JPH03219235A - Silver halide photographic sensitive material improved in antistatic and coating performance - Google Patents
Silver halide photographic sensitive material improved in antistatic and coating performanceInfo
- Publication number
- JPH03219235A JPH03219235A JP1536890A JP1536890A JPH03219235A JP H03219235 A JPH03219235 A JP H03219235A JP 1536890 A JP1536890 A JP 1536890A JP 1536890 A JP1536890 A JP 1536890A JP H03219235 A JPH03219235 A JP H03219235A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- silver halide
- photographic
- group
- denotes
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 Silver halide Chemical class 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 title claims abstract description 63
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 47
- 239000004332 silver Substances 0.000 title claims abstract description 47
- 239000011248 coating agent Substances 0.000 title abstract description 38
- 238000000576 coating method Methods 0.000 title abstract description 38
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract 4
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000000084 colloidal system Substances 0.000 claims description 17
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001340 alkali metals Chemical group 0.000 claims description 3
- 230000003068 static effect Effects 0.000 abstract description 11
- 230000002411 adverse Effects 0.000 abstract description 5
- 230000002265 prevention Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 125000004429 atom Chemical group 0.000 abstract 1
- 230000009193 crawling Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 60
- 239000000839 emulsion Substances 0.000 description 40
- 238000000034 method Methods 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000000203 mixture Substances 0.000 description 23
- 108010010803 Gelatin Proteins 0.000 description 19
- 229920000159 gelatin Polymers 0.000 description 19
- 239000008273 gelatin Substances 0.000 description 19
- 235000019322 gelatine Nutrition 0.000 description 19
- 235000011852 gelatine desserts Nutrition 0.000 description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 238000012545 processing Methods 0.000 description 13
- 239000011241 protective layer Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 11
- 239000012190 activator Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 239000000975 dye Substances 0.000 description 10
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 8
- 238000011161 development Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 8
- 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 7
- 229910021612 Silver iodide Inorganic materials 0.000 description 7
- 125000000129 anionic group Chemical group 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000035945 sensitivity Effects 0.000 description 7
- 229940045105 silver iodide Drugs 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 239000003518 caustics Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 238000000586 desensitisation Methods 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 description 3
- 230000002940 repellent Effects 0.000 description 3
- 239000005871 repellent Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229930182490 saponin Natural products 0.000 description 3
- 150000007949 saponins Chemical class 0.000 description 3
- 235000017709 saponins Nutrition 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000004378 air conditioning Methods 0.000 description 2
- 239000002519 antifouling agent Substances 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000003493 decenyl group Chemical group [H]C([*])=C([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 125000002960 margaryl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 2
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001846 repelling effect Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 125000005063 tetradecenyl group Chemical group C(=CCCCCCCCCCCCC)* 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 125000005040 tridecenyl group Chemical group C(=CCCCCCCCCCCC)* 0.000 description 2
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 125000005065 undecenyl group Chemical group C(=CCCCCCCCCC)* 0.000 description 2
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- WFNHDWNSTLRUOC-UHFFFAOYSA-M (2-nitrophenyl)-triphenylphosphanium;chloride Chemical compound [Cl-].[O-][N+](=O)C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WFNHDWNSTLRUOC-UHFFFAOYSA-M 0.000 description 1
- LQZDDWKUQKQXGC-UHFFFAOYSA-N 2-(2-methylprop-2-enoxymethyl)oxirane Chemical compound CC(=C)COCC1CO1 LQZDDWKUQKQXGC-UHFFFAOYSA-N 0.000 description 1
- ZZXILYOBAFPJNS-UHFFFAOYSA-N 2-octylbenzene-1,4-diol Chemical compound CCCCCCCCC1=CC(O)=CC=C1O ZZXILYOBAFPJNS-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 1
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- 102100038916 Caspase-5 Human genes 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical class OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 101100112336 Homo sapiens CASP5 gene Proteins 0.000 description 1
- 235000019687 Lamb Nutrition 0.000 description 1
- 101100273286 Mus musculus Casp4 gene Proteins 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 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
- GNPHADHWEUDSJZ-UHFFFAOYSA-M S(=O)([O-])[O-].[Na+].S(=S)(=O)(O)O.[NH4+] Chemical compound S(=O)([O-])[O-].[Na+].S(=S)(=O)(O)O.[NH4+] GNPHADHWEUDSJZ-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical class [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 1
- YEDTWOLJNQYBPU-UHFFFAOYSA-N [Na].[Na].[Na] Chemical compound [Na].[Na].[Na] YEDTWOLJNQYBPU-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005599 alkyl carboxylate group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 229940045714 alkyl sulfonate alkylating agent Drugs 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- PBGKVJXGTXXFLO-UHFFFAOYSA-N azanium azane bromide Chemical compound N.[NH4+].[Br-] PBGKVJXGTXXFLO-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- CJPQIRJHIZUAQP-MRXNPFEDSA-N benalaxyl-M Chemical compound CC=1C=CC=C(C)C=1N([C@H](C)C(=O)OC)C(=O)CC1=CC=CC=C1 CJPQIRJHIZUAQP-MRXNPFEDSA-N 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N benzene carboxamide Natural products NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005394 methallyl group Chemical group 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000005375 organosiloxane group Chemical group 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 125000005156 substituted alkylene group Chemical group 0.000 description 1
- 235000000346 sugar Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing 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
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000004886 thiomorpholines Chemical class 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は帯電防止されたハロゲン化銀写真感光材料に関
し、詳しくは写真特性に悪影響を及ぼすことなく帯電防
止されたハロゲン化銀写真感光材料に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic material that is antistatic, and more particularly to a silver halide photographic material that is antistatic without adversely affecting photographic properties. .
近年、ハロゲン化銀写真感光材料（以下、写真感光材料
または単に感光材料という）に対する要求は益々複雑多
岐に亙り、特に写真性能が安定した高感度にしてカブリ
の発生が少なく、シかも高画質の感光材料が要望されて
いる。In recent years, the demands for silver halide photographic materials (hereinafter referred to as photographic materials or simply referred to as photosensitive materials) have become increasingly complex and diverse.In particular, the requirements for silver halide photographic materials (hereinafter referred to as photographic materials or simply photosensitive materials) have become increasingly complex and diverse. Photosensitive materials are in demand.
特にＸ線用感光材料等においては、人体に対するＸ線の
被曝量を少なくするために、より少ないＸ線量で多くの
情報が得られるような高感度、高画質で、しかも早く情
報を得るため迅速現像処理に適合した感光材料が望まれ
ている。In particular, for X-ray photosensitive materials, etc., in order to reduce the amount of X-rays the human body is exposed to, high sensitivity and high image quality are required to obtain a lot of information with a smaller amount of X-rays. A photosensitive material that is suitable for development processing is desired.
感光材料は一般に電気絶縁性の支持体および写真構成層
から成っているので、感光材料の製造工程中ならびに使
用時に同種または異種物質の表面との間の接触摩擦また
は剥離を受けることにより静電電荷が蓄積され易い。現
像処理前に蓄積された静電電荷が放電することによって
感光性乳剤層が感光し、写真フィルムを現像処理した際
に点状スポットまたは樹枝状や羽毛状の線環、いわゆる
スタチックマークを生ずる。これは写真フィルムの商品
価値を著しく損ねる。例えば医療用または工業用Ｘ−レ
イフィルム等に現れるスタチックマークは非常に危険な
判断に繋がるが、この現象は現像してみて初めて明らか
になるもので非常に厄介な問題の１つである。また、こ
れらの蓄積された静電電荷は、フィルム表面へ塵挨が付
着したり、塗布が均一に行えないなどの第２次的故障を
誘起する原因ともなる。このスタチックマークは感光材
料の高感度化および高速塗布、高速撮影、高速自動処理
化等により一層発生し易くなっている。Since photosensitive materials generally consist of an electrically insulating support and photographic constituent layers, they are subject to electrostatic charges due to contact friction or peeling between the surfaces of the same or different materials during the manufacturing process and during use. is likely to accumulate. The photosensitive emulsion layer is sensitized by the discharge of electrostatic charges accumulated before processing, resulting in dot-like spots or dendritic or feather-like wire rings, so-called static marks, when photographic film is processed. . This significantly reduces the commercial value of photographic film. For example, static marks that appear on medical or industrial X-ray films can lead to extremely dangerous judgments, but this phenomenon is one of the most troublesome problems as it becomes apparent only after the film is developed. In addition, these accumulated electrostatic charges may cause secondary failures such as dust adhering to the film surface or inability to apply uniformly. These static marks are becoming more likely to occur due to the increased sensitivity of photosensitive materials, high-speed coating, high-speed photographing, high-speed automatic processing, etc.
従来から感光材料の支持体や各種塗布表面層の導電性を
向上させる方法が考えられ、種々の吸湿性物質や水溶性
無機塩、ある種の界面活性剤、ポリマー等の利用が試み
られてきた。Methods have been considered to improve the conductivity of photosensitive material supports and various coated surface layers, and attempts have been made to use various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers, etc. .
しかしながら、これら多くの物質は支持体の種類や写真
組成物の違いによって特異性を示したり写真性能にも悪
影響を及ぼす場合がある。特に親水性コロイド層に対す
る帯電防止は非常に困難で、低温で表面抵抗の低下が十
分でなかったり、高温高湿において感光材料同士または
他の物質との間で接着故障を生ずることがしばしばある
。また、ポリエチレンオキサイド系化合物のように帯電
防止効果を有しながら、カプリの増加、減感、粒状性の
劣化等、写真特性への悪影響を与えるものも多く、医療
用Ｘ−レイ感材のように支持体の両面に乳剤層を有する
感光材料への使用に適する帯電防止剤を見い出すのは困
難であった。However, many of these substances may exhibit specificity depending on the type of support or photographic composition, or may have an adverse effect on photographic performance. In particular, it is very difficult to prevent static electricity on a hydrophilic colloid layer, and the reduction in surface resistance is often insufficient at low temperatures, or adhesion failures often occur between photosensitive materials or other substances at high temperatures and high humidity. In addition, although they have an antistatic effect like polyethylene oxide compounds, there are many that have negative effects on photographic properties such as increased capri, desensitization, and deterioration of graininess, such as medical X-ray sensitive materials. However, it has been difficult to find antistatic agents suitable for use in light-sensitive materials having emulsion layers on both sides of the support.
前述の接触摩擦或いは剥離による静電気発生に関連して
、感光材料表面の滑り特性の改良も重要である。In connection with the aforementioned generation of static electricity due to contact friction or peeling, it is also important to improve the sliding properties of the surface of the photosensitive material.
即ち、感光材料の塗布、乾燥、加工包装をはじめとした
製造工程時、さらにはフィルム装填、撮影、自動現像機
処理工程あるいは影写などで各種のローラー、機器や感
材同士などとの接触摩擦の機会が極めて多い。In other words, contact friction with various rollers, equipment, and photosensitive materials during manufacturing processes such as coating, drying, and processing and packaging of photosensitive materials, as well as during film loading, photographing, processing in automatic processors, and photocopying. There are many opportunities.
そのため、感光材料の滑り特性の改良は、帯電防止性と
併せて摩擦による表面の擦り傷、引掻き傷の防止、或は
フィルム送行性改良などの上から感材の滑り摩擦を減少
させることが要求される。Therefore, in order to improve the sliding properties of photosensitive materials, there is a need to reduce the sliding friction of photosensitive materials in order to prevent surface abrasions and scratches caused by friction, as well as to improve film transportability, in addition to antistatic properties. Ru.
従来よりこの種の研究として提案されている代表的なも
のにはオルガノシロキサン類を用いた、例えば米国特許
３４２．５２２号、特開昭６０−１４０３４２号或は特
開昭６２−２６４９９などがある。Typical research studies of this type have been proposed using organosiloxanes, such as U.S. Pat. .
これらの公知の改良手段は、それぞれある程度の滑り性
は向上するものの充分でなかったり、他の特性例えば剥
離帯電性を悪化したりするなど必らずしも満足するもの
ではなかった。Although each of these known improvement means improves the slipperiness to some extent, it is not always satisfactory, as it is not sufficient or deteriorates other properties such as peeling chargeability.
一方、多くの親水性有機コロイド層から形成される写真
感光材料は、その製造に際して、これらの塗布液をハジ
キ、塗布ムラ等を生ぜず、均一かつ高速で薄層塗布され
ることが要求される。感光材料を製造するに当って、し
ばしば支持体に写真乳剤その他のゼラチンなど親水性有
機コロイドを含む塗布液を同時多層塗布することがある
。このようなゼラチン等の有機コロイド層にゼラチンま
たは他の有機コロイド液を塗布する場合に必要とされる
塗布特性を得ることは、支持体に直接ゼラチンコロイド
液を塗布する場合に比べ多くの困難を伴う。特に下の塗
布された層が塗布直後の冷却セットした状態にある場合
には向夏である。On the other hand, during production of photographic light-sensitive materials formed from many hydrophilic organic colloid layers, it is required that these coating solutions be coated in a thin layer uniformly and at high speed without causing repelling or uneven coating. . In producing light-sensitive materials, a support is often coated with multiple layers of coating solutions containing photographic emulsions and other hydrophilic organic colloids such as gelatin. Obtaining the required coating characteristics when applying gelatin or other organic colloid liquids to such an organic colloid layer presents many difficulties compared to applying gelatin colloid liquids directly to the support. Accompany. Especially when the lower coated layer is in a cool set state immediately after coating, it is early summer.
従来から感光材料の各種塗布液の塗布助剤として、乳化
剤として、あるいは写真表面層の表面物性を改良するた
めの添加剤として種々の界面活性剤（以下、活性剤とい
う）が使用されてきた。特にサポニンは写真工業におい
て塗布助剤として広汎に利用されてきたが、泡立ち易い
こと、天然物であるため品質の変動が大きく、しかも塗
布助剤としての特性が弱いなどの欠点があった。また、
その他各種の合成活性剤においても種々の写真塗布液も
しくは写真塗布層の塗布特性および表面特性に及ぼす作
用が活性剤の種類によって特異性を示し、従ってその用
途範囲が限定されるため多くの異なった型の活性剤が特
定の用途に応じて選択され利用されている。Various surfactants (hereinafter referred to as activators) have conventionally been used as coating aids in various coating solutions for photosensitive materials, as emulsifiers, or as additives for improving the surface properties of photographic surface layers. In particular, saponin has been widely used as a coating aid in the photographic industry, but it has drawbacks such as easy foaming, large fluctuations in quality because it is a natural product, and poor properties as a coating aid. Also,
Various other synthetic activators also exhibit specificity depending on the type of activator in their effects on the coating properties and surface properties of various photographic coating solutions or photographic coating layers. The type of active agent selected and utilized depends on the particular application.
しかしながら、これらの中には写真特性、特に高温多湿
時での膜物性の悪化や、化合物そのものの安定性、ある
いは高速塗布性が不十分なものもあり、満足できる現状
ではない。However, some of these have poor photographic properties, particularly poor film properties at high temperatures and high humidity, insufficient stability of the compound itself, or insufficient high-speed coating properties, and the current state of the art is not satisfactory.
本発明は上記の事情に鑑み為されたもので、本発明の第
１の目的は、泡・ハジキその他の塗布故障がなく高速塗
布が可能な帯電防止されたハロゲン化銀写真感光材料を
提供することにある。The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide an antistatic silver halide photographic light-sensitive material that is free from bubbles, repelling, and other coating failures and can be coated at high speed. There is a particular thing.
本発明の第２の目的は、表面の滑り性を改良したハロゲ
ン化銀写真感光材料を提供することである。A second object of the present invention is to provide a silver halide photographic material with improved surface slipperiness.
本発明の第３の目的は、写真性能に悪影響を及ぼすこと
のない帯電防止剤を用いて帯電防止されたハロゲン化銀
写真感光材料を提供することである。A third object of the present invention is to provide a silver halide photographic material that is antistatic using an antistatic agent that does not adversely affect photographic performance.
本発明の上記目的は、支持体上に、少なくとも１層の親
水性コロイド層と感光性ハロゲン化銀を含有する層を有
するハロゲン化銀写真感光材料において、前記の少なく
とも１層に、下記一般式〔Ｉ〕及び一般式（ｎ）で表さ
れる化合物の少なくとも１種を含有することを特徴とす
るハロゲン化銀写真感光材料により達成される。The above object of the present invention is to provide a silver halide photographic material having, on a support, at least one hydrophilic colloid layer and a layer containing photosensitive silver halide, in which at least one layer has the following general formula: This is achieved by a silver halide photographic material containing at least one compound represented by [I] and general formula (n).
一般式〔Ｉ〕
３
一般式〔ＩＩ〕
３
３
〔式中、Ｒ１は炭素数３〜１８のアルキル基、アルケニ
ル基、もしくはアラルキル基、Ｒ２は水素または炭素数
３〜１８ノアルキル基、アルケニル基、もしくはアラル
キル基、Ｒ３は水素もしくはメチル基、Ａは炭素数２〜
４のアルキレン基、ｎはＯ〜１００の整数、ｍは１〜２
００の整数、Ｍはアルカリ金属原子、ＮＨ，、アルカノ
ールアミン残基、または水素原子を表す。〕
以下、本発明についてさらに具体的に説明する。General formula [I] 3 General formula [II] 3 3 [wherein R1 is an alkyl group having 3 to 18 carbon atoms, an alkenyl group, or an aralkyl group, R2 is hydrogen or a noalkyl group having 3 to 18 carbon atoms, an alkenyl group, or an aralkyl group, R3 is hydrogen or a methyl group, and A has 2 or more carbon atoms.
4 alkylene group, n is an integer of O to 100, m is 1 to 2
An integer of 00, M represents an alkali metal atom, NH, an alkanolamine residue, or a hydrogen atom. ] Hereinafter, the present invention will be explained in more detail.
前記一般式中、Ｒｏは炭素数３〜１８のアルキル基、ア
ルケニル基、またはアラルキル基であり、アルキル基と
しては、例えば、プロピル、イソプロピル、ブチル、イ
ソブチル、ペンチル、ヘキシル、ヘプチル、オクチル、
ノニル、デシル、ドデシル、ウンデシル、トリデシル、
テトラデシル、ペンタデシル、ヘキサデシル、ヘプタデ
シル、オクタデシル、等が挙げられる。In the general formula, Ro is an alkyl group, alkenyl group, or aralkyl group having 3 to 18 carbon atoms, and examples of the alkyl group include propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl,
nonyl, decyl, dodecyl, undecyl, tridecyl,
Examples include tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, and the like.
アルケニル基としは、例えば、プロペニル、ブテニル、
インブテニル、ペンテニル、ヘキセニル、ヘプテニル、
オクテニル、ノネニル、デセニル、ウンデセニル、ドデ
セニル、トリデセニル、テトラデセニル、ペンタデセニ
ル、ヘキサデセニル、ヘプタデセニル、オクタデセニル
、等が挙げられる。Examples of alkenyl groups include propenyl, butenyl,
imbutenyl, pentenyl, hexenyl, heptenyl,
Examples include octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, and the like.
アラルキル基としては、スチリルベンジル、クミル、等
が挙げられ、これらの混合物であってもよい。Examples of the aralkyl group include styrylbenzyl, cumyl, etc., and mixtures thereof may be used.
Ｒ２は水素または炭素数３〜１８のアルキル基、アルケ
ニル基、またはアラルキル基であり、アルキル基として
は、例えば、プロピル、イングロビル、ブチルイソブチ
ル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル
、デシル、ウンデシル、ドデシル、トリデシル、テトラ
デシル、ペンタデシル、ヘキサデシル、ヘプタデシル、
オクタデシル、等が挙げられる。R2 is hydrogen or an alkyl group, alkenyl group, or aralkyl group having 3 to 18 carbon atoms, and examples of the alkyl group include propyl, inglovil, butyl isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl,
Octadecyl, etc. are mentioned.
アルケニル基としては、例えば、プロペニル、ブテニル
、インブテニル、ペンテニル、ヘキセニル、ヘズテニル
、オクテニル、ノネニル、デセニル、ウンデセニル、ド
デセニル、トリデセニル、テトラデセニル、ペンタデセ
ニル、ヘキサデセニル、ヘプタデセニル、オクタデセニ
ル、等が挙げられる。Examples of the alkenyl group include propenyl, butenyl, imbutenyl, pentenyl, hexenyl, heztenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, and the like.
アラルキル基としては、スチリル、ベンジル、クミル、
等が挙げられ、これらの混合物であってもよい。Aralkyl groups include styryl, benzyl, cumyl,
etc., and a mixture thereof may also be used.
また、Ａは炭素数２〜４のアルキレン基または置換アル
キレン基であり、例えば、エチレン、プロピレン、ブチ
レン、イソブチレン等があり、それらの単独またはブロ
ックあるいはランダムの混合物であっても良い。Further, A is an alkylene group or substituted alkylene group having 2 to 4 carbon atoms, such as ethylene, propylene, butylene, isobutylene, etc., and may be a single group or a block or random mixture thereof.
ｎはθ〜１００の整数、より好ましくは０または１〜５
０であり、ｍは１〜２００の整数であり、より好ましく
は２〜１００の範囲である。n is an integer of θ to 100, more preferably 0 or 1 to 5
0, and m is an integer from 1 to 200, more preferably from 2 to 100.
Ｍは水素原子、またはナトリウム、カリウム等のアルカ
リ金属原子、ＮＨいアルカノールアミン残基または水素
原子である。M is a hydrogen atom, an alkali metal atom such as sodium or potassium, an NH alkanolamine residue, or a hydrogen atom.
次に本発明の一般式で表される化合物の合成例をあげる
。Next, an example of synthesis of a compound represented by the general formula of the present invention will be given.
合成例１
撹拌後、温度計、還流管を備えた反応容器にアリルノニ
ルフェノール２６０ｇ、触媒としてトリエチルアミン１
．５ｇを仕込み、つぎにアリルグリシジルエーテル１１
４ｇを滴下し、８０℃にて５時間撹拌反応した。Synthesis Example 1 After stirring, 260 g of allylnonylphenol was added to a reaction vessel equipped with a thermometer and a reflux tube, and 1 1 of triethylamine was added as a catalyst.
．． Prepare 5g, then allyl glycidyl ether 11
4 g was added dropwise, and the reaction was stirred at 80° C. for 5 hours.
次に、得られた反応組成物をオートクレーブに移し、苛
性カリウムを触媒として、圧力１．５ｋｇ／ｃｍ”、温
度１３０°Ｃの条件にてエチレンオキシド反応組成物に
対して２モル、および１０モル付加した。Next, the obtained reaction composition was transferred to an autoclave, and using caustic potassium as a catalyst, 2 mol and 10 mol were added to the ethylene oxide reaction composition at a pressure of 1.5 kg/cm'' and a temperature of 130°C. did.
次に、撹拌後、温度計、還流管を備えた反応容器に、上
記のエチレンオキシド２モル付加体ヲ２３１ｇ１無水リ
ン酸２３ｇを仕込み８０℃にて、５時間リン酸エステル
化反応を行ない得られた組成物を本発明化合物（Ａ）と
した。Next, after stirring, 231 g of the above 2 mole adduct of ethylene oxide and 23 g of phosphoric anhydride were charged into a reaction vessel equipped with a thermometer and a reflux tube, and a phosphoric acid esterification reaction was carried out at 80° C. for 5 hours. The composition was designated as the compound (A) of the present invention.
同様の操作にて得られたエチレンオキシド２モル付加体
のリン酸エステル化物を本発明化合物（Ｂ）とした。本
発明乳化剤（Ｂ）のモノエステル、ジエステルの混合モ
ル比は、６０／４０であった。A phosphoric acid ester of a 2 mole ethylene oxide adduct obtained in the same manner was designated as the compound (B) of the present invention. The mixing molar ratio of monoester and diester in the emulsifier (B) of the present invention was 60/40.
合成例２
撹拌後、温度計、還流管を備えた反応容器にメタリルオ
クチルフェノール２４６ｇ、触媒としてトリエチルアミ
ン０．５ｇを仕込み、つぎにアリルグリシジルエーテル
１１４ｇを滴下し、８０℃にて５時間撹拌反応した。Synthesis Example 2 After stirring, 246 g of methallyl octylphenol and 0.5 g of triethylamine as a catalyst were placed in a reaction vessel equipped with a thermometer and a reflux tube, and then 114 g of allyl glycidyl ether was added dropwise, followed by stirring and reaction at 80°C for 5 hours. .
次に、得られた反応組成物をオートクレーブに移し、苛
性カリウムを触媒として、圧力１．５ｋｇ／ｃｍ”、ｉ
度１３０℃の条件にてプロピレンオキシドを反応組成
物に対して５モル付加した。Next, the obtained reaction composition was transferred to an autoclave, and caustic potassium was used as a catalyst at a pressure of 1.5 kg/cm'', i.
5 mol of propylene oxide was added to the reaction composition at 130°C.
次に撹拌後、温度計、還流管を備えた反応容器に、上記
のプロピレンオキシド５モル付加体を３１５ｇ１無水リ
ン酸２３ｇを仕込み８０°Ｃにて、５時間リン酸エステ
ル化反応を行ない、得られた組成物を本発明化合物（Ｃ
）とした。このモノエステル、ジエステルの混合物モル
比は６２／ ３８であった。Next, after stirring, 315 g of the above 5 mol propylene oxide adduct and 23 g of phosphoric anhydride were placed in a reaction vessel equipped with a thermometer and a reflux tube, and a phosphoric acid esterification reaction was carried out at 80°C for 5 hours. The resulting composition was added to the compound of the present invention (C
). The molar ratio of the mixture of monoester and diester was 62/38.
合成例３
撹拌後、温度計、還流管を備えた反応容器にアリルジス
チレン化フェノールプロピレンオキシド２モル、エチレ
ンオキシド５モルブロック付加体６７６ｇ、触媒として
トリエチルアミン２ｇを仕込み、つぎにアリルグリシジ
ルエーテル１１４ｇを滴下し、８０℃にて５時間撹拌反
応した。Synthesis Example 3 After stirring, 2 moles of allyl distyrenated phenol propylene oxide, 676 g of a 5 mole block adduct of ethylene oxide, and 2 g of triethylamine as a catalyst were placed in a reaction vessel equipped with a thermometer and a reflux tube, and then 114 g of allyl glycidyl ether was added dropwise. The mixture was stirred and reacted at 80°C for 5 hours.
次に、得られた反応組成物をオートクレーブに移し、苛
性カリウムを触媒として、圧力１−５ｋｇ／ ｃｍ’ｓ
温度１３０℃の条件いてエチレンオキシドを反応組酸物
に対して３０モル、および１００モル付加した。Next, the obtained reaction composition was transferred to an autoclave and heated with caustic potassium as a catalyst at a pressure of 1-5 kg/cm's.
Ethylene oxide was added at a temperature of 130°C at 30 moles and 100 moles based on the reaction mixture acid.
次に撹拌後、温度計、還流管を備えた反応容器に、上記
のエチレンオキシド３０モル付加体ヲ１０５５ｇ、無水
リン酸３０ｇを仕込み８０℃にて、５時間リン酸エステ
ル化反応を行ない、得られた組成物を本発明化合物（Ｄ
）とした。このモノエステル、ジエステルの混合モル比
は７５／ ２５であった。同様の操作にて得られたエチ
レンオキシド１００モル付加体のリン酸エステル化物を
本発明化合物（Ｅ）とした。このモルエステル、ジエス
テルの混合モル比は８０／ ２０であった。Next, after stirring, 1055 g of the above 30 mole ethylene oxide adduct and 30 g of phosphoric anhydride were placed in a reaction vessel equipped with a thermometer and a reflux tube, and a phosphoric acid esterification reaction was carried out at 80°C for 5 hours. The composition of the present invention (D
). The mixing molar ratio of monoester and diester was 75/25. A phosphoric acid ester of a 100 mol ethylene oxide adduct obtained in the same manner was designated as the compound (E) of the present invention. The mixing molar ratio of this molar ester and diester was 80/20.
合成例４
撹拌後、温度計、還流管を備えた反応容器にメタリルド
デシルフェノールエチレンオキシド５０モル付加体２５
１４ｇ、触媒としてトリエチルアミン５ｇを仕込み、つ
ぎにメタリルグリシジルエーテル１２８ｇを滴下し、８
０℃にて５時間撹拌反応した。Synthesis Example 4 After stirring, 50 mol of methallyldodecylphenol ethylene oxide adduct 25 was placed in a reaction vessel equipped with a thermometer and a reflux tube.
14 g, 5 g of triethylamine as a catalyst was added, and then 128 g of methallyl glycidyl ether was added dropwise.
The reaction was stirred at 0°C for 5 hours.
次に、得られた反応組成物をオートクレーブに移し、苛
性カリウムを触媒として、圧力１．５ｋｇ／ｃ■２、温
度１３０°Ｃの条件にてエチレンオキシドを反応組成物
に対して２０モル付加した。Next, the obtained reaction composition was transferred to an autoclave, and 20 moles of ethylene oxide was added to the reaction composition at a pressure of 1.5 kg/cm2 and a temperature of 130°C using caustic potassium as a catalyst.
合成例５
撹拌後、温度計、還流管を備えた反応容器にアリルクミ
ルフェノールプロピレンオキシドｌＯモル付加体８３２
ｇ、触媒としてトリエチルアミン４ｇを仕込み、つぎに
アリルグリシジルエーテルアミン１１４ｇを滴下し、８
０℃にて、５時間撹拌反応した。Synthesis Example 5 After stirring, add 1O mol of allylcumylphenol propylene oxide adduct 832 to a reaction vessel equipped with a thermometer and a reflux tube.
g, 4 g of triethylamine was charged as a catalyst, and then 114 g of allyl glycidyl etheramine was added dropwise.
The reaction was stirred at 0° C. for 5 hours.
次に、得られた反応組成物をオートクレーブに移し、苛
性カリウムを触媒として、圧力１．５ｋｇ／ｃｍ”、温
度１３０℃の条件ｌ；でエチレンオキシドを反応組成物
に対して２０モル付加した。Next, the obtained reaction composition was transferred to an autoclave, and 20 moles of ethylene oxide was added to the reaction composition under conditions of a pressure of 1.5 kg/cm'' and a temperature of 130° C. using caustic potassium as a catalyst.
次に撹拌後、温度計、還流管を備えた反応容器に、上記
のエチレンオキシド２０モル付加体を９１３ｇ１無水リ
ン酸２３ｇを仕込み８０００にて、５時間リン酸エステ
ル化反応を行ない、ジェタノールアミン５０ｇにて中和
して得られた組成物を、本発明化合物（Ｇ）とした。こ
のモノエステル、ジェステ本発明の化合物は感光材料を
構成する親水性コロイド層（ハロゲン化銀乳剤層、中間
層、フィルター層、ハレーション防止層、保護層等）の
いずれに添加してもよいが、好ましくは保護層および／
または乳剤層である。Next, after stirring, 913 g of the above 20 mole adduct of ethylene oxide and 23 g of phosphoric anhydride were placed in a reaction vessel equipped with a thermometer and a reflux tube, and a phosphoric acid esterification reaction was carried out at 8,000 ℃ for 5 hours, followed by 50 g of jetanolamine. The composition obtained by neutralization was designated as the compound (G) of the present invention. The monoester and the compound of the present invention may be added to any of the hydrophilic colloid layers (silver halide emulsion layer, intermediate layer, filter layer, antihalation layer, protective layer, etc.) constituting the photosensitive material, but Preferably a protective layer and/or
or an emulsion layer.
添加量は感光材料の種類、層構成等により一定でないが
塗布液ｌＱ当り１０ｍｇ −１０ｇの範囲で用いられる
のが好ましく、特に好ましくは１００ｍｇ〜５ｇである
。Although the amount added is not constant depending on the type of photosensitive material, layer structure, etc., it is preferably used in the range of 10 mg to 10 g, particularly preferably 100 mg to 5 g, per 1Q of coating liquid.
本発明の化合物はアニオン系活性剤が併用された場合、
帯電防止性能が向上される。併用されるアニオン系活性
剤は特に制限されない。アニオン系活性剤の使用量は、
塗布液１ｄ当りｌＱｍｇ”ｌＯｇが好ましく １００ｍ
ｇ〜５ｇが特に好ましい。When the compound of the present invention is used in combination with an anionic activator,
Antistatic performance is improved. The anionic active agent used in combination is not particularly limited. The amount of anionic activator used is
Preferably 1Qmg"lOg per 1d of coating liquid 100m
g to 5 g is particularly preferred.
本発明の化合物はアニオン系活性剤の他に更にポリオキ
シエチレン系活性剤が併用されると更に好ましい効果が
得られる。この場合、本発明の化合物とアニオン系活性
剤、ポリオキシエチレン系活性剤は同じ塗布液に添加し
ても、別々の塗布液に添加してもよい。When the compound of the present invention is used in combination with a polyoxyethylene activator in addition to an anionic activator, more favorable effects can be obtained. In this case, the compound of the present invention, anionic activator, and polyoxyethylene activator may be added to the same coating solution or to separate coating solutions.
カチオン系の添加剤とアニオン系の添加剤を同一溶液で
用いることは、反応により種々の故障（塗布故障、減感
、カブリ等）を生ずるので好ましくない。しかしながら
、本発明の化合物はカチオン系添加剤とアニオン系活性
剤を含む系に用いるのが特に好ましい。そのメカニズム
は明らかでないが、本発明の化合物の添加により、塗布
故障、減感、カブリ増加などを著しく軽減できる。It is not preferable to use a cationic additive and an anionic additive in the same solution because various problems (coating failure, desensitization, fog, etc.) may occur due to the reaction. However, it is particularly preferred for the compounds of the invention to be used in systems containing cationic additives and anionic activators. Although the mechanism is not clear, coating failure, desensitization, increased fog, etc. can be significantly reduced by adding the compound of the present invention.
カチオン系添加剤としては、下記に示す増感色素、活性
剤の他に特公昭４８−３４１６６号、同５０−４０６６
５号に記載されるカブリ抑制剤が挙げられる。As cationic additives, in addition to the sensitizing dyes and activators shown below, Japanese Patent Publication Nos. 48-34166 and 50-4066
For example, the fog suppressant described in No. 5 may be mentioned.
（増感色素）
ＲＮ（ＣＨ３）３ ｒ
本発明の感光材料に用いられるハロゲン化銀乳剤には、
ハロゲン化銀として通常使用される任意のものを用いる
ことができる。また、写真乳剤中のハロゲン化銀粒子の
粒子サイズ分布は任意であるが、単分散であってもよい
。(Sensitizing dye) RN(CH3)3 r The silver halide emulsion used in the light-sensitive material of the present invention includes:
Any commonly used silver halide can be used. Further, the grain size distribution of silver halide grains in the photographic emulsion is arbitrary, and may be monodisperse.
写真乳剤中のハロゲン化銀粒子は、立方体、八面体、１
４面体、１２面体のような規則的（ｒｅｇｕｌａｒ）な
結晶体を有するものでもよく、また球状、板状などのよ
うな変則的（ｉｒｒｅｇｕｌａｒ）な結晶形をもつもの
、あるいはこれらの結晶形の複合形をもつものでもよい
。種々の結晶形の粒子の混合から成ってもよい。Silver halide grains in photographic emulsions are cubic, octahedral, 1
It may have a regular crystal shape such as a tetrahedron or a dodecahedron, or it may have an irregular crystal shape such as a spherical shape or a plate shape, or a composite of these crystal shapes. It can be something that has a shape. It may also consist of a mixture of particles of various crystalline forms.
また、例えばＰｂＯのような酸化物結晶と塩化銀のよう
なハロゲン化銀結晶を結合させた。接合型ハロゲン化銀
結晶、エピタキシャル成長をさせたハロゲン化銀結晶（
例えば臭化銀上に塩化銀、沃臭化銀、沃化銀等をエピタ
キシャルに成長させる。）六方晶形、正八面体沃化銀に
正六面体の塩化銀が配向重複した結晶などでもよい。Also, for example, oxide crystals such as PbO and silver halide crystals such as silver chloride were combined. Junction type silver halide crystal, epitaxially grown silver halide crystal (
For example, silver chloride, silver iodobromide, silver iodide, etc. are grown epitaxially on silver bromide. ) A hexagonal crystal, a crystal in which a regular hexahedral silver chloride is aligned over a regular octahedral silver iodide, or the like may be used.
また、粒子の直径がその厚みの５倍以上の超平板のハロ
ゲン化銀粒子が全投影面積の５０％以上を占めるような
乳剤を使用してもよい。詳しくは、特開昭５８−１２７
９２１号、同５８−１１３９２７号などの明細書に記載
されている。Further, an emulsion may be used in which ultratabular silver halide grains having a grain diameter of 5 times or more the grain thickness occupy 50% or more of the total projected area. For details, see JP-A-58-127.
It is described in specifications such as No. 921 and No. 58-113927.
特公昭４１−２０８６号公報に記載された内部潜像盤ハ
ロゲン化銀粒子と表面潜像型ハロゲン化銀粒子とを組合
せて用いることもできる。It is also possible to use a combination of internal latent image plate silver halide grains and surface latent image type silver halide grains described in Japanese Patent Publication No. 41-2086.
本発明の実施において、そのハロゲン化銀乳剤中に用い
るハロゲン化銀粒子は、写真分野でよく知られている中
性法、酸性法、アンモニア法、順混合法、逆混合法、ダ
ブルジェット法、コントロルド・ダブルジェット法、コ
ングアージョン法、コア／シェル法などの方法を適用し
て製造することができる。In carrying out the present invention, the silver halide grains used in the silver halide emulsion may be prepared by the neutral method, acidic method, ammonia method, forward mixing method, back mixing method, double jet method, etc., which are well known in the photographic field. It can be manufactured by applying a method such as a controlled double jet method, a concursion method, or a core/shell method.
またダブルジェット法の別の形式として異なる組成の可
溶性ハロゲン塩を各々独立に添加するトリプルジェット
法（例えば可溶性銀塩、可溶性臭素塩及び可溶性沃素塩
）も用いることができる。Further, as another form of the double jet method, a triple jet method in which soluble halogen salts of different compositions are added independently (for example, soluble silver salt, soluble bromine salt, and soluble iodine salt) can also be used.
粒子を銀イオン過剰の下において形成させる方法（いわ
ゆる逆混合法）を用いることもできる。It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
同時混合法の一つの形式としてハロゲン化銀の生成され
る液相中のｐＡｇを一定に保つ方法、すなわちいわゆる
コントロールトリダブルジェット法を用いることもでき
る。As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called controlled tri-double jet method can also be used.
別々に形成した２種以上のハロゲン化銀乳剤を混合して
用いてもよい。Two or more types of silver halide emulsions formed separately may be mixed and used.
また、これらのハロゲン化銀粒子またはハロゲン化銀乳
剤中には、イリジウム、タリウム、パラジウム、ロジウ
ム、亜鉛、ニッケル、コバルト、ウラン、トリウム、ス
トロンチウム、タングステン、プラチナの塩（可溶性塩
）の内、少なくとも１種類が含有されるのが好ましい。In addition, these silver halide grains or silver halide emulsions contain at least one of salts (soluble salts) of iridium, thallium, palladium, rhodium, zinc, nickel, cobalt, uranium, thorium, strontium, tungsten, and platinum. It is preferable that one type is contained.
その含有量は、好ましくは１モルＡｇ当りｌｏ−６〜ｌ
０−１モルである。Its content is preferably from lo-6 to l/mol Ag.
It is 0-1 mole.
特に好ましくは、タリウム、パラジウム、イリジウムの
塩の内の少なくとも１種類が含有されることである。こ
れらは単独でも混合しても用いられ、その添加位置（時
間）は任意である。これにより、閃光露光特性の改良、
圧力減感の防止、潜像退行の防止、増感その他の効果が
期待される。Particularly preferably, at least one of thallium, palladium, and iridium salts is contained. These may be used alone or in combination, and the addition position (time) is arbitrary. This improves flash exposure characteristics,
It is expected to have effects such as prevention of pressure desensitization, prevention of latent image regression, and sensitization.
ハロゲン化銀乳剤は、化学増感しても、しなくてもよい
。すなわち、活性ゼラチン銀と反応し得る硫黄を含む化
合物（例えば、チオ硫酸塩、チオ尿素類、メルカプト化
合物類、ローダニン類）を用いる硫黄増感法：還元性物
質（例えば、銀−錫塩、アミン類、ヒドラジン誘導体、
ホルムアミジンスルフィン酸、シラン化合物）を用いる
還元増感法：貴金属化合物（例えば、全錯塩のほか、Ｐ
ｔ、Ｉｒ、Ｐｄなどの周期律表■族の金属の錯塩）を用
いる貴金属増感法などを単独または組み合わせで用いる
ことができる。The silver halide emulsion may or may not be chemically sensitized. Namely, sulfur sensitization using sulfur-containing compounds (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines) that can react with active gelatin silver; reducing substances (e.g., silver-tin salts, amines); hydrazine derivatives,
Reduction sensitization method using noble metal compounds (e.g., total complex salts, P
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as t, Ir, and Pd can be used alone or in combination.
本発明に用いられる写真乳剤は、メチン色素類その他に
よって分光増感されてもよい。増感色素は単独に用いて
もよいが、それらの組み合わせを用いてもよく、増感色
素の組み合わせは特に、強色増感の目的でしばしば用い
られる。The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. Sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.
本発明に用いられる写真乳剤には、感光材料の製造工程
、保存中あるいは写真処理中のカブリを防止し、あるい
は写真性能を安定化させる目的で、種々の安定剤、カブ
リ抑制剤を含有させることができる。The photographic emulsion used in the present invention may contain various stabilizers and fog suppressants for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. I can do it.
本発明の感光材料には親水性コロイド層に・フィルター
染料として、あるいはイラジェーション防止、ハレーシ
ョン防止その他種々の目的で水溶性染料を含有してもよ
い。The light-sensitive material of the present invention may contain a water-soluble dye in the hydrophilic colloid layer, as a filter dye, or for various purposes such as preventing irradiation and halation.
本発明の写真感光材料の写真乳剤層には感度上昇、コン
トラスト上昇、または現像促進の目的で、例えばポリア
ルキレンオキシドまたはそのエーテル、エステル、アミ
ンなどの誘導体、チオエーテル化合物、チオモルホリン
類、四級アンモニウム塩化合物、ウレタン誘導体、尿素
誘導体、イミダゾール誘導体、３−ピラゾリドン類等を
含んでも良い。The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, and quaternary ammonium for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.
本発明の感光材料の乳剤層や中間層に用いることのでき
る結合剤または保護コロイドとしては、ゼラチンを用い
るのが有利であるが、それ以外の親水性コロイドも単独
あるいはゼラチンと共に用いることができる。As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin.
本発明の写真感光材料には、写真乳剤層その他の親水性
コロイド層に無機または有機の硬膜剤を含有してよい。The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer.
本発明の写真感光材料には、写真乳剤層その他の親水性
コロイド層に寸度安定性の改良などの目的で、水不溶ま
たは難溶性合成ポリマーの分散物を含むことができる。The photographic material of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability.
本発明の感光材料には保護層が好ましく設けられるが、
この保護層は親水性コロイドからなる層であり、使用さ
れる親水性コロイドとしては前述したものが用いられる
。また保護層は、単層であっても重層となっていてもよ
い。Although the photosensitive material of the present invention is preferably provided with a protective layer,
This protective layer is a layer made of a hydrophilic colloid, and the hydrophilic colloid used is one described above. Further, the protective layer may be a single layer or a multilayer.
本発明の感光材料の乳剤層または保護層中に、好ましく
は保護層中にはマット剤及び／または平滑剤などを添加
してもよい。A matting agent and/or a smoothing agent may be added to the emulsion layer or protective layer of the light-sensitive material of the present invention, preferably to the protective layer.
本発明の感光材料には、その他必要に応じて種々の添加
剤を用いることができる。例えば、染料、現像促進剤、
蛍光増白剤、色カブリ防止剤、紫外線吸収剤などである
。具体的には、リサーチ・ディスクロージャー（ＲＥＳ
ＥＡＲＣＨＤＩＳＣＬＯ５ＵＲＥ）１７６号、第２２〜
３１頁（ＲＤ−１７６４３、１９７８年）に記載された
ものを用いることができる。Various other additives may be used in the photosensitive material of the present invention, if necessary. For example, dyes, development accelerators,
These include optical brighteners, color antifoggants, and ultraviolet absorbers. Specifically, research disclosure (RES)
EARCHDISCLO5URE) No. 176, No. 22~
31 (RD-17643, 1978) can be used.
本発明の感光材料において写真乳剤層その他の層は、感
光材料に通常用いられている可視性支持体の片面または
両面に塗布されて具体化されることができる。In the light-sensitive material of the present invention, the photographic emulsion layer and other layers can be embodied by being coated on one or both sides of a visible support commonly used in light-sensitive materials.
本発明の感光材料は、具体的にはＸ−レイ感光材料、リ
ス感光材料、黒白撮影感光材料、カラーネガ感光材料、
カラー反転感光材料、カラー印画紙、コロイド・トラン
スファー・プロセス、銀塩拡散転写プロセス、グイトラ
ンスファープロセス、銀色素漂白法、プリントアウト感
材、熱現像用感材などに用いることができる。Specifically, the photosensitive material of the present invention includes an X-ray photosensitive material, a Lith photosensitive material, a black and white photographic photosensitive material, a color negative photosensitive material,
It can be used in color reversal photosensitive materials, color photographic papers, colloid transfer processes, silver salt diffusion transfer processes, gui transfer processes, silver dye bleaching methods, printout photosensitive materials, photosensitive materials for heat development, etc.
写真像を得るための露光は、通常の方法を用いて行えば
よい。Exposure to obtain a photographic image may be performed using a conventional method.
本発明の感光材料の写真処理には、例えばリサーチ・デ
ィスクロージャー１７６号、第２５〜３０頁（ＲＤ−１
７６４３）に記載されているような、種々の方法及び種
々の処理液のいずれをも適用することができる。この写
真処理は、目的に応じて、銀画像を形成する写真処理（
黒白写真処理）、あるいは色素像を形成する写真処理（
カラー写真処理）のいずれであってもよい。処理温度は
普通１８℃から５０００の間に選ばれるが、１８℃より
低い温度または５０°Ｃを越える温度としてもよい。For example, Research Disclosure No. 176, pp. 25-30 (RD-1
Any of the various methods and various treatment liquids can be applied, such as those described in US Pat. No. 7,643. Depending on the purpose, this photo processing can be used to form a silver image (
black-and-white photographic processing) or a photographic process that forms a dye image (
color photographic processing). The processing temperature is usually chosen between 18°C and 5000°C, but it may also be below 18°C or above 50°C.
本発明の感光材料には種々の添加物を含有させることが
できるが、帯電防止効果を高めるために、その他の界面
活性剤を併せて用いることができる。The photosensitive material of the present invention can contain various additives, and other surfactants can also be used in order to enhance the antistatic effect.
本発明の実施において用いることができる界面活性剤と
しては、例えばサポニン（ステロイド系）、アルキレン
オキサイド誘導体、グリシドール誘導体、多価アルコー
ルの脂肪酸エステル類、糖のアルキルエステル類などの
非イオン性界面活性剤が挙げられる。また、アルキルカ
ルボン酸塩、アルキルスルホン酸塩、アルキルベンゼン
スルホン酸塩、アルキルナフタレンスルホン酸塩、アル
キル硫酸エステル類、アルキル燐酸エステル類、Ｎ−ア
シル−Ｎ−アルキルタウリン類、スルホコハク酸エステ
ル類、スルホアルキルポリオキシエチレンアルキルフェ
ニルエーテル類、ホリオキシエチレンアルキル燐酸エス
テル類などのような、カルボキシ基、スルホ基、ホスホ
基、硫酸エステル基、燐酸エステル基等の酸性基を含む
アニオン界面活性剤が挙げられる。さらにアミノ酸類、
アミノアルキルスルホン酸類、アミノアルキル硫酸また
は燐酸エステル類、アルキルベタイン類、アミンオキシ
ド類などの両性界面活性剤が挙げられる。Surfactants that can be used in the practice of the present invention include nonionic surfactants such as saponins (steroids), alkylene oxide derivatives, glycidol derivatives, fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. can be mentioned. In addition, alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl Examples include anionic surfactants containing acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, and phosphate ester groups, such as polyoxyethylene alkylphenyl ethers and holoxyethylene alkyl phosphate esters. Furthermore, amino acids,
Examples include amphoteric surfactants such as aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, and amine oxides.
以下に具体的実施例を示して本発明を更に詳しく説明す
る。The present invention will be explained in more detail by showing specific examples below.
実施例１
平均粒径０．３μｍの沃素２モル％、塩素０．２モル％
を含有する単分散塩沃臭化銀の内部核およびその外側に
、沃素４０モル％および臭素６０モル％の比率で沃臭化
銀層を設け、０．５μ−の粒径まで成長させ、引続き沃
素１モル％、臭素９９モル％の比率で０．９５μｍまで
沃臭化銀層を成長させ、やや丸味を帯びた１４面体状の
ハロゲン化銀粒子を得た。Example 1 2 mol% of iodine and 0.2 mol% of chlorine with an average particle size of 0.3 μm
A silver iodobromide layer was provided on the inner core of monodispersed silver chloroiodobromide containing and on the outside thereof in a ratio of 40 mol% iodine and 60 mol% bromine, and was grown to a grain size of 0.5 μ-. A silver iodobromide layer was grown to a thickness of 0.95 μm at a ratio of 1 mol % iodine and 99 mol % bromine to obtain slightly rounded dodecahedral silver halide grains.
これらの粒子に塩化金酸塩、ロダンアンモン、チオ硫酸
ナトリウムおよびチオ尿素系化合物を添加し化学熟成し
た。Chlorauric acid salt, rhodanammonium, sodium thiosulfate, and thiourea-based compounds were added to these particles for chemical ripening.
この粒子７０ｇ当り安定剤として４−ヒドロキシ−６−
メチル−１，３，３ａ、７−チトラザインデン２．３ｇ
を加えて乳剤調製液を作成した。この乳剤調部液および
下記に示す保護層液に、各種添加剤および表１に示す塗
布助剤を添加した。4-hydroxy-6- as a stabilizer per 70 g of these particles.
Methyl-1,3,3a,7-chitrazaindene 2.3g
was added to prepare an emulsion preparation solution. Various additives and coating aids shown in Table 1 were added to this emulsion preparation solution and the protective layer solution shown below.
次に、ポリエチレンテレフタレート支持体上に、乳剤液
は、銀量として４．５ｇ／ａ＋”、ゼラチン量として３
．８ｇ／ｍ”、保護層液は、ゼラチン量として１．０ｇ
／ｍ２となるように毎分１５０＋＋＋で同時塗布し、２
分３０秒で乾燥させて２６種の試料を作成した。Next, the emulsion liquid was coated on a polyethylene terephthalate support with a silver content of 4.5 g/a+'' and a gelatin content of 3.
．． 8g/m”, protective layer liquid is 1.0g as gelatin amount
/m2 at the same time at 150+++ per minute,
Twenty-six types of samples were prepared by drying in minutes and 30 seconds.
乳剤添加剤（ハロゲン化銀１モル当り）ｔ−ブチルカテ
コール ４００１ｇポリビニルピロリ
ドン （分子量１０．０００） １．０ｇスチレン−無
水マレイン酸共重合体 ２．５ｇトリメチロールプロ
パン １０ｇジエチレングリコール
５．０ｇニトロフェニル・トリフェニル
ホスホニウムクロリド ５０＋ｇ１．３
−ジヒドロキシベンゼン−４−
スルホン酸アンモニウム
ｇ
２−メルカプトベンツイミダゾール−
５−スルホン酸ナトリウム
５ｔａｇ
ＣＨ２ＣＯＯ（ＣＨｉ） ＩＣＨ３
ＣＨＣＯＯＣＨｚＣＨｚＣＨ（ＣＨｓ）ｚＳｏ ３ Ｎ
ａ
７■ｇ
ＣａＨｓＯＣＨ２ＣＨＣＨｚＮ（ＣＨｚＣＯＯＨ）ｚＨ
ｇ
１．１−ジメチロール−１−ブロモ−ｌニトロメタン
７０ａ＋ｇ
（ｎは２〜５の混合物）
平均粒径７μ■のポリメチルメタクリレートからなるマ
ット剤
７ｍｇ
平均粒径０．０１３μ禦のコロイダルシリカ７ｈ＋ｇ
保護層添加剤（ゼラチンＩｇ当り）
この様にして得られた試料の現像処理前、及び処理され
た各試料について以下のテストを行った。Emulsion additives (per mole of silver halide) t-butylcatechol 4001g polyvinylpyrrolidone (molecular weight 10.000) 1.0g styrene-maleic anhydride copolymer 2.5g trimethylolpropane 10g diethylene glycol
5.0g nitrophenyl triphenylphosphonium chloride 50+g1.3
-dihydroxybenzene-4- ammonium sulfonate g 2-mercaptobenzimidazole- 5-sodium sulfonate 5tag CH2COO(CHi) ICH3 CHCOOCHzCHzCH(CHs)zSo 3 N
a 7 g CaHsOCH2CHCHzN(CHzCOOH)zH g 1.1-dimethylol-1-bromo-l nitromethane 70a+g (n is a mixture of 2 to 5) Matting agent made of polymethyl methacrylate with an average particle size of 7μ■ Average particle size 0 Colloidal silica with a thickness of .013 μm 7h+g Protective layer additive (per Ig of gelatin) The following tests were conducted on the sample thus obtained before development processing and on each processed sample.
ｌ）塗布性能の測定
■処理前の各試料ｌＩＩ！当りに存在するハジキの個数
を調べた。ハジキの個数が多い程塗布性が悪いことを示
す。l) Measurement of coating performance ■Each sample before treatment lII! We investigated the number of repellents present in each area. The larger the number of repellents, the worse the coating properties.
■塗布ムラを以下の試験法によって評価した。(2) Coating unevenness was evaluated by the following test method.
巾３０ｃｍ ｘ長さ１００ｃｍの試料を濃度１．０にな
るように均一に露光し、現像処理後の試料を目視により
判定する。A sample with a width of 30 cm and a length of 100 cm is uniformly exposed to light so that the density becomes 1.0, and the developed sample is visually judged.
く塗布ムラの評価〉
◎：非常に良好
Ｏ：良好
△ ：やや不良
× ：不良
２）帯電防止性能の測定
未露光の試料を２３°０２０％ＲＨで、２時調湿した後
、同一空調条件の暗室内において、試料をゴムローラで
摩擦した後、自動現像機５ＲＸ−５０１（コニカ株式会
社製）でＸレイ自動現像機用現像液ＸＤ−５Ｒ１定着液
ＸＦ−５Ｒ（いずれもコニカ株式会社製）で、４５秒処
理を行い添加した化合物の帯電防止性能を調べた。Evaluation of coating unevenness> ◎: Very good O: Good △: Slightly poor ×: Poor 2) Measurement of antistatic performance An unexposed sample was conditioned at 23°, 020% RH for 2 hours, then subjected to the same air conditioning conditions. After rubbing the sample with a rubber roller in a dark room, an automatic processor 5RX-501 (manufactured by Konica Corporation) was used to apply X-ray automatic processor developer XD-5R1 and fixer XF-5R (both manufactured by Konica Corporation). Then, the antistatic performance of the added compound was investigated after treatment for 45 seconds.
スタチックマークの発生度の評価は、目視により判定し
た。評価基準は次の通りである。The degree of occurrence of static marks was evaluated visually. The evaluation criteria are as follows.
Ａ：全く発生しない。A: It does not occur at all.
Ｂ：面積で３％未満発生する。B: Occurs in less than 3% of the area.
Ｃ：面積で３％以上ｌＯ％未満発生する。C: Occurs in an area of 3% or more and less than 10%.
Ｄ二面積でｌθ％以上発生する。It occurs by lθ% or more in the area of D2.
３）写真性能の測定
作成した試料をタングステンランプでコニカ株式会社製
のＫＳ−１型センシトメーターでＪＩＳ法に基づき白色
光で露光した後、上記自動現像機を用いて、同様の方法
で現像を行い、写真性能の測定を行った。なお感度は試
料ｌの感度を１００とした時の相対値で示し、カプリ＋
０．２０の濃度を与える露光量より計算した。3) Measurement of photographic performance The prepared sample was exposed to white light using a tungsten lamp using a KS-1 sensitometer manufactured by Konica Corporation in accordance with the JIS method, and then developed in the same manner using the above-mentioned automatic developing machine. The photographic performance was measured. Note that the sensitivity is expressed as a relative value when the sensitivity of sample 1 is taken as 100.
Calculated from the exposure amount that gives a density of 0.20.
４）処理性 表面汚れ 処理で得られた試料を以下の３段階で評価した。4) Processability surface dirt The samples obtained through the treatment were evaluated on the following three levels.
Ａ：汚れの付着が認められない。A: No dirt was observed.
Ｂ： 〃 少し認められる。B: Slightly acceptable.
Ｃ： ／／ 著しく認められる。C: // Significantly recognized.
比較化合物 ■）サポニン ＩＩ ） ＣＨ。comparative compound ■) Saponin II) CH.
Ｃ，Ｈ，、−Ｎ・−ＣＨ，Ｂｒｅ ＣＨ。C,H,, -N・-CH,Bre CH.
あり、又写真性能に何等悪影響を及ぼさないことがわか
る。添加量の変化を試料３．９及び１０で行っているが
、写真性能、帯電防止性能、塗布性の面において添加量
５０ｏ＋ｇ／ａ＋”付近が最も好ましいことがわかる。It can be seen that there is no adverse effect on photographic performance. The amount added was varied in Samples 3.9 and 10, and it can be seen that an amount around 50 o+g/a+'' is most preferable in terms of photographic performance, antistatic performance, and coating properties.
更に、例示化合物と含沸素界面活性剤、と併用させた試
料については、特にその効果が著しく認これらの結果を
併せて表−１に示す。尚表中のカブリはベース濃度を差
引いた値である。Furthermore, the effect of the sample in which the exemplified compound and the fluorine-containing surfactant were used in combination was particularly significant, and these results are shown in Table 1. The fog in the table is the value obtained by subtracting the base density.
尚、試料１〜１４．１７〜２６について、各帯電防止剤
を保護層に加えたもの、ただし、試料１６については、
乳剤層に加えたものであり、更に試料１５については、
例示化合物を保護層と乳剤層に別々に加えたものである
。For samples 1 to 14 and 17 to 26, each antistatic agent was added to the protective layer, however, for sample 16,
It was added to the emulsion layer, and for sample 15,
The exemplified compounds are added separately to the protective layer and the emulsion layer.
表−１から明らかなように、本発明を用いて帯電防止し
た試料については、比較試料に比べ、スタチックマーク
の発生も少なく、塗布性も良好で実施例２
下引加工したセルローストリアセテートフィルムからな
り、ハレーション防止層（黒色コロイド銀０．３８ｇお
よびゼラチン３．２ｇを含有）を有する透明支持体上に
、下記の各層を順番に塗設することにより試料２７〜３
７を作成した。尚、以下の実施例において、感光材料中
への添加量はｌ ＩＩ＋”当りのものを示し、またハロ
ゲン化銀乳剤およびコロイド銀は銀に換算して示した。As is clear from Table 1, the samples that were antistatic using the present invention produced fewer static marks and had better coating properties than the comparative samples. Samples 27 to 3 were prepared by sequentially coating the following layers on a transparent support having an antihalation layer (containing 0.38 g of black colloidal silver and 3.2 g of gelatin).
7 was created. In the following examples, the amounts added to the light-sensitive materials are shown per l II+'', and the amounts of silver halide emulsions and colloidal silver are shown in terms of silver.
層ｌ ：赤感性に色増感された１、３ｇの低感度赤感性
沃臭化銀（沃化銀５モル％含有）乳剤および１．３ｇの
ゼラチンならびに０．７ｇの１−ヒドロキシ−Ｎ［δ−
（２，４−ジ−ｔ−アミルフェノキシ）ブチル］−２−
す７トアミド （シアンカプラー）、０．０７ｇの１−
ヒドロキン−４−［４−（１−ヒドロキシ−δ−アセト
アミド−３，６ジスルホー２−ナフチルアゾ）フェノキ
シ］−Ｎ−［δ−（２゜４−ジ−ｔ−アミルフェノキシ
）ブチル−２−ナフトアミド・ジナトリウム （カラー
ドシアンカプラー）および０．０７ｇの４−オクタデシ
ルスクシンイミド−２−（ｌフェニル−５−テトラゾリ
ルチオ）−１−インダノン（ＤＩＲ化合物）を溶解した
０、７ｇのトリクレジルホスフェ−１−（ＴＣＰ）を含
有している低感度赤感性乳剤層。Layer 1: 1.3 g of low-sensitivity red-sensitive silver iodobromide (containing 5 mol % silver iodide) emulsion sensitized to red, 1.3 g of gelatin and 0.7 g of 1-hydroxy-N[ δ−
(2,4-di-t-amylphenoxy)butyl]-2-
Su7 toamide (cyan coupler), 0.07g of 1-
Hydroquine-4-[4-(1-hydroxy-δ-acetamide-3,6disulfo-2-naphthylazo)phenoxy]-N-[δ-(2゜4-di-t-amylphenoxy)butyl-2-naphthamide. 0.7 g of tricresyl phosphate-1-indanone (DIR compound) dissolved in sodium disodium (colored cyan coupler) and 0.07 g of 4-octadecylsuccinimide-2-(l-phenyl-5-tetrazolylthio)-1-indanone (DIR compound). A low-speed red-sensitive emulsion layer containing (TCP).
層２ ： １．２ｇの高感度赤感性沃臭化銀乳剤（６
モル％の沃臭化銀含有）、１．４ｇのゼラチンならびに
０．２０ｇの層１で用いたシアンカプラーおよび０．０
２ｇの層ｌで用いたカラードシアンカプラーを溶解した
０、２２ｇのＴＣＰを含有している高感度赤感性乳剤層
。Layer 2: 1.2 g of highly sensitive red-sensitive silver iodobromide emulsion (6
mol % of silver iodobromide), 1.4 g of gelatin and 0.20 g of the cyan coupler used in layer 1 and 0.0
A high-speed red-sensitive emulsion layer containing 0.22 g of TCP in which 2 g of the colored cyan coupler used in layer 1 was dissolved.
層３ ： ０．０５ｇの２，５−シートオクチルハイ
ドロキノン（汚染防止剤）を溶解した０、０５ｇのジブ
チル７タレート （ＤＢＰ）および０．７ｇのゼラチン
を含有している中間層。Layer 3: Intermediate layer containing 0.05 g dibutyl heptatarate (DBP) dissolved in 0.05 g 2,5-sheet octylhydroquinone (antifouling agent) and 0.7 g gelatin.
層４ ：緑感性に色増感された０、９０ｇの低感度緑感
性沃臭化銀（沃化銀５モル％含有）乳剤および２．１ｇ
のゼラチンならびに０．８ｇの１−（２，４，６−トリ
クロロフェニル）−３−（［σ−（２１４−ジーｔ−ア
ミルフェノキシ）−アセトアミド］ベンズアミド）−５
−ピラゾロン （マゼンタカプラー）、０．１５ｇの１
−（２，４，６−トリクロロフェニル）−４−（１−す
７チルアゾ）−３−（２−りコロ−５−オクタデセニル
スクシンイミドアニリノ）−５−ピラゾロン（カラード
マゼンタカプラー）、０．０１６ｇの層ｌで用いたＤＩ
Ｒ化合物を溶解した０、９５ｇのＴＣＰを含有している
低感度緑感性乳剤層。Layer 4: 0.90 g of low-sensitivity green-sensitive silver iodobromide (containing 5 mol% silver iodide) emulsion color-sensitized to green sensitivity and 2.1 g
of gelatin and 0.8 g of 1-(2,4,6-trichlorophenyl)-3-([σ-(214-di-t-amylphenoxy)-acetamido]benzamide)-5
- Pyrazolone (magenta coupler), 0.15 g 1
-(2,4,6-trichlorophenyl)-4-(1-su7tylazo)-3-(2-lycoro-5-octadecenylsuccinimidoanilino)-5-pyrazolone (colored magenta coupler), DI used in layer 1 of 0.016 g
A low-speed green-sensitive emulsion layer containing 0.95 g of TCP in which the R compound was dissolved.
層５ ：緑感性に色増感された１、７ｇの高感度緑感性
沃臭化銀乳剤（４モル％の沃化銀含有） １．９ｇのゼ
ラチンならびに０．２０ｇの層４で用いたマゼンタカプ
ラーおよび０．０４９ｇの層４で用いたカラードマゼン
タカプラーを溶解した０、６０ｇのＤＮＰを含有してい
る高感度緑感性乳剤層。Layer 5: 1.7 g of high-sensitivity green-sensitive silver iodobromide emulsion (containing 4 mol% silver iodide) color sensitized to green, 1.9 g of gelatin and 0.20 g of magenta used in layer 4. A high speed green sensitive emulsion layer containing 0.60 g of DNP dissolved in the coupler and 0.049 g of the colored magenta coupler used in layer 4.
層６ ： ０．１５ｇの黄色コロイド銀、０．２ｇの
汚染防止剤（層３に含有と同じもの）を溶解した０、１
１ｇのＤＢＰおよび１．５ｇのゼラチンを含有するイエ
ローフィルター層。Layer 6: 0,1 dissolved in 0.15g yellow colloidal silver, 0.2g antifouling agent (same as contained in layer 3)
Yellow filter layer containing 1 g DBP and 1.5 g gelatin.
層７ ：青感性に色増感された０、２５ｇの低感度青感
性沃臭化銀乳剤（沃化銀４モル％含有）および１．９ｇ
のゼラチンならびに１．５ｇのσ−ピバロイルー（ｌ−
ベンジル−２−フェニル−３，５−ジオキソイミダゾリ
ジン−４−イル）−２７−クロロ−５’−［（σ−ドデ
シルオキシカルボニル）エトキシカルボニル］アセドア
ニライド （イエローカプラー）を溶解した０、６ｇの
ＴＣＰを含有している低感度青感性乳剤層。Layer 7: 0.25 g of low-speed blue-sensitive silver iodobromide emulsion (containing 4 mol% silver iodide) color-sensitized to blue sensitivity and 1.9 g
of gelatin and 1.5 g of σ-pivaloyl (l-
0.6 g of benzyl-2-phenyl-3,5-dioxoimidazolidin-4-yl)-27-chloro-5'-[(σ-dodecyloxycarbonyl)ethoxycarbonyl]acedoanilide (yellow coupler) dissolved in A low-speed blue-sensitive emulsion layer containing TCP.
層８ ：青感性に色増感された０、９ｇの高感度青感性
沃臭化銀乳剤（２モル％の沃化銀含有）、１．５ｇのゼ
ラチンならびに１．３０ｇの層７で用いたイエローカプ
ラーを溶解した０、６５ｇのＴＣＰを含有している高感
度青感性乳剤層。Layer 8: 0.9 g of highly sensitive blue-sensitive silver iodobromide emulsion (containing 2 mole % silver iodide), color sensitized to blue, 1.5 g of gelatin and 1.30 g used in layer 7 A high-speed blue-sensitive emulsion layer containing 0.65 g of TCP in which a yellow coupler was dissolved.
ＩＩ ９ ： ２．３ｇのゼラチン、０．１ｇの本発
明の例示化合物または比較化合物を含有する保護層。尚
、それぞれの層には硬膜剤、延展剤を加えた。II 9 : Protective layer containing 2.3 g of gelatin, 0.1 g of an exemplary compound of the invention or a comparative compound. A hardening agent and a spreading agent were added to each layer.
以上のようにして作成した試料を２３°Ｃ１２３％ＲＨ
の下で１２時間調整し、同一空調条件の暗室内において
試料をゴムローラ、ナイロンローラで摩擦した後、以下
の現像処理を行いスタチックマークの度合いを実施例１
と同様の方法で判定した。The sample prepared as above was heated at 23°C, 123%RH.
After rubbing the sample with a rubber roller and a nylon roller in a dark room under the same air-conditioning conditions for 12 hours, the following development process was performed to evaluate the degree of static marks as shown in Example 1.
Judgment was made in the same manner.
また、塗布ムラ及び１ｍ２当りのハジキ数を調べた。塗
布ムラは巾３０ｃｍ ｘ長さ１００ｃｍの試料を濃度１
．０になるように均一露光し以下の現像処理を行い、塗
布性能を実施例１と同様の方法で判定した。In addition, coating unevenness and the number of repellents per 1 m2 were investigated. For coating unevenness, use a sample 30cm wide x 100cm long at a concentration of 1.
．． The coating performance was evaluated in the same manner as in Example 1.
静摩擦係数による評価
ｔ、 ａｎｖｅｌｔ、 ｊ、 ｆ、 ｃａｒｒ
ｏｌ、 ｊｒ、 ａｎｄ １． Ｊ、 ｓｕ
ｇｄｅｎｊ、 ｓｍｐｔｅ、 ８０ ［９］ ］７３４
−７３９［１９７１］に記載のペーパークリップ法を用
いて、塗布後のフィルム表面の最大静摩擦係数を求めた
。Evaluation by static friction coefficient t, anvelt, j, f, carr
ol, jr, and 1. J, su
gdenj, smpte, 80 [9] ]734
-739 [1971], the maximum static friction coefficient of the film surface after coating was determined.
値が小さい程、フィルム面の摩擦が少ないことを意味す
る。A smaller value means less friction on the film surface.
［現像処理処方］ 処理時間発色現像
３分１５秒（３８℃）漂 白
６分３０秒水 洗
３分１５秒定 着
６分３０秒水 洗
３分１５秒安定浴 ３分１５
秒
各処理工程において使用した処理液組成は下記の如くで
あった。[Development processing prescription] Processing time Color development
Bleach for 3 minutes 15 seconds (38℃)
Wash with water for 6 minutes and 30 seconds
Fixed for 3 minutes and 15 seconds
Wash with water for 6 minutes and 30 seconds
Stable bath for 3 minutes and 15 seconds 3 minutes and 15 seconds
The composition of the treatment liquid used in each treatment step was as follows.
［発色現像液］
ニトリロ三酢酸ナトリウム １．０ｇ亜硫酸
ナトリウム ４．０ｇ炭酸ナトリウ
ム ３０．０ｇ臭化カリウム
１．４ｇヒドロキシルアミン硫酸
塩
４−（Ｎ−エチル−Ｎ−１−ヒドロキシエチルアミノ）
−２−メチルアニリン硫酸塩
水を加えて１１２とする。[Color developer] Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide
1.4g Hydroxylamine sulfate 4-(N-ethyl-N-1-hydroxyethylamino)
Add -2-methylaniline sulfate solution to make 112.
［漂白液］ 臭化アンモニウム アンモニア水（２８％） エチレンジアミン四酢酸ナトリ １６０．０ｇ ２５．０ｍ＋２ ラム鉄塩 １３０．０ｇ １４．０＋ａ（２ ２，４ｇ ４．５ｇ 氷酢酸 水を加えてＩＱとする。[Bleach solution] ammonium bromide Ammonia water (28%) Sodium ethylenediaminetetraacetate 160.0g 25.0m+2 lamb iron salt 130.0g 14.0+a(2 2.4g 4.5g glacial acetic acid Add water to obtain IQ.
［定着液］ テトラポリリン酸ナトリウム 亜硫酸ナトリウム チオ硫酸アンモニウム（７０％） 重亜硫酸ナトリウム 水を加えて１４とする。[Fixer] Sodium tetrapolyphosphate sodium sulfite Ammonium thiosulfate (70%) sodium bisulfite Add water to make 14.
［安定化液］ ホルマリン（３７％水溶液） 水を加えてｉｆｆとする。[Stabilizing liquid] Formalin (37% aqueous solution) Add water to make if.
２．０ｇ ４．０ｇ １７５．０＋ｏ４ ４．６ｇ ８．０ｍｇ その結果を表−２に示す。2.0g 4.0g 175.0+o4 4.6g 8.0mg The results are shown in Table-2.
かつ、写真特性に悪影響を及ぼすことなく優れた帯電防
止性能を有したハロゲン化銀写真感光材料を得ることが
できる。更に含フツ素界面活性剤と、一般式〔Ｉ〕で示
される界面活性剤を併用すると更に好ましい帯電防止性
能が、得られると共にフィルム表面の摩擦係数の小さい
ハロゲン化銀写真感光材料を提供することができる。Moreover, a silver halide photographic material having excellent antistatic performance can be obtained without adversely affecting photographic properties. Furthermore, it is an object of the present invention to provide a silver halide photographic light-sensitive material in which even more preferable antistatic performance is obtained when a fluorine-containing surfactant and a surfactant represented by the general formula [I] are used in combination, and the film surface has a small coefficient of friction. I can do it.
上記の表−２の結果からも明らかなように、本発明の実
施によってカラー用多層フィルムの場合にも帯電防止性
能、塗布性及び摩擦性の改良が得られている。As is clear from the results in Table 2 above, improvements in antistatic performance, coating properties, and friction properties have been obtained even in the case of color multilayer films by implementing the present invention.
Claims (1)
性ハロゲン化銀を含有する層を有するハロゲン化銀写真
感光材料において、前記の少なくとも１層に、下記一般
式〔 I 〕及び一般式〔II〕で表される化合物の少なく
とも１種を含有することを特徴とするハロゲン化銀写真
感光材料。 一般式〔 I 〕 ▲数式、化学式、表等があります▼ 一般式〔II〕 ▲数式、化学式、表等があります▼ 〔式中、Ｒ＿１は炭素数３〜１８のアルキル基、アルケ
ニル基、もしくはアラルキル基、Ｒ＿２は水素または炭
素数３〜１８ノアルキル基、アルケニル基、もしくはア
ラルキル基、Ｒ＿３は水素もしくはメチル基、Ａは炭素
数２〜４のアルキレン基、ｎは０〜１００の整数、ｍは
１〜２００の整数、Ｍはアルカリ金属原子、ＮＨ＿４、
アルカノールアミン残基、または水素原子を表す。〕[Scope of Claims] A silver halide photographic material having at least one hydrophilic colloid layer and a layer containing photosensitive silver halide on a support, in which at least one layer has the following general formula [ A silver halide photographic material comprising at least one compound represented by the general formula [I] and the general formula [II]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 is an alkyl group, alkenyl group, or aralkyl group having 3 to 18 carbon atoms. group, R_2 is hydrogen or a C3-C18 noalkyl group, alkenyl group, or aralkyl group, R_3 is hydrogen or a methyl group, A is an alkylene group having C2-4, n is an integer from 0 to 100, m is 1 An integer of ~200, M is an alkali metal atom, NH_4,
Represents an alkanolamine residue or a hydrogen atom. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1536890A JPH03219235A (en) | 1990-01-25 | 1990-01-25 | Silver halide photographic sensitive material improved in antistatic and coating performance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1536890A JPH03219235A (en) | 1990-01-25 | 1990-01-25 | Silver halide photographic sensitive material improved in antistatic and coating performance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03219235A true JPH03219235A (en) | 1991-09-26 |
Family
ID=11886851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1536890A Pending JPH03219235A (en) | 1990-01-25 | 1990-01-25 | Silver halide photographic sensitive material improved in antistatic and coating performance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03219235A (en) |
-
1990
- 1990-01-25 JP JP1536890A patent/JPH03219235A/en active Pending
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