving the silver image with a reduction solution, so generally speaking, the greater the amount of silver forming the silver image per unit area, the more the silver image is reduced. This is because the range in which images can be corrected by force processing becomes wider. Therefore, by increasing the amount of silver halide applied per unit area used in photosensitive materials for plate making, the reduction range can be widened, but as is well known, silver is extremely expensive and valuable, so it is difficult to apply it unnecessarily. Increasing the amount of silver is not preferable from the viewpoint of both the cost of the plate-making photosensitive material and resource conservation. From the above, in order to widen the reduction range, a technique is required in which the dissolution rate of developed silver is different in the vertical and horizontal directions with respect to the emulsion layer. That is, it is preferable that the anisotropy of the dissolution rate of developed silver is large. In order to realize this idea, the present inventors investigated various measures. As a result, a curing technology that allows the degree of hardening of the non-photosensitive upper layer and the hardening degree of the silver halide emulsion layer to be independently controlled (curing technology for each coated layer)
By applying this technology, we discovered that by increasing the degree of hardening of the non-photosensitive upper layer, the reduction width was widened and the suitability for reduction treatment was significantly improved.
No. 140669). In the above coating layer-by-layer curing technology, a non-diffusible polymer curing agent is added to the non-photosensitive upper layer;
The most effective method is to use a diffusible low-molecular curing agent in this layer or other layers, but depending on the type of diffusible low-molecular curing agent used in combination, the composition of the reducing fluid may be changed. An undesirable phenomenon may occur in which the change in the force reduction width and the force reduction time increases. On the other hand, since the degree of curing of the constituent layers of a photographic material often has a significant effect on its photographic properties, photographic materials are usually stocked until the curing reaction after coating has been completed and the photographic properties have stabilized, and only then. Will be shipped. Therefore, the faster the curing reaction progresses, the shorter the storage period will be, which is undesirable because the storage cost will be lower. Furthermore, the less the progress of the curing reaction is affected by the ambient temperature and humidity (particularly humidity), the easier the temperature and humidity control during the stock period will be. However, since the curing reaction rate of polymeric curing agents is generally slow, the stock period is longer for photosensitive materials for plate making using the coating layer-by-layer curing technique described above, and the progress of the curing reaction is affected by temperature and humidity during the storage period. The problem was that it was easily influenced by Therefore, the first object of the present invention is to have a large force reduction range;
Another object of the present invention is to provide a photosensitive material for plate making in which the reduction performance is less likely to fluctuate depending on the composition of the reduction liquid. The second object of the present invention is that the curing reaction progresses quickly;
Another object of the present invention is to provide a photosensitive material for plate making which is subjected to a curing technology that is less dependent on ambient temperature and humidity. A third object of the present invention is to provide a force reduction processing method that can perform substantially the same excellent force reduction even when using force reduction liquids having different compositions. The object of the present invention is to provide a photosensitive material for plate making comprising at least one photosensitive silver halide emulsion layer on a support and at least one non-photosensitive upper layer on top of the emulsion layer. at least one non-photosensitive top layer
A plate-making sensitive material cured using a combination of a polymer hardener and a low-molecular hardener having an active vinyl group so that the melting time of the layer is longer than the melting time of the photosensitive silver halide emulsion layer, and this plate-making sensitive material. This was achieved using a reduction processing method in which the photosensitive material is exposed and developed and then subjected to reduction processing. The non-photosensitive upper layer in the present invention is a layer essentially consisting of a hydrophilic colloid provided over the entire upper surface of the photosensitive silver halide emulsion layer. There may be only one such non-photosensitive upper layer, or in some cases, two or more layers may be provided. Further, the photosensitive silver halide emulsion layer in the present invention is a layer in which photosensitive silver halide grains are dispersed in a hydrophilic colloid, and the number of such photosensitive silver halide emulsion layers may be only one layer, and in some cases In some cases, two or more layers may be provided. In the present invention, the fact that the melting time of at least one of the non-light-sensitive upper layers is greater than the melting time of the light-sensitive silver halide emulsion layer means that the non-light-sensitive upper layer is more strongly hardened than the emulsion layer. It means that. As a method to evaluate the degree of hardening of the hardened layer,
In the industry, the degree of swelling when a cured layer is swollen with a certain solution, or the scratch strength expressed as the load at which scratches are produced when scratched using a loaded needle-like stylus, are well known. In order to evaluate the objective of the present invention, it is best to immerse the cured film in a solution kept at a certain temperature and evaluate it using the time it takes for the film to start melting, that is, the melting time (MT). Most effective. Melting time measurements are best (but not necessarily) carried out in a 0.2N NaOH solution kept at 75°C. The photosensitive material for plate making of the present invention uses a polymer curing agent and a low molecular curing agent having an active vinyl group in combination, so that at least one of the non-photosensitive upper layers has a longer melting time than the photosensitive silver halide emulsion layer. It has been hardened to look like this. Since the polymer curing agent is a polymer, it has diffusion resistance, so when it is added to at least one of the non-photosensitive upper layers, only that layer is selectively hardened.
Other layers are cured with low molecular weight curing agents having active vinyl groups. Since many low molecular weight curing agents having active vinyl groups have diffusivity, this curing agent may be added to either the non-photosensitive upper layer or the photosensitive silver halide emulsion layer. In this case, the low-molecular-weight curing agent having an active vinyl group also diffuses into the non-photosensitive upper layer to which the above-mentioned polymeric curing agent is added, but since this layer is hardened by both curing agents, the photosensitive silver halide emulsion is It will be hardened more strongly than the layer. It is difficult to unambiguously define the amounts of the polymeric curing agent and the low-molecular curing agent having active vinyl groups, and these are determined by trial and error by measuring the melting time of each layer. For the purpose of the present invention, the amount of curing agent used is such that the melting time of the non-photosensitive upper layer is preferably at least 50 seconds or more, in particular at least 100 seconds longer than the melting time of the photosensitive silver halide, as measured by the aforementioned measuring method. It is preferable to set The polymer curing agent used in the present invention is
66841, UK Patent No. 1322971, UK Patent No.
No. 3671256, etc., and DMBurness J.
Pouradier “The Theory of the Photographic
Process”4th ed. (THJames ed.),
Macmillan, New York, 1977.pp84, GA
Campbell, LR Hamilton, ISPonticello,
“Polymeric Amine and Ammonium Salts”
(EJGoethals ed.) Pergamon Press, New
It is a polymer with a functional group that reacts with gelatin, which is well known from books such as York 1979, pp 321-332. In particular, a polymer curing agent having a molecular weight of 10,000 or more is preferred. As this polymer curing agent, those of the following general formulas (), () and () are preferable, and those of the general formula () are particularly preferable. In the formula, A represents an ethylenically unsaturated monomer copolymerizable with the monomer unit shown to the right. In the formula, R 1 represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms. Q is-
CO 2 -,
【式】〔但しR1は上述のものと
同じものを表わす〕又は６から10個の炭素原子を
有するアリーレン基のいずれかである。Ｌは―
CO2―，or an arylene group having from 6 to 10 carbon atoms. L is-
CO 2 -,
【式】〔但しR1は上述のものと同
じものを表わす〕結合のうち少なくとも一つ含む
３から15個の炭素原子を有する二価の基、あるい
は―Ｏ―，[Formula] [However, R 1 represents the same as above] A divalent group having 3 to 15 carbon atoms containing at least one bond, or -O-,
【式】―CO―，―SO―，―SO2―， ―SO3―，[Formula] ―CO―, ―SO―, ―SO 2 ―, ―SO 3 ―,
【式】【formula】
【式】〔R1は上述のものと同じものを表わ
す〕結合のうち少なくとも一つ含む１から12個の
炭素原子を有する二価の基のいずれかである。
R2はビニル基あるいはその前駆体となる官能基
を表わし、―CH＝CH2，―CH2CH2Xのいずれ
かである。Ｘは求核基によつて置換されうる基、
または塩酸によつてHXの形で脱離しうる基を表
わす。
式中ｘ，ｙはモル百分率を表わし、ｘは０ない
し99、ｙは１ないし100の値をとる。
式（）のＡで表わされるエチレン性不飽和モ
ノマーの例は、エチレン、プロピレン、１―ブテ
ン、イソブテン、スチレン、クロロメチルスチレ
ン、ヒドロキシメチルスチレン、ビニルベンゼン
スルホン酸ソーダ、ビニルベンジルスルホン酸ソ
ーダ、Ｎ，Ｎ，Ｎ―トリメチル―Ｎ―ビニルベン
ジルアンモニウムクロライド、Ｎ，Ｎ―ジメチル
―Ｎ―ベンジル―Ｎ―ベニルベンジルアンモニウ
ムクロライド、α―メチルスチレン、ビニルトル
エン、４―ビニルピリジン、２―ビニルピリジ
ン、ベンジルビニルピリジニウムクロライド、Ｎ
―ビニルアセトアミド、Ｎ―ビニルピロリドン、
１―ビニル―２―メチルイミダゾール、脂肪族酸
のモノエチレン性不飽和エステル（例えば酢酸ビ
ニル、酢酸アリル）、エチレン性不飽和のモノカ
ルボン酸もしくはジカルボン酸およびその塩（例
えばアクリル酸、メタクリル酸、イタコン酸、マ
レイン酸、アクリル酸ソーダ、アクリル酸カリウ
ム、メタクリル酸ソーダ）、無水マレイン酸、エ
チレン性不飽和モノカルボン酸もしくはジカルボ
ン酸のエステル（例えばｎ―ブチルアクリレー
ト、ｎ―ヘキシルアクリレート、ヒドロキシエチ
ルアクリレート、シアノエチルアクリレート、
Ｎ，Ｎ―ジエチルアミノエチルアクリレート、メ
チルメタクリレート、ｎ―ブチルメタクリレー
ト、ベンジルメタクリレート、ヒドロキシエチル
メタクリレート、クロロエチルメタクリレート、
メトキシエチルメタクリレート、Ｎ，Ｎ―ジエチ
ルアミノエチルメタクリレート、Ｎ，Ｎ，Ｎ―ト
リエチル―Ｎ―メタクリロイルオキシエチルアン
モニウムｐ―トルエンスルホナート、Ｎ，Ｎ―ジ
エチル―Ｎ―メチル―Ｎ―メタクリロイルオキシ
エチルアンモニウムｐ―トルエンスルホナート、
イタコン酸ジメチル、マレイン酸モノベンジルエ
ステル）、エチレン性不飽和のモノカルボン酸も
しくはジカルボン酸のアミド（例えばアクリルア
ミド、Ｎ，Ｎ―ジメチルアクリルアミド、Ｎ―メ
チロールアクリルアミド、Ｎ―（Ｎ，Ｎ―ジメチ
ルアミノプロピル）アクリルアミド、Ｎ，Ｎ，Ｎ
―トリメチル―Ｎ―（Ｎ―アクリロイルプロピ
ル）アンモニウムｐ―トルエンスルホナート、２
―アクリルアミド―２―メチルプロパンスルホン
酸ソーダ、アクリロイルモルホリン、メタクリル
アミド、Ｎ，Ｎ―ジメチル―N′―アクリロイル
プロパンジアミンプロピオナートベタイン、Ｎ，
Ｎ―ジメチル―N′―メタクリロイルプロパンジ
アミンアセテートベタイン）。
又、本発明の重合体を架橋されたラテツクスと
して用いる場合には、Ａとして上記のエチレン性
不飽和モノマー以外に、少くとも共重合可能なエ
チレン性不飽和基を２個以上もつモノマー（例え
ばジビニルベンゼン、メチレンビスアクリルアミ
ド、エチレングリコールジアクリレート、トリメ
チレングリコールアクリレート、エチレングリコ
ールジメタクリレート、トリメチレングリコール
ジメタクリレート、ネオペンチルグリコールジメ
タクリレート等）を用いる。
式（）の中のR1の例にはメチル基、エチル
基、ブチル基、ｎ―ヘキシル基が含まれる。
Ｑには次のような基が含まれる。
―CO2―，―CONH―，[Formula] [R 1 represents the same as defined above] Any divalent group having 1 to 12 carbon atoms containing at least one bond.
R 2 represents a vinyl group or a functional group serving as a precursor thereof, and is either -CH=CH 2 or -CH 2 CH 2 X. X is a group that can be substituted by a nucleophilic group,
Alternatively, it represents a group that can be eliminated in the form of HX by hydrochloric acid. In the formula, x and y represent molar percentages, x takes a value of 0 to 99, and y takes a value of 1 to 100. Examples of the ethylenically unsaturated monomer represented by A in formula () are ethylene, propylene, 1-butene, isobutene, styrene, chloromethylstyrene, hydroxymethylstyrene, sodium vinylbenzenesulfonate, sodium vinylbenzylsulfonate, N , N,N-trimethyl-N-vinylbenzylammonium chloride, N,N-dimethyl-N-benzyl-N-benylbenzylammonium chloride, α-methylstyrene, vinyltoluene, 4-vinylpyridine, 2-vinylpyridine, Benzylvinylpyridinium chloride, N
-vinylacetamide, N-vinylpyrrolidone,
1-vinyl-2-methylimidazole, monoethylenically unsaturated esters of aliphatic acids (e.g. vinyl acetate, allyl acetate), ethylenically unsaturated mono- or dicarboxylic acids and their salts (e.g. acrylic acid, methacrylic acid, itaconic acid, maleic acid, sodium acrylate, potassium acrylate, sodium methacrylate), maleic anhydride, esters of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. n-butyl acrylate, n-hexyl acrylate, hydroxyethyl acrylate) , cyanoethyl acrylate,
N,N-diethylaminoethyl acrylate, methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, hydroxyethyl methacrylate, chloroethyl methacrylate,
Methoxyethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N,N-triethyl-N-methacryloyloxyethylammonium p-toluenesulfonate, N,N-diethyl-N-methyl-N-methacryloyloxyethylammonium p- toluene sulfonate,
dimethyl itaconate, maleic acid monobenzyl ester), amides of ethylenically unsaturated monocarboxylic or dicarboxylic acids (e.g. acrylamide, N,N-dimethylacrylamide, N-methylolacrylamide, N-(N,N-dimethylaminopropyl) ) Acrylamide, N, N, N
-Trimethyl-N-(N-acryloylpropyl)ammonium p-toluenesulfonate, 2
-acrylamide-2-methylpropanesulfonate sodium, acryloylmorpholine, methacrylamide, N,N-dimethyl-N'-acryloylpropanediamine propionate betaine, N,
N-dimethyl-N'-methacryloylpropanediamine acetate betaine). In addition, when the polymer of the present invention is used as a crosslinked latex, in addition to the above-mentioned ethylenically unsaturated monomers, A may be a monomer having at least two or more copolymerizable ethylenically unsaturated groups (for example, divinyl). benzene, methylene bisacrylamide, ethylene glycol diacrylate, trimethylene glycol acrylate, ethylene glycol dimethacrylate, trimethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, etc.). Examples of R 1 in formula () include a methyl group, an ethyl group, a butyl group, and an n-hexyl group. Q includes the following groups. ―CO 2 ―, ―CONH―,
【式】【formula】
【式】【formula】
【式】 Ｌには次のような基が含まれる。 ―CH2CO2CH2― ―CH2CO2CH2CH2― ―CH2CH2CO2CH2CH2― （―CH2）―5CO2CH2CH2― （―CH2）―10CO2CH2CH2― ―CH2NHCOCH2― ―CH2NHCOCH2CH2― （―CH2）―3NHCOCH2CH2― （―CH2）―5NHCOCH2CH2― （―CH2）―10NHCOCH2CH2― ―CH2OCH2― ―CH2CH2OCH2CH2CH2―[Formula] L includes the following groups. ―CH 2 CO 2 CH 2 ― ―CH 2 CO 2 CH 2 CH 2 ― ―CH 2 CH 2 CO 2 CH 2 CH 2 ― (―CH 2 )― 5 CO 2 CH 2 CH 2 ― (―CH 2 )― 10 CO 2 CH 2 CH 2 ― ―CH 2 NHCOCH 2 ― ―CH 2 NHCOCH 2 CH 2 ― (―CH 2 )― 3 NHCOCH 2 CH 2 ― (―CH 2 )― 5 NHCOCH 2 CH 2 ― (―CH 2 )― 10 NHCOCH 2 CH 2 ― ―CH 2 OCH 2 ― ―CH 2 CH 2 OCH 2 CH 2 CH 2 ―
【式】
―COCH2CH2―
―CH2COCH2CH2―
―SOCH2CH2―
―CH2SOCH2CH2―
―SO2CH2CH2―
―SO2CH2CH2SO2CH2CH2―
―SO3CH2CH2CH2―
―SO3CH2CO2CH2CH2―
―SO3CH2CH2CO2CH2CH2―
―SO2NHCH2CO2CH2CH2―
―SO2NHCH2CH2CO2CH2CH2―
―NHCONHCH2CH2―
―CH2NHCONHCH2CH2―
―NHCO2CH2CH2―
―CH2NHCO2CH2CH2―
式（）中のR2には次のような基が含まれる。
―CH＝CH2，―CH2CH2Cl，―CH2CH2Br，
―CH2CH2O3SCH3，
[Formula] ―COCH 2 CH 2 ― ―CH 2 COCH 2 CH 2 ― ―SOCH 2 CH 2 ― ―CH 2 SOCH 2 CH 2 ― ―SO 2 CH 2 CH 2 ― ―SO 2 CH 2 CH 2 SO 2 CH 2 CH 2 ― ―SO 3 CH 2 CH 2 CH 2 ― ―SO 3 CH 2 CO 2 CH 2 CH 2 ― ―SO 3 CH 2 CH 2 CO 2 CH 2 CH 2 ― ―SO 2 NHCH 2 CO 2 CH 2 CH 2 ― ―SO 2 NHCH 2 CH 2 CO 2 CH 2 CH 2 ― ―NHCONHCH 2 CH 2 ― ―CH 2 NHCONHCH 2 CH 2 ― ―NHCO 2 CH 2 CH 2 ― ―CH 2 NHCO 2 CH 2 CH 2 ― R in formula () 2 includes the following groups: --CH=CH 2 , --CH 2 CH 2 Cl, --CH 2 CH 2 Br,
--CH 2 CH 2 O 3 SCH 3 ,
―CH2CH2OH，―CH2CH2O2CCH3，―
CH2CH2O2CCF3，―CH2CH2O2CCHCl2，
高分子硬化剤の他の好ましい米国特許4161407
号に記載されており、次式（）で表わされる繰
り返し単位を有している。
式中Ａはその右に示したモノマー単位と共重合
可能なエチレン性不飽和モノマー単位あるいはモ
ノマーの混合物である。
式中ｘ，ｙはモル百分率を表わし、ｘは10ない
し95パーセント、ｙは５ないし90パーセントの値
をとる。Ｒは水素原子または１から６個の炭素原
子を有するアルキル基；R′は―CH＝CH2，ある
いは―CH2CH2Xである。Ｘは求核基によつて置
換されうる基、または塩基によつてHXの形で脱
離しうる基を表わす。
L′はアルキレン（さらに好ましくは１から６個
の炭素原子を有するアルキレン例えばメチレン、
エチレン、イソブチレン等から選ばれる連結基）、
６から12個の炭素原子を有するアリーレン（例え
ばフエニレン、トリレン、ナフタレン等から選ば
れる連絡基）、あるいは、―COZ―、あるいは―
COZR3―、〔ここでR3は１から６個の炭素原子を
有するアルキレン、あるいは６から12個の炭素原
子を有するアリーレン、Ｚは酸素原子あるいは
NHである。〕から選ばれる連結基である。
式中（）のＡの例としては式（）のＡと同
じものが含まれる。式（）のＲの例としては式
（）のR1と同じ例が含まれる。式（）のR′の
例としては式（）のR2と同じ例が含まれる。
更に他の好ましい高分子硬化剤は英国特許
1534455号に記載されているように、次式（）
で表わされる繰り返し単位を有している。
式中Ａはその右に示したモノマー単位と共重合
可能なエチレン性不飽和モノマー単位をあらわ
し；Ｒは水素原子または１から６個の炭素原子を
有するアルキル基、Ｌは１から20個の炭素原子を
有する二価の連結基（更に好ましくは―CONH
―又は―CO―結合のうち少なくとも１つを含む
炭素数１〜12の２価基）；Ｘは活性エステル基；
ｘ，ｙはモル百分率をあらわし、ｘは０から95、
ｙは５から100の値をとり、ｍは０あるいは１で
ある。
式（）のＡの例としては式（）のＡの例と
同じものが含まれる。式（）のＲには式（）
のR1の例と同じものが含まれ、上記されている。
式（）のＬには次のような基が含まれる。
―CONHCH2―，―CONHCH2CH2―，
―CONHCH2CH・CH2―，
―CONHCH2CH2CH2CH2CH2―，
―COCH2CH2OCOCH2CH2―，
―CONHCH2CONHCH2―，
―CONHCH2CONHCH2CONH2CH2―，
―COCH2―，
―CONHCH2NHCOCH2CH2SCH2CH2―，
―CONHCH2OCOCH2CH2―など。
式（）のＸには次のような基が含まれる。 ―CH 2 CH 2 OH, ―CH 2 CH 2 O 2 CCH 3 , ―
CH 2 CH 2 O 2 CCF 3 , --CH 2 CH 2 O 2 CCHCl 2 , Other preferred US Pat. No. 4,161,407 for polymeric curing agents
It has a repeating unit represented by the following formula (). In the formula, A is an ethylenically unsaturated monomer unit or a mixture of monomers copolymerizable with the monomer unit shown to the right. In the formula, x and y represent mole percentages, where x takes a value of 10 to 95 percent and y takes a value of 5 to 90 percent. R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R' is -CH=CH 2 or -CH 2 CH 2 X. X represents a group that can be substituted by a nucleophilic group or a group that can be eliminated in the form of HX by a base. L' is alkylene (more preferably alkylene having 1 to 6 carbon atoms, such as methylene,
(linking group selected from ethylene, isobutylene, etc.),
Arylene having 6 to 12 carbon atoms (for example, a connecting group selected from phenylene, tolylene, naphthalene, etc.), or -COZ-, or -
COZR 3 --, [where R 3 is alkylene with 1 to 6 carbon atoms or arylene with 6 to 12 carbon atoms, Z is oxygen atom or
It is NH. ] is a linking group selected from. Examples of A in formula () include the same as A in formula (). Examples of R in formula () include the same example as R 1 in formula (). Examples of R' in formula () include the same example as R 2 in formula (). Yet another preferred polymeric curing agent is a British patented
As stated in issue 1534455, the following formula ()
It has a repeating unit represented by In the formula, A represents an ethylenically unsaturated monomer unit copolymerizable with the monomer unit shown to the right; R is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; L is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; A divalent linking group having an atom (more preferably -CONH
- or -CO-- a divalent group having 1 to 12 carbon atoms containing at least one bond); X is an active ester group;
x, y represent mole percentage, x is from 0 to 95,
y takes a value from 5 to 100, and m is 0 or 1. Examples of A in formula () include the same examples as A in formula (). R in formula () is the formula ()
Contains the same thing as the R1 example and is described above. L in formula () includes the following groups. ―CONHCH 2 ―, ―CONHCH 2 CH 2 ―, ―CONHCH 2 CH・CH 2 ―, ―CONHCH 2 CH 2 CH 2 CH 2 CH 2 ―, ―COCH 2 CH 2 OCOCH 2 CH 2 ―, ―CONHCH 2 CONHCH 2 ―, ―CONHCH 2 CONHCH 2 CONH 2 CH 2 ―, ―COCH 2 ―, ―CONHCH 2 NHCOCH 2 CH 2 SCH 2 CH 2 ―, ―CONHCH 2 OCOCH 2 CH 2 ―, etc. X in formula () includes the following groups.
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】【formula】
【式】―CO2CH2CN ―
CO2CH2CO2C2H5 ―CO2CH2CONH2 ―
CO2CH2COCH3 [Formula] - CO 2 CH 2 CN - CO 2 CH 2 CO 2 C 2 H 5 - CO 2 CH 2 CONH 2 -
CO 2 CH 2 COCH 3
【式】―
CO2CH2CO2CH＝CH2 ―CO2N＝CHCH3 ―
CO2N＝Ｃ（CH3）2 [Formula] - CO 2 CH 2 CO 2 CH=CH 2 - CO 2 N=CHCH 3 -
CO2N =C( CH3 ) 2
【式】【formula】
【式】―CO2CH2CH2Br
―CO2CH2CH2CN
次に本発明に使用し得る化合物の具体例を示す
がこれらに限定されるものではない。
但し、Ｍは水素原子、ナトリウム原子、カリウ
ム原子であり、ｘ，ｙはそれぞれ各ユニツトの仕
込のモル百分率であり上記にかぎられるものでは
なくｘは０ないし99、ｙは１ないし100の値をと
りうる。
以下に本発明に用いられる高分子硬化剤の合成
に用いられる代表的なビニルスルホン基あるいは
その前駆体となる官能基を有するエチレン性不飽
和モノマーの合成例を具体的に示す。
合成例 １
２―（３―クロロエチルスルホニル）―プロピ
オイルオキシ）―エチルアクリレートの合成
反応容器にテトラヒドロフラン600ml、ヒドロ
キシエチルアクリレート45.8ｇ、３―（２―クロ
ロエチルスルホニル）―プロピオン酸クロライド
72ｇを加え、氷水により冷却しながら、５℃以下
で、ピリジン31.2ｇをテトラヒドロフラン100ml
に溶解したものを1.75時間で滴下した。その後室
温で２時間撹拌を続け、反応試料を、2.5の氷
水中に注ぎ込み、クロロホルム300mlにより４回
抽出した。有機層を硫酸ナトリウムにより乾燥
後、濃縮して、２―（３―（クロロエチルスルホ
ニル）―プロピオイルオキシ）―エチルアクリレ
ート87ｇを得た。（収率88％）
合成例 ２
Ｎ―（（３―（クロロエチルスルホニル）プロ
ピオイル）アミノメチル）―アクリルアミドの
合成
２の反応容器に、蒸留水1400ml、亜硫酸ナト
リウム224ｇ、炭酸水素ナトリウム220ｇを加え、
撹拌して溶解させた後、氷水により冷却しながら
約５℃で、クロロエタンスルホニルクロリド260
ｇを1.5時間で滴下した。その後49％硫酸160ｇを
約15分ほどで滴下し、５℃で１時間撹拌を続け
て、析出した結晶を濾過した後、結晶を400mlの
蒸留水で洗滌し、濾液と洗滌液とをいつしよにし
て３の反応容器に入れた。この中に、メチレン
ビスアクリルアミド246ｇを蒸留水480ml、エタノ
ール1480mlに溶解させたものを、氷冷しながら約
５℃で、30分間で滴下した後、全体を冷蔵庫に５
日間放置して反応を完結させた。析出した結晶を
濾取した後、冷却した蒸留水800mlで洗滌し、
2000の50％エタノール水溶液から再結晶して、
219ｇのモノマーを得た。収率は49％であつた。
（分析結果、実測値、Ｈ：5.17，Ｃ：37.90，Ｎ：
9.48，Cl：12.58）
合成例 ３
（３―（クロロエチルスルホニル）―プロピオ
イル）―アミノメチルスチレンの合成
反応容器にテトラヒドロフラン100ml、ビニル
ベンジルアミン20.1ｇ、トリエチルアミン16.7
ｇ、ハイドロキノン0.1ｇを入れ、氷水により冷
却しながら、β―クロロエチルスルホニルプロピ
オン酸クロライド36.1ｇを200mlのテトラヒドロ
フランに溶解させたものを30分で滴下した。その
後室温で一夜間放置し、反応試料を濃塩酸を16.5
ｇを氷水1.5で希釈した溶液中に注ぎ込み、生
成する沈澱を濾取した。この沈澱をエタノール
200ml、水200mlの混合溶媒から再結して、26.8ｇ
のＮ―ビニルベンジル―β―クロロエチルスルホ
ニルプロピオン酸アミドを得た。（収率57％、分
析結果 実測値、Ｈ：5.74、Ｃ：53.47、、Ｎ：
4.83、Cl：10.99、Ｓ：10.49）
合成例 ４
１―（（２―（４―ビニルベンゼンスルホニル）
―エチル）―スルホニル）―３―クロロエチル
スルホニル―２―プロパノールの合成
反応容器に１，３―ビスクロロエチルスルホニ
ル―２―プロパノール157ｇ（合成法日本国特許
特願昭51―132929参照）、メタノール１、蒸留
水１を加え、46℃に加熱しながら、ビニルベン
ゼンスルフイン酸カリウム52ｇをメタノール100
ml、蒸留水100mlに溶解させたものを１時間で滴
下した。その後46℃に保つたまま5.5時間撹拌を
続け、生成する沈澱を濾取して55ｇの２―（１―
ビニルベンゼンスルホニル）―エチルスルホニル
―３―クロロエチルスルホニル―２―プロパノー
ルを得た。（収率49％、分析結果 実測値、Ｈ：
4.67、Ｃ：39.89、Ｓ：21.43）
さらに本発明に好ましく用いられる高分子硬化
剤の合成例を示す。
合成例 ５
ポリ―（２―（３―（ビニルスルホニル）―プ
ロピオイルオキシ）―エチルアクリレート―コ
―アクリルアミド―２―メチルプロパンスルホ
ン酸ソーダ）（Ｐ―１）の合成
反応容器にＮ，Ｎ―ジメチルホルムアミド60
ml、２―（３―（クロロエチルスルホニル）―プ
ロピオイルオキシ）―エチルアクリレート14.5
ｇ、アクリルアミド―２―メチルプロパンスルホ
ン酸23.5ｇを入れ、窒素ガスで脱気後、60℃に加
熱して、２，2′―アゾビス（２，４―ジメチルバ
レロニトリル）0.40ｇを加え、２時間加熱撹拌を
続けた。その後さらに２，2′―アゾビス（２，４
―ジメチルバレロニトリル）0.2ｇを加え、２時
間加熱、撹拌を続けた後、５℃に冷却して炭酸ソ
ーダ12ｇ、トリエチルアミン4.9ｇを加え、１時
間撹拌を行ない、室温で１時間撹拌を続けた後、
反応試料をセルロースチユーブに入れて２日間透
析し、凍結乾燥によつて35ｇの白色ポリマーを得
た。（収率95％）、このポリマーのビニルスルホン
含量は0.51×10-3当量／ｇであつた。
合成例 ６
ポリ―〔Ｎ―（（３―（ビニルスルホニル）プ
ロピオイル）アミノメチル）アクリルアミド〕
―コ―アクリルアミド―２―メチルプロパンス
ルホン酸ソーダ（Ｐ―２）の合成
200mlの反応容器に、合成例―２のモノマー
5.65ｇ、アクリルアミド―２―メチルプロパンス
ルホン酸ソーダ9.16ｇ、50％エタノール水溶液80
mlを加え、撹拌しながら80℃に加熱し、２，2′―
アゾビス―（２，４―ジメチルバレロニトリル）
（Ｖ―65として和光純薬工業(株)から市販されてい
るもの）0.1ｇを加え、さらに30分後にも同じも
のを0.1ｇ加えて、１時間、加熱、撹拌を続けた。
その後、氷水により約10℃に冷却して、トリエチ
ルアミン2.5ｇを80mlのエタノールに溶解させた
ものを加え、１時間撹拌を続けてから、反応試料
を撹拌しながら１のアセトンに注ぎ込み、生成
した沈澱を濾取して、12.4ｇのＰ―２を得た。収
率は85％で、極限粘度〔η〕＝0.227、ビニルスル
ホン含量は0.95×10-3当量／ｇであつた。
合成例 ７
ポリ（（３―クロロエチルスルホニル）―プロ
ピオイル）―アミノメチルスチレン―コ―アク
リルアミド―２―メチルプロパンスルホン酸ソ
ーダ）（Ｐ―16）の合成
反応容器に、（３―（ビニルスルホニル）―プ
ロピオイル）―アミノメチルスチレン15.8ｇ―、
アクリルアミド―２―メチルプロパンスルホン酸
ソーダ23.6ｇ、Ｎ，Ｎ―ジメチルホルムアミド75
mlを入れ、窒素ガスで脱気後、80℃に加熱して、
２，2′―アゾビス（２，４―ジメチルバレロニ
リル）0.75ｇを加え、３時間、加熱、撹拌を続け
た。その後Ｎ，Ｎ―ジメチルホルムアルデヒド25
mlを加え、室温で、トリエチルアミン6.1ｇを滴
下し、１時間撹拌を続け、濾過して濾液をアセト
ン800ml中に投入し、生成する沈澱を濾取して、
乾燥し、36.2ｇの淡黄色ポリマーを得た。（収率
94％）、このポリマーのビニルスルホン含量は
0.80×10-3当量／ｇであつた。
合成例 ８
ポリ―（１―（（２―（４―ビニルベンゼンス
ルホニル）―エチル）―スルホニル）―３―ク
ロロエチルスルホニル―２―プロパノール―コ
―アクリル酸ソーダ）（Ｐ―17）の合成
反応容器にＮ，Ｎ―ジメチルホルムアミド300
ml、２―（１―ビニルベンゼンスルホニル）―エ
チルスルホニル―３―クロロエチルスルホニル―
２―プロパノール40.1ｇ、アクリル酸13.0ｇを入
れ、窒素ガスで脱気後、70℃に加熱して、２，
2′―アゾビス（２，４―ジメチルバレロニトリ
ル）0.53ｇを加え、1.5時間、加熱、撹拌を続け
た。その後２，2′―アゾビス（２，４―ジメチル
バレロニトリル）0.53ｇを加え、１時間、加熱、
撹拌を続けた。室温に放冷してから、ナトリウム
メチラート28％メタノール溶液54.8ｇを滴下し、
１時間撹拌を続け、反応試料をセルロースチユー
ブに入れて、２日間透析し、凍結乾燥によつて30
ｇの淡黄色ポリマーを得た。（収率56％）このポ
リマーのビニルスルホン含量は1.4×10-3当量／
ｇであつた。
なお合成例５〜８によつて合成された高分子硬
化剤の分子量はすべて１万以上であつた。
本発明に使用される活性ビニル基を有する低分
子硬化剤は、アクリロイル系硬化剤およびビニル
スルホン系硬化剤を包含する。これら低分子硬化
剤は好ましくは1000以下の分子量を持つ化合物で
ある。
本発明に適用されるアクリロイル系硬化剤とし
ては、分子中に少なくとも２個のアクリロイル基
を有する化合物があげられるが、１個のカルボニ
ル基が２個のビニル基に連結している化合物（例
えば下記例示化合物Ａ―４）も包含する。次にそ
の代表例を示す。
これらの化合物は、例えば米国特許3640720号、
英国特許994869号、西独特許872153号、特公昭46
―105号、同47―13141号等に記された方法にした
がつて合成することができる。
本発明に使用する活性ビニル基を有する化分子
硬化剤としてはビニルスルホン系低分子硬化剤が
特に好ましい。
ビニルスルホン系低分子硬化剤は、写真感光材
料の分野で多くのものが知られており、本発明で
はそのいずれをも用いることができる。例えば米
国特許3490911号、同3642486号、同3811891号、
同3841872号、同3850639号、同3868257号、同
4088495号、同4134765号、同4134770号、同
4137082号、同4137440号、同4142897号、同
4179976号等に記載されている炭素原子若くはヘ
テロ原子で結合されたビニルスルホニルアルキル
化合物、アミド基若くはエステル基を介して結合
されたビニルスルホン化合物、トリアジン環等の
ヘテロ環若しくはフエニレン基などの芳香環を介
して結合されたビニルスルホン化合物などの他
に、１個のスルホニル基が２個のビニル基に連結
している化合物（例えば下記例示化合物のＶ―
38）も使用できる。
一方、本発明に用いられる活性ビニル基を有す
る低分子量の硬化剤の代表的具体例を上げると次
のようなものがある。[Formula] - CO 2 CH 2 CH 2 Br - CO 2 CH 2 CH 2 CN Next, specific examples of compounds that can be used in the present invention will be shown, but the invention is not limited thereto. However, M is a hydrogen atom, a sodium atom, or a potassium atom, and x and y are the mole percentages of each unit, and are not limited to the above. Possible. Specific examples of synthesis of ethylenically unsaturated monomers having a typical vinyl sulfone group or a functional group serving as a precursor thereof used in the synthesis of the polymer curing agent used in the present invention are shown below. Synthesis Example 1 Synthesis of 2-(3-chloroethylsulfonyl)-propioyloxy)-ethyl acrylate In a reaction vessel, 600 ml of tetrahydrofuran, 45.8 g of hydroxyethyl acrylate, and 3-(2-chloroethylsulfonyl)-propionic acid chloride.
Add 72g of pyridine and add 31.2g of pyridine to 100ml of tetrahydrofuran at below 5℃ while cooling with ice water.
was added dropwise over 1.75 hours. Afterwards, stirring was continued for 2 hours at room temperature, and the reaction sample was poured into 2.5 g of ice water and extracted four times with 300 ml of chloroform. The organic layer was dried over sodium sulfate and concentrated to obtain 87 g of 2-(3-(chloroethylsulfonyl)-propioyloxy)-ethyl acrylate. (Yield 88%) Synthesis Example 2 Synthesis of N-((3-(chloroethylsulfonyl)propioyl)aminomethyl)-acrylamide Into the reaction vessel from step 2, add 1400 ml of distilled water, 224 g of sodium sulfite, and 220 g of sodium hydrogen carbonate.
After stirring to dissolve, add chloroethanesulfonyl chloride 260 at about 5°C while cooling with ice water.
g was added dropwise over 1.5 hours. Then, 160 g of 49% sulfuric acid was added dropwise over about 15 minutes, stirring was continued for 1 hour at 5°C, and the precipitated crystals were filtered. The crystals were washed with 400 ml of distilled water, and the filtrate and washing solution were combined. The mixture was then placed in the reaction vessel No. 3. A solution of 246 g of methylene bisacrylamide dissolved in 480 ml of distilled water and 1,480 ml of ethanol was added dropwise to this solution at approximately 5°C for 30 minutes while cooling with ice, and the whole was placed in the refrigerator for 5 minutes.
The reaction was allowed to stand for several days to complete the reaction. After collecting the precipitated crystals by filtration, they were washed with 800 ml of cooled distilled water.
Recrystallize from 50% ethanol aqueous solution of 2000,
219 g of monomer was obtained. The yield was 49%.
(Analysis results, measured values, H: 5.17, C: 37.90, N:
9.48, Cl: 12.58) Synthesis Example 3 Synthesis of (3-(chloroethylsulfonyl)-propioyl)-aminomethylstyrene In a reaction vessel: 100 ml of tetrahydrofuran, 20.1 g of vinylbenzylamine, 16.7 g of triethylamine.
g and 0.1 g of hydroquinone were added thereto, and while cooling with ice water, a solution of 36.1 g of β-chloroethylsulfonylpropionic acid chloride dissolved in 200 ml of tetrahydrofuran was added dropwise over 30 minutes. After that, leave it at room temperature overnight, and add 16.5 ml of concentrated hydrochloric acid to the reaction sample.
g was poured into a solution diluted with 1.5 g of ice water, and the resulting precipitate was collected by filtration. Ethanol this precipitate.
26.8g by reconsolidating from a mixed solvent of 200ml and 200ml of water.
N-vinylbenzyl-β-chloroethylsulfonylpropionic acid amide was obtained. (Yield 57%, analysis results actual values, H: 5.74, C: 53.47, N:
4.83, Cl: 10.99, S: 10.49) Synthesis example 4 1-((2-(4-vinylbenzenesulfonyl)
Synthesis of -ethyl)-sulfonyl)-3-chloroethylsulfonyl-2-propanol In a reaction vessel, add 157 g of 1,3-bischloroethylsulfonyl-2-propanol (see synthesis method Japanese Patent Application No. 132929/1989) and methanol. 1. Add 1 part of distilled water and heat to 46℃, add 52 g of potassium vinylbenzenesulfinate to 100 g of methanol.
ml, dissolved in 100 ml of distilled water, was added dropwise over 1 hour. Afterwards, stirring was continued for 5.5 hours while maintaining the temperature at 46°C, and the precipitate formed was collected by filtration, and 55 g of 2-(1-
Vinylbenzenesulfonyl)-ethylsulfonyl-3-chloroethylsulfonyl-2-propanol was obtained. (Yield 49%, analysis result actual value, H:
4.67, C: 39.89, S: 21.43) Furthermore, a synthesis example of a polymer curing agent preferably used in the present invention will be shown. Synthesis Example 5 Synthesis of poly-(2-(3-(vinylsulfonyl)-propioyloxy)-ethyl acrylate-co-acrylamide-2-methylpropanesulfonic acid sodium) (P-1) N, N- in the reaction vessel dimethylformamide 60
ml, 2-(3-(chloroethylsulfonyl)-propioyloxy)-ethyl acrylate 14.5
g, 23.5 g of acrylamide-2-methylpropanesulfonic acid, degassed with nitrogen gas, heated to 60°C, added 0.40 g of 2,2'-azobis(2,4-dimethylvaleronitrile), Heating and stirring was continued for an hour. Then, 2,2′-azobis(2,4
- Dimethylvaleronitrile) 0.2g was added, heated and stirred for 2 hours, cooled to 5°C, added 12g of soda carbonate and 4.9g of triethylamine, stirred for 1 hour, and continued stirring at room temperature for 1 hour. rear,
The reaction sample was placed in a cellulose tube and dialyzed for 2 days, and 35 g of white polymer was obtained by lyophilization. (yield 95%), and the vinyl sulfone content of this polymer was 0.51×10 -3 equivalent/g. Synthesis Example 6 Poly-[N-((3-(vinylsulfonyl)propioyl)aminomethyl)acrylamide]
-Synthesis of sodium co-acrylamide-2-methylpropanesulfonate (P-2) In a 200ml reaction vessel, add the monomer of Synthesis Example-2.
5.65g, sodium acrylamide-2-methylpropanesulfonate 9.16g, 50% ethanol aqueous solution 80
ml and heated to 80℃ with stirring, 2,2'-
Azobis-(2,4-dimethylvaleronitrile)
0.1 g (commercially available as V-65 from Wako Pure Chemical Industries, Ltd.) was added, and 30 minutes later, 0.1 g of the same was added, and heating and stirring were continued for 1 hour.
Thereafter, the mixture was cooled to approximately 10°C with ice water, and a solution of 2.5 g of triethylamine dissolved in 80 ml of ethanol was added. After stirring for 1 hour, the reaction sample was poured into acetone (1) with stirring, and the precipitate formed. was collected by filtration to obtain 12.4 g of P-2. The yield was 85%, the intrinsic viscosity [η] was 0.227, and the vinyl sulfone content was 0.95×10 -3 equivalent/g. Synthesis Example 7 Synthesis of poly((3-chloroethylsulfonyl)-propioyl)-aminomethylstyrene-co-acrylamide-2-methylpropanesulfonate sodium) (P-16) In a reaction vessel, (3-(vinylsulfonyl)) -propioyl) -aminomethylstyrene 15.8g-,
Sodium acrylamide-2-methylpropanesulfonate 23.6g, N,N-dimethylformamide 75g
ml, degassed with nitrogen gas, and heated to 80℃.
2,2'-azobis(2,4-dimethylvaleroni)
0.75 g of Ril) was added, and heating and stirring were continued for 3 hours. Then N,N-dimethylformaldehyde 25
ml, add 6.1 g of triethylamine dropwise at room temperature, continue stirring for 1 hour, filter, pour the filtrate into 800 ml of acetone, collect the formed precipitate by filtration,
After drying, 36.2 g of pale yellow polymer was obtained. (yield
94%), the vinyl sulfone content of this polymer is
It was 0.80×10 −3 equivalent/g. Synthesis Example 8 Synthesis of poly-(1-((2-(4-vinylbenzenesulfonyl)-ethyl)-sulfonyl)-3-chloroethylsulfonyl-2-propanol-co-sodium acrylate) (P-17) Reaction N,N-dimethylformamide 300 in a container
ml, 2-(1-vinylbenzenesulfonyl)-ethylsulfonyl-3-chloroethylsulfonyl-
Add 40.1 g of 2-propanol and 13.0 g of acrylic acid, degas with nitrogen gas, and heat to 70°C.
0.53 g of 2'-azobis(2,4-dimethylvaleronitrile) was added, and heating and stirring were continued for 1.5 hours. Then, 0.53 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added and heated for 1 hour.
Stirring was continued. After cooling to room temperature, 54.8 g of a 28% methanol solution of sodium methylate was added dropwise.
Stirring was continued for 1 hour, the reaction sample was placed in a cellulose tube, dialyzed for 2 days, and lyophilized for 30 minutes.
g of pale yellow polymer was obtained. (Yield 56%) The vinyl sulfone content of this polymer is 1.4×10 -3 equivalent/
It was hot at g. The molecular weights of the polymer curing agents synthesized in Synthesis Examples 5 to 8 were all 10,000 or more. The low molecular weight curing agent having an active vinyl group used in the present invention includes an acryloyl curing agent and a vinyl sulfone curing agent. These low molecular curing agents are preferably compounds having a molecular weight of 1000 or less. Examples of the acryloyl curing agent applicable to the present invention include compounds having at least two acryloyl groups in the molecule, and compounds in which one carbonyl group is linked to two vinyl groups (for example, the following Exemplary compound A-4) is also included. A typical example is shown below. These compounds are described, for example, in US Pat. No. 3,640,720;
British Patent No. 994869, West German Patent No. 872153, Special Publication No. 1977
It can be synthesized according to the method described in No. 105, No. 47-13141, etc. As the molecular curing agent having an active vinyl group used in the present invention, a vinyl sulfone type low molecular curing agent is particularly preferable. Many vinyl sulfone-based low-molecular curing agents are known in the field of photographic materials, and any of them can be used in the present invention. For example, US Patent No. 3490911, US Patent No. 3642486, US Patent No. 3811891,
No. 3841872, No. 3850639, No. 3868257, No.
No. 4088495, No. 4134765, No. 4134770, No. 4134765, No. 4134770, No.
No. 4137082, No. 4137440, No. 4142897, No. 4137082, No. 4137440, No. 4142897, No.
4179976 etc., vinylsulfonylalkyl compounds bonded via carbon atoms or heteroatoms, vinylsulfone compounds bonded via amide groups or ester groups, heterocycles such as triazine rings, or phenylene groups. In addition to vinyl sulfone compounds bonded via an aromatic ring, compounds in which one sulfonyl group is bonded to two vinyl groups (for example, V-
38) can also be used. On the other hand, typical specific examples of the low molecular weight curing agent having an active vinyl group used in the present invention are as follows.
【表】【table】
【表】【table】
【表】
高分子硬化剤の添加方法としては、水または有
機溶媒にとかした硬化剤を硬化度をコントロール
したい層に直接添加する。活性ビニル基を有する
低分子硬化剤は、高分子硬化剤を添加した非感光
性上部層へ添加しても良いが、他の非感光性上部
又は乳剤層へ添加して全層に拡散させても良い。
耐拡散性の高分子硬化剤の添加量は、高分子硬化
剤の反応基の量で規定して添加する。
このようにして非感光性上部層の少なくとも１
層をその融解時間が感光性ハロゲン化銀乳剤層の
融解時間よりも大きくなるように選択的に硬化せ
しめることによつて、減力液が銀画像を酸化し溶
解する速度に異方性をもたせることができるよう
になる。すなわち非感光性上部層の少なくとも１
層が銀画像の形成される感光性ハロゲン化銀乳剤
層よりも強く硬化されているため、減力液は銀画
像の画像濃度の低下をもたらす方向（乳剤層に対
して垂直の方向）からよりも銀画像の画像面積の
減小をもたらす方向（乳剤層に対して水平の方
向）からより多く銀画像を攻撃することになる。
従つて本発明においては銀画像の濃度低下に対す
る画像面積の縮小巾すなわち減力巾を大きくする
ことが可能になるのである。
写真感光材料の上部層を下部層よりも強く硬化
すると劣化した処理液で高温処理した場合に、レ
チキユレーシヨンと称する網状模様を生ずること
がある〔R.J.Cox編集、Tojoら、Photographic
Gelatin（1972）、Academic Press，P49〜61〕
本発明においてはかかるレチキユレーシヨン発
生を、非感光性上部層にポリマーラテツクスを含
有させることにより防止することができる。
本発明において非感光性上部層に用いられるポ
リマーラテツクスとは、例えば米国特許第
2772166号、同3325286号、同3411911号、同
3311912号、同3525620号、リサーチ デイスクロ
ージヤー（Research Disclosure）誌No.195
19551（1980年７月）等に記載されている如き、ア
クリル酸エステル、メタアクリル酸エステル；ス
チレン等のビニル重合体の水和物である。特に好
ましいものは、メチルアクリレート、エチルアク
リレート、ブチルアクリレート、メチルメタアク
リレート、エチルアクリレートなどのアルキルア
クリレート、アルキルメタアクリレートの単独重
合体又はこれらのアルキルアクリレート、アルキ
ルメタアクリレートと他のビニル重合体、例え
ば、アクリル酸、Ｎ―メチロールアクリルアミド
等との共重合体などが挙げられる。
本発明で用いるポリマーラテツクスの平均粒径
の好ましい範囲は0.005〜1μ特に0.02〜0.1μであ
る。かかるポリマーラテツクスの使用によつてレ
チキユレーシヨンの発生を極めて効果的に防止で
きる。また上記のポリマーラテツクスの中で、ガ
ラス転移点（Tg）の高いラテツクスはさらに耐
接着性能の改良のために好ましい。特にTgが室
温以上のものが好ましい。例えば、メチルメタア
クリレート、エチルメタアクリレート、スチレン
等の単独ビニル重合体の水和物又はこれらのビニ
ル重合体と他のビニル重合体、例えばアクリル
酸、Ｎ―メチロールアクリルアミド等との共重合
体が特に好ましい。
ポリマーラテツクスの添加量としては添加すべ
き層の親水性コロイドの重量当り５〜200％特に
10〜100％が好ましい。
本発明に使用し得るポリマーラテツクスの具体
例を示すがこれらに限定されるものではない。
合成例
ポリマーラテツクス（メタクリル酸メチル）
ガス導入管、還流冷却器、かきまぜ装置を備え
た1000mlの三つ口フラスコ中、蒸留水800mlに
4.28ｇのラウリル硫酸ナトリウムを溶かした溶液
に150.0ｇのメタクリル酸メチルを乳化分散させ、
塩化第一鉄9.6mgを加えた。内温を60℃に保ち、
20mlの蒸留水に0.41ｇの過硫酸カリウムを溶解、
さらに0.16ｇの亜硫酸水素ナトリウムを溶解後、
2Nのアンモニア水2.0mlを加え、これを重合開始
剤として添加した。２時間後、さらに同上の重合
開始剤を加え、２時間ポスト重合を行つた。冷却
後、薄手の濾紙にて濾過をし、濃度15.9wt％、粒
径0.04μ、PH6.13の蛋白色のメタクリル酸メチル
のポリマーラテツクスを得た。
一般的に本方法を用いてポリマーラテツクスを
合成することができる。
本発明の非感光性上部層及び感光性ハロゲン化
銀乳剤層に用いられる親水性コロイドとしてはゼ
ラチンが好ましい。ゼラチンはその製造過程にお
いて、ゼラチン抽出前、アルカリ浴に浸漬される
所謂アルカリ処理（石灰処理）ゼラチン、酸浴に
浸漬される酸処理ゼラチン、または、「Bull Soc
Sci Photo Japan」No.16 30頁（1966）に記載さ
れているような酵素処理ゼラチン、さらに誘導体
ゼラチン、変性ゼラチンのいずれでも良い。更
に、非感光性上部層に用いられるゼラチンとし
て、減力処理液の拡散をコントロールする上から
も、上述のゼラチンに加えて、高粘度ゼラチン、
高ゼリー強度ゼラチン、デユアルソークゼラチン
等を上げることができる。
このゼラチンと組合せて、または単独でゼラチ
ン以外の親水性コロイドを用いることができる。
たとえば、ゼラチンと他の高分子とのグラフトポ
リマー、アルブミン、カゼイン等の蛋白質；ヒド
ロキシエチルセルロース、カルボキシメチルセル
ロース、セルローズ硫酸エステル類等の如きセル
ロース誘導体、アルギン酸ソーダ、澱粉誘導体な
どの糖誘導体；ポリビニルアルコール、ポリビニ
ルアルコール部分アセタール、ポリ―Ｎ―ビニル
ピロリドン、ポリアクリル酸、ポリメタクリル
酸、ポリアクリルアミド、ポリビニルイミダゾー
ル、ポリビニルピラゾール等の単一あるいは共重
合体の如き多種の合成親水性高分子物質を用いる
ことができる。
本発明の非感光性上部層には、前記の如き親水
性コロイドバインダー（たとえばゼラチン）とポ
リマーラテツクスの他に、界面活性剤、帯電防止
剤、マツト剤、滑り剤、コロイダルシリカ、ゼラ
チン可塑化剤、等を含有させることが出来る。
マツト剤としてはポリメチルメタアクリレー
ト、二酸化ケイ素の0.1〜10μ、特に１〜5μ程度の
粒子が好ましい。
マツト剤は非感光性上部層より下の層に添加し
ても良く、または高分子硬膜剤を含む塗布液に添
加しても良い。
本発明の非感光性上部層は乾燥厚みが全層で
0.3〜5μ、特に0.5〜3μになるように塗布されるの
が好ましい。
本発明に於ける製版用感材とは、前記の如く、
印刷工業分野に於て、網点画像や線画像を写真製
版法により印刷する際に用いる感材であり、その
種類・性能は特に限定されないが、最も一般的な
感材は、云わゆるリスフイルムの如き硬調感材で
ある。
本発明の製版用感材の感光性ハロゲン化銀乳剤
層に用いられるハロゲン化銀としては特に限定は
なく塩臭化銀、塩沃臭化銀、沃臭化銀、臭化銀等
を用いることができるが特に、塩化銀を少くとも
60モル％（好ましくは75モル％以上）含み、沃化
銀を０〜５モル％含む塩臭化銀もしくは塩沃臭化
銀が好ましい。ハロゲン化銀粒子の形態、晶癖、
サイズ分布等に制限はないが粒径0.7μ以下のもの
が好ましい。
ハロゲン化銀乳剤は塩化金酸塩、三塩化金など
のような金化合物、ロジウム、イリジウムの如き
貴金属の塩、銀塩と反応して硫酸銀を形成するイ
オウ化合物、第一スズ塩、アミン類の如き還元性
物質で粒子を粗大化しないで感度を上昇させるこ
とが出来る。又ロジウム、イリジウムの如き貴金
族の塩、赤血塩等鉄化合物をハロゲン化銀粒子の
物理熟成時、又は核生成時に存在せしめることも
出来る。
本発明に用いられる写真乳剤は、メチン色素類
その他によつて分光増感されてよい。これらの増
感色素は単独に用いてもよいが、それらの組合せ
を用いてもよく、増感色素の組合せは特に強色増
感の目的でしばしば用いられる。増感色素ととも
に、それ自身分光増感作用をもたない色素あるい
は可視光を実質的に吸収しない物質であつて、強
色増感を示す物質を乳剤中に含んでもよい。
有用な増感色素、強色増感を示す色素の組合せ
及び強色増感を示す物質は、リサーチ・デスクロ
ージヤ（Research Disclosure）176巻17643
（1978年12月発行）第23頁のＪ項に記載されて
いる。
写真乳剤にはカブリ防止剤として、４―ヒドロ
キシ―６―メチル―１，３，3a，７―テトラア
ザインデン、３―メチルベンゾチアゾール、１―
フエニル―５―メルカプトテトラゾーンをはじめ
多もの複素環化合物、含水銀化合物、メルカプト
化合物などの他特開昭49―81024、同50―6306、
同50―19429、米国特許3850639号に記載されてい
るような当業界でよく知られた化合物を用いるこ
とが出来る。
本発明の感光性ハロゲン化銀乳剤層には、塗布
助剤、写真特性の改良等の目的で界面活性剤を添
加することが出来る。
界面活性剤としては、サポニンの如き天然界面
活性剤、アルキレンオキサイド系、クリシドール
系などのノニオン界面活性剤、カルボン酸、スル
ホン酸（例えば米国特許3415649号記載の界面活
性剤）、燐酸、硫酸エステル基、燐酸エステル基
などの酸性基を含むアニオン界面活性剤、アミノ
酸類、アミノスルホン酸類、アミノアルコールの
硫酸又は燐酸エステル等の両性界面活性剤が好ま
しく用いられる。
本発明に用いるポリアルキレンオキシド化合物
は、炭素数２〜４のアルキレンオキシド、たとえ
ばエチレンオキシド、プロピレン―１，２―オキ
シド、ブチレン―１，２―オキシドなど、好まし
くはエチレンオキシドの、少くとも10単位から成
るポリアルキレンオキシドと、水、脂肪族アルコ
ール、芳香族アルコール、脂肪酸、有機アミン、
ヘキシトール誘導体などの活性水素原子を少くと
も１個有する化合物との縮合物あるいは二種以上
のポリアルキレンオキシドのブロツクコポリマー
などを包含する。すなわち、ポリアルキレンオキ
シド化合物として、具体的には
ポリアルキレングリコール類
ポリアルキレングリコールアルキルエーテル類
ポリアルキレングリコールアリールエーテル類
ポリアルキレングリコール（アルキルアリー
ル）エステル類
ポリアルキレングリコールエステル類
ポリアルキレングリコール脂肪酸アミド類
ポリアルキレングリコールアミン類
ポリアルキレングリコール・ブロツク共重合体
ポリアルキレングリコールグラフト重合物
などを用いることができる。
本発明で好ましく用いられるポリアルキレンオ
キシド化合物の具体例をあげると次の如くであ
る。
ポリアルキレンオキシド化合物例[Table] The method for adding a polymeric curing agent is to directly add the curing agent dissolved in water or an organic solvent to the layer whose degree of curing is desired to be controlled. A low-molecular curing agent having an active vinyl group may be added to a non-photosensitive upper layer to which a polymeric curing agent has been added, but it may also be added to another non-photosensitive upper layer or an emulsion layer and diffused into the entire layer. Also good.
The amount of the diffusion-resistant polymer curing agent to be added is determined by the amount of reactive groups in the polymer curing agent. In this way at least one of the non-photosensitive top layers
Provide anisotropy in the rate at which the reducing fluid oxidizes and dissolves the silver image by selectively curing the layer such that its melting time is greater than the melting time of the light-sensitive silver halide emulsion layer. You will be able to do this. i.e. at least one of the non-photosensitive upper layers.
Because the layer is more strongly hardened than the light-sensitive silver halide emulsion layer on which the silver image is formed, the reducing liquid is applied more strongly in the direction (perpendicular to the emulsion layer) that results in a decrease in the image density of the silver image. Also, the silver image will be attacked more from the direction (horizontal to the emulsion layer) resulting in a reduction in the image area of the silver image.
Therefore, in the present invention, it is possible to increase the reduction width of the image area, that is, the reduction width of the image area with respect to the decrease in the density of the silver image. If the upper layer of a photographic light-sensitive material is hardened more strongly than the lower layer, a net-like pattern called reticle formation may occur when processed at high temperature with a degraded processing solution [edited by RJCox, Tojo et al., Photographic
Gelatin (1972), Academic Press, P49-61] In the present invention, such retickling can be prevented by containing a polymer latex in the non-photosensitive upper layer. The polymer latex used for the non-photosensitive upper layer in the present invention includes, for example, the polymer latex disclosed in U.S. Pat.
No. 2772166, No. 3325286, No. 3411911, No.
No. 3311912, No. 3525620, Research Disclosure No. 195
19551 (July 1980), etc., are acrylic esters, methacrylic esters; hydrates of vinyl polymers such as styrene. Particularly preferred are alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl acrylate, homopolymers of alkyl methacrylates, or other vinyl polymers of these alkyl acrylates, alkyl methacrylates, e.g. Examples include copolymers with acrylic acid, N-methylolacrylamide, and the like. The average particle size of the polymer latex used in the present invention is preferably in the range of 0.005 to 1μ, particularly 0.02 to 0.1μ. By using such a polymer latex, the occurrence of retickling can be extremely effectively prevented. Further, among the above-mentioned polymer latexes, latexes having a high glass transition temperature (Tg) are preferable in order to further improve adhesive resistance. In particular, those having a Tg of room temperature or higher are preferred. For example, hydrates of homovinyl polymers such as methyl methacrylate, ethyl methacrylate, and styrene, or copolymers of these vinyl polymers with other vinyl polymers, such as acrylic acid, N-methylolacrylamide, etc., are particularly suitable. preferable. The amount of polymer latex added is preferably 5 to 200% based on the weight of the hydrophilic colloid in the layer to be added.
10-100% is preferred. Specific examples of polymer latexes that can be used in the present invention are shown below, but the invention is not limited thereto. Synthesis example Polymer latex (methyl methacrylate) Added to 800 ml of distilled water in a 1000 ml three-necked flask equipped with a gas inlet, reflux condenser, and stirring device.
Emulsifying and dispersing 150.0 g of methyl methacrylate in a solution of 4.28 g of sodium lauryl sulfate,
9.6 mg of ferrous chloride was added. Keep the internal temperature at 60℃,
Dissolve 0.41g of potassium persulfate in 20ml of distilled water,
After dissolving further 0.16g of sodium bisulfite,
2.0 ml of 2N ammonia water was added as a polymerization initiator. After 2 hours, the same polymerization initiator was further added, and post-polymerization was carried out for 2 hours. After cooling, the mixture was filtered through thin filter paper to obtain a protein-colored methyl methacrylate polymer latex with a concentration of 15.9 wt%, a particle size of 0.04 μ, and a pH of 6.13. Polymer latexes can generally be synthesized using this method. Gelatin is preferred as the hydrophilic colloid used in the non-photosensitive upper layer and the photosensitive silver halide emulsion layer of the present invention. During the manufacturing process, gelatin is produced using so-called alkali-treated (lime-treated) gelatin, which is soaked in an alkaline bath, acid-treated gelatin, which is soaked in an acid bath, or "Bull Soc" gelatin, which is soaked in an alkaline bath before gelatin extraction.
Any of enzyme-treated gelatin as described in "Sci Photo Japan" No. 16 p. 30 (1966), derivative gelatin, and modified gelatin may be used. Furthermore, in addition to the above-mentioned gelatin, high-viscosity gelatin,
High jelly strength gelatin, dual soak gelatin etc. can be raised. Hydrophilic colloids other than gelatin can be used in combination with the gelatin or alone.
For example, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of alcohol partial acetals, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. . In addition to the above-mentioned hydrophilic colloid binder (eg gelatin) and polymer latex, the non-photosensitive upper layer of the present invention contains surfactants, antistatic agents, matting agents, slip agents, colloidal silica, gelatin plasticizers, etc. agent, etc. can be contained. As the matting agent, particles of polymethyl methacrylate or silicon dioxide having a size of about 0.1 to 10 microns, particularly about 1 to 5 microns are preferable. The matting agent may be added to a layer below the non-photosensitive upper layer or may be added to a coating solution containing a polymeric hardener. The dry thickness of the non-photosensitive upper layer of the present invention is
It is preferable to apply the coating to a thickness of 0.3 to 5μ, particularly 0.5 to 3μ. As mentioned above, the photosensitive material for plate making in the present invention is
In the printing industry, this is a photosensitive material used when printing halftone images and line images using photolithography, and its type and performance are not particularly limited, but the most common photosensitive material is so-called lithium film. It is a high-contrast sensitive material like . The silver halide used in the photosensitive silver halide emulsion layer of the photosensitive material for plate making of the present invention is not particularly limited, and silver chlorobromide, silver chloroiodobromide, silver iodobromide, silver bromide, etc. may be used. In particular, at least silver chloride
Silver chlorobromide or silver chloroiodobromide containing 60 mol % (preferably 75 mol % or more) and 0 to 5 mol % of silver iodide is preferred. Form of silver halide grains, crystal habit,
There are no restrictions on the size distribution, etc., but particles with a particle size of 0.7 μm or less are preferred. Silver halide emulsions include gold compounds such as chlorauric acid salts and gold trichloride, salts of noble metals such as rhodium and iridium, sulfur compounds that react with silver salts to form silver sulfate, stannous salts, and amines. It is possible to increase the sensitivity without making the particles coarser by using reducing substances such as. Further, salts of noble metals such as rhodium and iridium, and iron compounds such as red blood salts may be present during physical ripening of silver halide grains or during nucleation. The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. Useful sensitizing dyes, dye combinations exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure, Vol. 176, 17643.
(Published December 1978) Page 23, Section J. Antifoggants used in photographic emulsions include 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, 3-methylbenzothiazole, 1-
In addition to phenyl-5-mercaptotetrazone, many heterocyclic compounds, mercury-containing compounds, mercapto compounds, etc., JP-A-49-81024, JP-A-50-6306,
Compounds well known in the art such as those described in US Pat. No. 50-19429 and US Pat. No. 3,850,639 can be used. A surfactant can be added to the photosensitive silver halide emulsion layer of the present invention for purposes such as a coating aid and improvement of photographic properties. Examples of the surfactant include natural surfactants such as saponin, nonionic surfactants such as alkylene oxide type and cricidol type, carboxylic acid, sulfonic acid (for example, the surfactant described in US Pat. No. 3,415,649), phosphoric acid, and sulfuric acid ester group. , anionic surfactants containing acidic groups such as phosphate ester groups, and amphoteric surfactants such as amino acids, aminosulfonic acids, and sulfuric or phosphoric esters of amino alcohols. The polyalkylene oxide compound used in the present invention consists of at least 10 units of alkylene oxide having 2 to 4 carbon atoms, such as ethylene oxide, propylene-1,2-oxide, butylene-1,2-oxide, etc., preferably ethylene oxide. Polyalkylene oxide, water, aliphatic alcohol, aromatic alcohol, fatty acid, organic amine,
It includes condensates with compounds having at least one active hydrogen atom such as hexitol derivatives, block copolymers of two or more types of polyalkylene oxides, and the like. That is, examples of polyalkylene oxide compounds include polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers, polyalkylene glycol (alkylaryl) esters, polyalkylene glycol esters, polyalkylene glycol fatty acid amides, and polyalkylenes. Glycolamines, polyalkylene glycol block copolymers, polyalkylene glycol graft polymers, and the like can be used. Specific examples of polyalkylene oxide compounds preferably used in the present invention are as follows. Examples of polyalkylene oxide compounds
乾燥膜厚が1μになる様に塗布した。
層―３ 第２非感光性上部層（最上層）
〔Γ ゼラチン １ｇ―／100c.c.H2O
Γ ドデシルベンゼンスルホン酸ナトリウム10
mg／ｇゼラチン
Γ 硬化剤 第１表記載のとうり添加〕
乾燥膜厚が1.0μになる様に塗布した。
It was applied so that the dry film thickness was 1μ. Layer-3 Second non-photosensitive upper layer (top layer) [Γ Gelatin 1g-/100c.cH 2 O Γ Sodium dodecylbenzenesulfonate 10
mg/g gelatin Γ Hardening agent Added as listed in Table 1] Coated so that the dry film thickness was 1.0μ.
【表】
次に各試料を25℃、60％RH、75％RHの湿度
条件で保存し、経時を追て、次式で表わされる膨
潤度を25℃の水中で測定し、膨潤度が一定となる
日数（塗布後）を求めた。
膨潤度＝膨潤して増加した膜厚／乾燥時の膜厚
更に、特公昭45―5331号明細書実施例１と同じ
方法で写真性を経時を追つて測定し、相対感度及
び、感度の安定化する日数（塗布後）を求めた。
得られた結果を第２表に示す。
更に、前述の方法により非感光性上部層と感光
性ハロゲン化銀乳剤層の融解時間を測定した。各
保存条件で安定化した時点での性能を第２表に示
す。[Table] Next, each sample was stored under humidity conditions of 25℃, 60%RH, and 75%RH, and over time, the degree of swelling expressed by the following formula was measured in water at 25℃, and the degree of swelling was constant. The number of days (after application) was determined. Swelling degree = film thickness increased by swelling / film thickness when dry In addition, photographic properties were measured over time using the same method as in Example 1 of Japanese Patent Publication No. 45-5331, and relative sensitivity and stability of sensitivity were determined. The number of days (after application) for it to change was determined.
The results obtained are shown in Table 2. Furthermore, the melting times of the non-photosensitive upper layer and the photosensitive silver halide emulsion layer were measured by the method described above. Table 2 shows the performance at the time of stabilization under each storage condition.
【表】
第２表の試料番号、１では本発明以外の低分子
硬化剤（グリオギザール）単独でかなり速い硬化
性能を示しているのに対し、高分子硬化剤を用い
てると非常に硬化速度が遅くなつているのがわか
るしかも25℃75％RHに保存すると硬化速度は速
くなつているが、他と比べてかなり遅い。さらに
重大な欠点は25℃60％RH保存品と比較して差が
大きすぎることである（すなわち保存時の湿度依
存性が大きい）。
これに対して試料番号３及び４、あるいは、５
及び６の比較から明白な様に本発明の試料４、６
は硬化進行性が大でかつその保存湿度依存性は非
常に小さく、極めてすぐれた性能を示しているこ
とがわかる。又、活性ビニル低分子硬化剤を非感
光性上部層と乳剤層に分配して添加し塗布した試
料（番号７）においても同様にすぐれた性能が得
られている。
第２表から明らかなように本発明以外の硬化剤
の組合せを用いた試料２は硬膜進行の湿度依存性
が大きいため、写真特性も極めて湿度依存性が大
きいことがわかるが、これに対して、本発明の硬
化剤の組合せを用いた場合は写真特性の保存湿度
依存性が顕著に改良されていることがわかる。
次に上記試料に、次の方法により網点画像を形
成した。
市販のネガ用グレイコンタクトスクリーン
（150線／インチ）を試料に密着せしめ、これに段
差が0.1の階段のウエツジを通して白色タングス
テン光を10秒間露光した。この試料を下記の現像
液を用い、38℃では20秒間高温迅速現像を行な
い、通常の方法によつて定着、水洗、乾燥した。
現像液
炭酸ナトリウム（１水塩 11ｇ
臭化カリウム ３ｇ
ハイドロキノン 23ｇ
１―フエニル―３―ピラゾリドン 0.4ｇ
亜硫酸ナトリウム 67ｇ
水酸化カリウム 11ｇ
水を加えて １
得られた網点ストリツプスを下記セリウム系減
力液（20℃）に浸漬し水洗した。
減力液 （）
硫酸第二セリウム 25ｇ
浸硫酸 30ｇ
水を加えて １
又、同じく得られた網点ストリツプスを下記エ
エチレンジアミンテトラ酢酸第２鉄塩系減力液
（20℃）に浸漬し水洗した。
減力液 （）
エチレンジアミンテトラ酢酸第２鉄ナトリウ
ム塩 85ｇ
チオ尿素 65ｇ
クエン酸 60ｇ
塩酸（PH0.03にする量）
水を加えて １
このようにして得られた網点ストリツプスの網
点面積の変化と網点１個あたりの濃度の変化をミ
クロデントメーターにて測定し、網点面積50％の
網点が減力処理した後、網点個々の濃度で2.5と
なる時の網点面積を求め、両者の差を求めて減力
巾値を得た。更に、濃度2.5となるまでに要した
減力時間を求めた。
得られた結果を第３表に示す。[Table] Sample number 1 in Table 2 shows fairly fast curing performance using a low-molecular curing agent other than the present invention (Glyogysal) alone, whereas using a polymeric curing agent shows a very fast curing performance. You can see that the curing speed is slowing down, and when stored at 25°C and 75% RH, the curing speed becomes faster, but it is still quite slow compared to the others. A more serious drawback is that the difference is too large compared to products stored at 25°C and 60% RH (that is, the humidity dependence during storage is large). On the other hand, sample numbers 3 and 4, or 5
As is clear from the comparison of Samples 4 and 6 of the present invention
It can be seen that the curing progress is large and its dependence on storage humidity is very small, indicating extremely excellent performance. Similarly, excellent performance was also obtained in the sample (No. 7) in which the activated vinyl low-molecular-weight curing agent was distributed and added to the non-photosensitive upper layer and the emulsion layer. As is clear from Table 2, the dura progression of Sample 2 using a combination of curing agents other than the present invention is highly dependent on humidity, so it can be seen that the photographic properties are also extremely dependent on humidity. It can be seen that when the combination of curing agents of the present invention is used, the dependence of photographic properties on storage humidity is significantly improved. Next, a halftone image was formed on the sample by the following method. A commercially available negative gray contact screen (150 lines/inch) was brought into close contact with the sample, and white tungsten light was exposed to the screen for 10 seconds through a step wedge with a step height of 0.1. This sample was subjected to rapid high-temperature development at 38° C. for 20 seconds using the following developer, followed by fixing, washing with water, and drying in a conventional manner. Developer solution Sodium carbonate (monohydrate 11g Potassium bromide 3g Hydroquinone 23g 1-phenyl-3-pyrazolidone 0.4g Sodium sulfite 67g Potassium hydroxide 11g Water was added.) 1. Added the obtained halftone dot strips to the following cerium-based reducing solution ( 20℃) and washed with water.Reducing solution (25g of ceric sulfate, 30g of sulfuric acid soaked) Add water. (20℃) and washed with water.Reducing solution () Ferric sodium salt of ethylenediaminetetraacetic acid 85g Thiourea 65g Citric acid 60g Hydrochloric acid (amount to make pH 0.03) Add water 1 Obtained in this way The changes in the dot area and the density per dot of the dot strips were measured using a microdentometer, and after the dots with a dot area of 50% were reduced, The halftone dot area when the density reached 2.5 was determined, and the difference between the two was found to obtain the reduction width value.Furthermore, the reduction time required until the density reached 2.5 was determined.The obtained results are shown in Table 3. Shown below.
【表】
第３表からも明らかなように、層別に硬化した
試料（番号２，４，６，７）はいずれも減力巾が
広くなつている。特に本発明の試料（番号４，
６，７，８）は減力液及びで性能差がなく
（すなわち減力液種依存性がなく）極めてすぐれ
た性能を示している。その上、減力時間は適度な
大きさであるかかる性能は本発明のすぐれた特徴
といえる。
又、試料番号１から８に上記と同一の現像処理
を施し、各試料につき処理後のレチキユレーシヨ
ンの発生の程度を顕微鏡を用いて観察したが、い
ずれの試料においてもレチキユレーシヨンは発生
しなかつた。
実施例 ２
実施例１と同様にして、試料９から13を第４表
のごとく、ポリマーラテツクス及び、高分子硬化
剤の添加量を変えて作成した。[Table] As is clear from Table 3, all of the samples (numbers 2, 4, 6, and 7) that were cured layer by layer had a wide range of force reduction. In particular, the sample of the invention (number 4,
Nos. 6, 7, and 8) show extremely excellent performance, with no difference in performance between the reducing fluids (that is, no dependence on the type of reducing fluid). Moreover, this performance, in which the force reduction time is of an appropriate length, can be said to be an excellent feature of the present invention. In addition, the same development process as above was applied to sample numbers 1 to 8, and the degree of reticleation after processing was observed for each sample using a microscope. It did not occur. Example 2 Samples 9 to 13 were prepared in the same manner as in Example 1 by changing the amounts of polymer latex and polymer curing agent added as shown in Table 4.
【表】
各試料について、膨潤度及び感度を実施例１と
同様に測定し、性能が一定となる日数（塗布後）
を求めた、得られた結果を第６表に示す。
本発明に係る試料（番号10〜13）から明白なよ
うに、保存湿度依存性が小さいことがわかる。さ
らに、高分子硬化剤の添加量が増加しても、実施
例１と同様に極めてすぐれた硬化性能を示してい
る。[Table] The swelling degree and sensitivity of each sample were measured in the same manner as in Example 1, and the number of days (after application) for which the performance remained constant.
The obtained results are shown in Table 6. As is clear from the samples according to the present invention (numbers 10 to 13), it can be seen that the dependence on storage humidity is small. Furthermore, even if the amount of polymer curing agent added increased, extremely excellent curing performance was shown as in Example 1.
【表】
実施例１記載の減力液（）を用いて同様に試
料を減力処理した。得られた結果を第７表に示す
高分子硬化剤の添加量を増したことにより非感光
性上部層の融解時間が大きくなり、硬化が大きく
なるにつれて減力巾が広くなつている。また、本
発明に係る試料はいずれも良い減力性能を示して
いる。又、減力時間も添加量を大きくすることに
より大きくなつていることがわかる。
更に上記試料を処理し、レチキユレーシヨン発
生の程度をしらべたが、いずれもレチキユレーシ
ヨンは発生しなかつた。[Table] A sample was similarly subjected to a reduction treatment using the reduction liquid () described in Example 1. The obtained results are shown in Table 7. By increasing the amount of polymer curing agent added, the melting time of the non-photosensitive upper layer became longer, and as the curing became longer, the force reduction width became wider. Moreover, all the samples according to the present invention exhibit good force reduction performance. It can also be seen that the force reduction time also increases as the amount added increases. The above samples were further processed to examine the degree of retickling, but no retickling occurred in any of them.
Claims (1)
化銀乳剤層及び該乳剤層の上部に少なくとも１層
の非感光性上部層を有して成る製版用ハロゲン化
銀感光材料に於て、非感光性上部層の少なくとも
１層の融解時間が感光性ハロゲン化銀乳剤層の融
解時間よりも大きくなるように、高分子硬化剤と
活性ビニル基を有する低分子硬化剤とを併用して
硬化したことを特徴とする製版用ハロゲン化銀写
真感光材料。 ２ 支持体上に少なくとも１層の感光性ハロゲン
化銀乳剤層及び該乳剤層の上部に少なくとも１層
の非感光性上部層を有して成る製版用ハロゲン化
銀感光材料に於て、非感光性上部層の少なくとも
１層の融解時間が感光性ハロゲン化銀乳剤層の融
解時間よりも大きくなるように高分子硬化剤とビ
ニルスルホン基を有する低分子硬化剤とを併用し
て硬化した製版用ハロゲン化銀写真感光材料を露
光・現像処理して得られた銀画像を減力処理する
ことを特徴とする製版用ハロゲン化銀写真感光材
料の減力処理方法。[Scope of Claims] 1. A silver halide photosensitive material for plate making, comprising at least one photosensitive silver halide emulsion layer on a support and at least one non-photosensitive upper layer on top of the emulsion layer. In this step, a polymeric curing agent and a low molecular curing agent having an active vinyl group are used such that the melting time of at least one of the non-photosensitive upper layers is longer than the melting time of the photosensitive silver halide emulsion layer. A silver halide photographic light-sensitive material for plate making characterized by being cured in combination. 2. In a silver halide photosensitive material for plate making, which has at least one photosensitive silver halide emulsion layer on a support and at least one non-photosensitive upper layer above the emulsion layer, a non-photosensitive silver halide emulsion layer is provided. For plate making, which is cured using a combination of a polymer curing agent and a low molecular curing agent having a vinyl sulfone group so that the melting time of at least one of the photosensitive upper layers is longer than the melting time of the photosensitive silver halide emulsion layer. 1. A method for reducing power of a silver halide photographic light-sensitive material for plate making, characterized in that a silver image obtained by exposing and developing the silver halide photographic light-sensitive material is subjected to power reduction processing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14182282A JPS5931944A (en) | 1982-08-16 | 1982-08-16 | Silver halide photosensitive material for plate making and its reduction process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14182282A JPS5931944A (en) | 1982-08-16 | 1982-08-16 | Silver halide photosensitive material for plate making and its reduction process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5931944A JPS5931944A (en) | 1984-02-21 |
| JPH0153768B2 true JPH0153768B2 (en) | 1989-11-15 |
Family
ID=15300927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14182282A Granted JPS5931944A (en) | 1982-08-16 | 1982-08-16 | Silver halide photosensitive material for plate making and its reduction process |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5931944A (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61147245A (en) * | 1984-12-20 | 1986-07-04 | Konishiroku Photo Ind Co Ltd | Silver halide photographic sensitive material |
| JPS62178949A (en) * | 1986-02-03 | 1987-08-06 | Konishiroku Photo Ind Co Ltd | Silver halide photographic sensitive material |
| DE3781311T2 (en) * | 1986-04-24 | 1993-04-01 | Konishiroku Photo Ind | LIGHT SENSITIVE PHOTOGRAPHIC SILVER HALOGENIDE MATERIAL. |
| JPH0625855B2 (en) * | 1986-05-06 | 1994-04-06 | コニカ株式会社 | Silver halide photographic light-sensitive material with improved antistatic property and adhesion resistance |
| JPH0619519B2 (en) * | 1986-05-16 | 1994-03-16 | コニカ株式会社 | Photosensitive material having improved transferability of organopolysiloxane |
| JP2532838B2 (en) * | 1986-05-29 | 1996-09-11 | コニカ株式会社 | Silver halide color photographic light-sensitive material capable of obtaining stable images |
| JP2532839B2 (en) * | 1986-05-30 | 1996-09-11 | コニカ株式会社 | Silver halide color photographic light-sensitive material with improved sharpness and color reproducibility |
| JP2532840B2 (en) * | 1986-06-02 | 1996-09-11 | コニカ株式会社 | Silver halide photographic light-sensitive material with excellent drying property |
| JPS63106644A (en) * | 1986-10-22 | 1988-05-11 | Konica Corp | Silver halide photographic sensitive material for photomechanical process ensuring improved reducibility and reducing method |
| JPH07101289B2 (en) * | 1987-03-11 | 1995-11-01 | コニカ株式会社 | High-speed processing silver halide photographic light-sensitive material |
| JPH0481841A (en) * | 1990-07-25 | 1992-03-16 | Konica Corp | Processing method for silver halide photographic sensitive material |
| JP2002144570A (en) | 2000-11-10 | 2002-05-21 | Canon Inc | Method of ejecting liquid drop, method of forming image, liquid jet apparatus and head |
-
1982
- 1982-08-16 JP JP14182282A patent/JPS5931944A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5931944A (en) | 1984-02-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0153769B2 (en) | ||
| US4822727A (en) | Silver halide photographic light-sensitive material | |
| US4396706A (en) | Silver halide photographic light-sensitive material and image forming method | |
| JPH0153768B2 (en) | ||
| US4533623A (en) | Silver halide photographic light-sensitive materials for plate making and method of reduction treatment for them | |
| US5561034A (en) | Core-shell latex for use in photographic materials | |
| JPH037927B2 (en) | ||
| JPH0466012B2 (en) | ||
| US3584391A (en) | Drying ei ement,chemical composition and process | |
| JPS6161146A (en) | Silver halide photosensitive material and reducing process thereof | |
| JPS5952416B2 (en) | photographic material | |
| EP0699952B1 (en) | A novel core-shell latex for use in photographic materials | |
| JPS6083936A (en) | Photosensitive silver halide material for photomechanical process and reducing method using it | |
| JP3521376B2 (en) | Silver halide photographic light-sensitive material and image forming method thereof | |
| JPH056174B2 (en) | ||
| JP2552444B2 (en) | Silver halide photographic material | |
| JPH037928B2 (en) | ||
| JP3409225B2 (en) | Silver halide photographic materials | |
| JP3429940B2 (en) | Silver halide photographic material and processing method thereof | |
| JP3243668B2 (en) | Silver halide photographic materials | |
| JPH0349089B2 (en) | ||
| JPH0244049B2 (en) | HAROGENKAGINSHASHINKANKOZAIRYO | |
| JPH0648348B2 (en) | Silver halide photographic light-sensitive material | |
| JPH11265039A (en) | Silver halide photographic sensitive material and its processing method | |
| JPH09281622A (en) | Silver halide photographic sensitive material |