JPS6130254B2 - - Google Patents
Info
- Publication number
- JPS6130254B2 JPS6130254B2 JP12710381A JP12710381A JPS6130254B2 JP S6130254 B2 JPS6130254 B2 JP S6130254B2 JP 12710381 A JP12710381 A JP 12710381A JP 12710381 A JP12710381 A JP 12710381A JP S6130254 B2 JPS6130254 B2 JP S6130254B2
- Authority
- JP
- Japan
- Prior art keywords
- silver halide
- halide photographic
- paper
- layer
- polyolefin resin
- 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
- -1 silver halide Chemical class 0.000 claims description 191
- 239000004332 silver Substances 0.000 claims description 160
- 229910052709 silver Inorganic materials 0.000 claims description 160
- 239000000839 emulsion Substances 0.000 claims description 96
- 239000000470 constituent Substances 0.000 claims description 59
- 229920005672 polyolefin resin Polymers 0.000 claims description 58
- 238000000576 coating method Methods 0.000 claims description 56
- 239000011248 coating agent Substances 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 44
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 238000000149 argon plasma sintering Methods 0.000 claims description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 239000010410 layer Substances 0.000 description 138
- 239000000123 paper Substances 0.000 description 104
- 238000000034 method Methods 0.000 description 37
- 108010010803 Gelatin Proteins 0.000 description 31
- 229920000159 gelatin Polymers 0.000 description 31
- 239000008273 gelatin Substances 0.000 description 31
- 235000019322 gelatine Nutrition 0.000 description 31
- 235000011852 gelatine desserts Nutrition 0.000 description 31
- 239000002585 base Substances 0.000 description 21
- 239000003795 chemical substances by application Substances 0.000 description 20
- 239000000975 dye Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 238000011282 treatment Methods 0.000 description 14
- 229920001577 copolymer Polymers 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 12
- 229920000573 polyethylene Polymers 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 230000002209 hydrophobic effect Effects 0.000 description 11
- 239000011241 protective layer Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 11
- 239000011347 resin Substances 0.000 description 11
- 239000004372 Polyvinyl alcohol Substances 0.000 description 10
- 239000002216 antistatic agent Substances 0.000 description 10
- 239000000084 colloidal system Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000003851 corona treatment Methods 0.000 description 8
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- 229920002678 cellulose Polymers 0.000 description 7
- 239000001913 cellulose Substances 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 150000001447 alkali salts Chemical class 0.000 description 6
- 229910052736 halogen Inorganic materials 0.000 description 6
- 230000001235 sensitizing effect Effects 0.000 description 6
- 206010070834 Sensitisation Diseases 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 5
- 238000004061 bleaching Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000000049 pigment Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 5
- 230000008313 sensitization Effects 0.000 description 5
- 159000000000 sodium salts Chemical class 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000006081 fluorescent whitening agent Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 229920006322 acrylamide copolymer Polymers 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- 229920006319 cationized starch Polymers 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 3
- 208000028659 discharge Diseases 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 description 3
- 229920001477 hydrophilic polymer Polymers 0.000 description 3
- 230000005661 hydrophobic surface Effects 0.000 description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000004848 polyfunctional curative Substances 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- 229920003169 water-soluble polymer Polymers 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 229920002307 Dextran Polymers 0.000 description 2
- 229920001353 Dextrin Polymers 0.000 description 2
- 239000004375 Dextrin Substances 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical class NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001253 acrylic acids Chemical class 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 239000000783 alginic acid Substances 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 150000004781 alginic acids Chemical class 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910001864 baryta Inorganic materials 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 235000019425 dextrin Nutrition 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 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
- 230000005611 electricity Effects 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 239000011121 hardwood Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- WTNULKDCIHSVKN-UHFFFAOYSA-N imidazo[1,2-a]pyridin-2-ol Chemical class C1=CC=CC2=NC(O)=CN21 WTNULKDCIHSVKN-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000006224 matting agent Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 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
- 238000012545 processing Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 2
- 239000011122 softwood Substances 0.000 description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- JXUKLFVKZQETHF-UHFFFAOYSA-N 1-$l^{1}-selanyl-n,n'-dimethylmethanimidamide Chemical compound CNC([Se])=NC JXUKLFVKZQETHF-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
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- IYPXPGSELZFFMI-UHFFFAOYSA-N 1-phenyltetrazole Chemical compound C1=NN=NN1C1=CC=CC=C1 IYPXPGSELZFFMI-UHFFFAOYSA-N 0.000 description 1
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- RDMIJQCFPQDYQN-UHFFFAOYSA-N 2-(2,4,4-trimethylpentan-2-yl)benzene-1,4-diol Chemical compound CC(C)(C)CC(C)(C)C1=CC(O)=CC=C1O RDMIJQCFPQDYQN-UHFFFAOYSA-N 0.000 description 1
- XNCSCQSQSGDGES-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]propyl-(carboxymethyl)amino]acetic acid Chemical compound OC(=O)CN(CC(O)=O)C(C)CN(CC(O)=O)CC(O)=O XNCSCQSQSGDGES-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
- DQSHFKPKFISSNM-UHFFFAOYSA-N 2-methylbenzoxazole Chemical compound C1=CC=C2OC(C)=NC2=C1 DQSHFKPKFISSNM-UHFFFAOYSA-N 0.000 description 1
- XEUDHEPUGOGCOE-UHFFFAOYSA-N 2-tert-butyl-1,3-benzoxazole;thiophene Chemical compound C=1C=CSC=1.C1=CC=C2OC(C(C)(C)C)=NC2=C1.C1=CC=C2OC(C(C)(C)C)=NC2=C1 XEUDHEPUGOGCOE-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- YTZWQUYIRHGHMJ-UHFFFAOYSA-N 3-(1,2-diamino-2-phenylethenyl)benzene-1,2-disulfonic acid Chemical compound NC(=C(C1=C(C(=CC=C1)S(=O)(=O)O)S(=O)(=O)O)N)C1=CC=CC=C1 YTZWQUYIRHGHMJ-UHFFFAOYSA-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
- AQSOTOUQTVJNMY-UHFFFAOYSA-N 7-(dimethylamino)-4-hydroxy-3-oxophenoxazin-10-ium-1-carboxylic acid;chloride Chemical compound [Cl-].OC(=O)C1=CC(=O)C(O)=C2OC3=CC(N(C)C)=CC=C3[NH+]=C21 AQSOTOUQTVJNMY-UHFFFAOYSA-N 0.000 description 1
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- 108091005944 Cerulean Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Chemical class 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical class CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- OAJHWYJGCSAOTQ-UHFFFAOYSA-N [Zr].CCCCCCCCO.CCCCCCCCO.CCCCCCCCO.CCCCCCCCO Chemical compound [Zr].CCCCCCCCO.CCCCCCCCO.CCCCCCCCO.CCCCCCCCO OAJHWYJGCSAOTQ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 1
- 229940063655 aluminum stearate Drugs 0.000 description 1
- WLDHEUZGFKACJH-UHFFFAOYSA-K amaranth Chemical compound [Na+].[Na+].[Na+].C12=CC=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=C1N=NC1=CC=C(S([O-])(=O)=O)C2=CC=CC=C12 WLDHEUZGFKACJH-UHFFFAOYSA-K 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 229940045985 antineoplastic platinum compound Drugs 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- UHHXUPJJDHEMGX-UHFFFAOYSA-K azanium;manganese(3+);phosphonato phosphate Chemical compound [NH4+].[Mn+3].[O-]P([O-])(=O)OP([O-])([O-])=O UHHXUPJJDHEMGX-UHFFFAOYSA-K 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- HRBZRZSCMANEHQ-UHFFFAOYSA-L calcium;hexadecanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O HRBZRZSCMANEHQ-UHFFFAOYSA-L 0.000 description 1
- 239000004202 carbamide Chemical class 0.000 description 1
- 239000000298 carbocyanine Substances 0.000 description 1
- 229920003090 carboxymethyl hydroxyethyl cellulose Polymers 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium 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
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- KZNICNPSHKQLFF-UHFFFAOYSA-N dihydromaleimide Natural products O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical class C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical class O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- PKWIYNIDEDLDCJ-UHFFFAOYSA-N guanazole Chemical class NC1=NNC(N)=N1 PKWIYNIDEDLDCJ-UHFFFAOYSA-N 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- OOCSVLHOTKHEFZ-UHFFFAOYSA-N icosanamide Chemical compound CCCCCCCCCCCCCCCCCCCC(N)=O OOCSVLHOTKHEFZ-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002504 iridium compounds Chemical class 0.000 description 1
- HTFVQFACYFEXPR-UHFFFAOYSA-K iridium(3+);tribromide Chemical compound Br[Ir](Br)Br HTFVQFACYFEXPR-UHFFFAOYSA-K 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical class O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical class NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- QWYZFXLSWMXLDM-UHFFFAOYSA-M pinacyanol iodide Chemical compound [I-].C1=CC2=CC=CC=C2N(CC)C1=CC=CC1=CC=C(C=CC=C2)C2=[N+]1CC QWYZFXLSWMXLDM-UHFFFAOYSA-M 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920005614 potassium polyacrylate Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- JEXVQSWXXUJEMA-UHFFFAOYSA-N pyrazol-3-one Chemical compound O=C1C=CN=N1 JEXVQSWXXUJEMA-UHFFFAOYSA-N 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 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
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000002002 slurry 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
- 239000011780 sodium chloride Substances 0.000 description 1
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229940082004 sodium laurate Drugs 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 229940045870 sodium palmitate Drugs 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 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
- GGXKEBACDBNFAF-UHFFFAOYSA-M sodium;hexadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCC([O-])=O GGXKEBACDBNFAF-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
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-N sulfamic acid Chemical class NS(O)(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- XJUNLJFOHNHSAR-UHFFFAOYSA-J zirconium(4+);dicarbonate Chemical compound [Zr+4].[O-]C([O-])=O.[O-]C([O-])=O XJUNLJFOHNHSAR-UHFFFAOYSA-J 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
- G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
- G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
Description
本発明はハロゲン化銀写真材料の製造方法に関
し、詳しくは天然パルプを主成分とする紙を基質
としてポリオレフイン樹脂で被覆されたポリオレ
フイン樹脂被覆紙を支持体として有し、該支持体
上にハロゲン化銀写真構成層が塗設されたハロゲ
ン化銀写真材料の製造方法に関し、更に詳しくは
ハロゲン化銀写真構成層の支持体のポリオレフイ
ン樹脂面上での接着性が良好であり、かつ塗布性
が均一良好なもので塗布ムラの認められないポリ
オレフイン樹脂被覆紙を支持体として有するハロ
ゲン化銀写真材料の製造方法に関するものであ
る。
通常、ハロゲン化銀写真材料は支持体と該支持
体上に設けられたハロゲン化銀写真構成層とから
構成されている。かかるハロゲン化銀写真構成層
としては、ハロゲン化銀写真乳剤層、保護層、下
引層、中間層あるいは色混り防止層、ハレーシヨ
ン防止層もしくはフイルター層、紫外線吸収層な
どおよびそれらの組み合わせから構成されたもの
である。例えば、単一なハロゲン化銀写真材料
は、支持体上にハロゲン化銀写真乳剤層とその保
護層を設けたものである。また、多層ハロゲン化
銀カラー材料は、支持体上に青感ハロゲン化銀写
真乳剤層と中間層、緑感ハロゲン化銀写真乳剤層
と紫外線吸収層、赤感ハロゲン化銀写真乳剤層と
保護層などが順に設けられて多層配置されたもの
である。
一方、ハロゲン化銀写真材料の支持体として
は、従来よりポリエチレンテレフタレートフイル
ム、トリ酢酸セルロースフイルム、ポリスチレン
などのフイルム、天然パルプを主成分とする紙を
基質としてその両面をフイルム形成能ある樹脂、
多くはポリオレフイン樹脂で被覆した樹脂被覆紙
などの疎水性支持体がよく知られている。特に、
写真印画紙用支持体としては、従来用いられてき
たバライタ紙に代わり、ポリオレフイン樹脂被覆
紙が多く用いられるようになつている。その理由
として、写真用支持体としてのポリオレフイン樹
脂被覆紙が疎水性であるために、バライタ紙の場
合と比較して、写真印画紙の現像、定着処理中に
処理液が基紙層に浸透しにくく、それ故水洗、乾
燥などの処理時間が短縮される利点があるためで
ある。
ところで、疎水性表面を有するポリオレフイン
樹脂被覆紙を支持体として用い、該支持体上にハ
ロゲン化銀写真構成層を塗設してハロゲン化銀写
真材料を製造する際に、支持体の疎水性ポリオレ
フイン樹脂表面とハロゲン化銀写真構成層との接
着性を良好にするために、疎水性ポリオレフイン
樹脂表面にある種の処理を必要とすることはよく
知られている。良好な接着性を与えるための最も
経済的で有効な方法の１つは疎水性ポリオレフイ
ン樹脂表面を電子衝撃することである。電子衝撃
はコロナ放電処理としても知られている。疎水性
ポリオレフイン樹脂表面を電子衝撃する方法は、
例えば英国特許第971058号、同第1060526号明細
書等に記載されている。また、支持体の疎水性ポ
リオレフイン樹脂表面を電子衝撃処理することに
よつて、疎水性ポリオレフイン樹脂表面とハロゲ
ン化銀写真構成層との接着性をより強固ならしめ
るためには、電子衝撃後１日以内に、好ましくは
30分以内に、特に好ましくは数秒以内にハロゲン
化銀写真構成層を電子衝撃処理した支持体の疎水
性ポリオレフイン樹脂表面に塗設する必要があ
る。
しかしながら、天然パルプを主成分とする紙を
基質とするポリオレフイン樹脂被覆紙を支持体と
して用い、該支持体のポリオレフイン樹脂面上に
電子衝撃を施した後30分以内にハロゲン化銀写真
構成層を塗設して製造したハロゲン化銀写真材料
では、ハロゲン化銀写真構成層の支持体への良好
な接着性は得られるけれども、ある種の重大な欠
点が発生することが明らかとなつた。即ち支持体
のポリオレフイン樹脂面上に電子衝撃を施した後
30分以内にハロゲン化銀写真構成層を塗設する
と、ハロゲン化銀写真構成層のポリオレフイン樹
脂支持体面への塗布性が不均一なものとなり、出
来あがつたハロゲン化銀写真材料のハロゲン化銀
写真構成層中に塗布ムラが発生するという問題で
ある。この塗布ムラのことを電子衝撃処理の影響
を強く受ける意味を含めることもあつて、以下単
にコロナ塗布ムラと呼称することにする。ことに
ハロゲン化銀写真乳剤層に発生したコロナ塗布ム
ラは、ハロゲン化銀写真材料に一様の露光を与え
た後に現像処理すると一層明確に観察される。コ
ロナ塗布ムラが写真印画紙の性能上著しい品質低
下をもたらすことは言うまでもない。
本発明者らの検討によれば、このコロナ塗布ム
ラは以下の様な状況にあることが明らかとなつ
た。第一に、コロナ塗布ムラは、支持体のポリオ
レフイン樹脂面上に電子衝撃後短時間例えば１時
間迄の間にハロゲン化銀写真構成層を塗設する場
合に顕著に認められる。もし、電子衝撃処理か
ら、かなり時間を経てから（例えば１日〜２日）
この電子衝撃ポリオレフイン樹脂面上にハロゲン
化銀写真構成層を塗設するならコロナ塗布ムラは
あまりひどくない。保持時間によりコロナ塗布ム
ラを避けることができるが、ハロゲン化銀写真材
料の製造工程の障害となる。即ちコロナ塗布ムラ
を避けるためには電子衝撃後、支持体を充分時間
貯蔵しなければならず、他方ハロゲン化銀写真構
成層は支持体との良好な接着性を得るために電子
衝撃後約１〜２日以内で支持体たるポリオレフイ
ン樹脂被覆紙に塗設されねばならない。第二に、
コロナ塗布ムラは、支持体のポリオレフイン樹脂
被覆紙面上に電子衝撃を施した後30分以内にハロ
ゲン化銀写真構成層を塗設してハロゲン化銀写真
材料を製造するにしても、単一なハロゲン化銀写
真材料ではそれほどひどくなく、少なくとも２つ
以上のハロゲン化銀写真乳剤層から成る多層ハロ
ゲン化銀写真材料、例えば多層ハロゲン化銀カラ
ー写真材料では一層顕著に認められる。即ち支持
体のポリオレフイン樹脂被覆紙面上に電子衝撃を
施した後30分以内に、支持体に隣接して順に黄色
カプラーを含む青感ハロゲン化銀写真乳剤層と色
混り防止層、マゼンタカプラーを含む緑感ハロゲ
ン化銀写真乳剤層と紫外線吸収層、シアンカプラ
ーを含む赤感ハロゲン化銀写真乳剤層とその保護
層を多層塗布用ホツパーから６層同時に塗布して
製造した多層ハロゲン化銀カラー写真材料では、
コロナ塗布ムラは緑感ハロゲン化銀写真乳剤層に
顕著に認められ、青感ハロゲン化銀写真乳剤層で
はあまりひどくなく、赤感ハロゲン化銀写真乳剤
層では更に軽度である。
しかるに、支持体の疎水性表面に電子衝撃を施
した後30分以内にハロゲン化銀カラー写真構成層
を塗設してハロゲン化銀カラー写真材料を製造す
る際の問題点及び改良に関する先行技術として
は、特公昭47−51905号に記載がある。それによ
れば、該問題点としては、ハロゲン化銀カラー写
真材料に染料班点が生じるという点であり、この
問題を特定の光学増感染料を用いて改良するとい
うものである。しかしながら、天然パルプを主成
分とする紙を基質としてポリオレフイン樹脂で被
覆したポリオレフイン樹脂被覆紙を支持体として
用い、該支持体のポリオレフイン樹脂面上に電子
衝撃を施した後30分以内にハロゲン化銀写真構成
層を塗設して製造したハロゲン化銀写真材料に発
生するコロナ塗布ムラの解決にはまだ不十分であ
つた。
従つて、本発明の目的は、第一に、天然パルプ
を主成分とする紙を基質としてポリオレフイン樹
脂で被覆されたポリオレフイン樹脂被覆紙を支持
体として有し、該支持体上に塗設されたハロゲン
化銀写真構成層の支持体面上での接着性が良好で
あり、かつ塗布性が均一なもので塗布ムラの認め
られないあるいは軽減された優れたハロゲン化銀
写真材料を製造工程上の障害や不利をもたらすこ
と無く製造する方法を提供することである。第二
に、天然パルプを主成分とする紙を基質としてポ
リオレフイン樹脂で被覆されたポリオレフイン樹
脂被覆紙を支持体として有し、該支持体上に多層
塗布用ホツパーから同時に塗設された少なくとも
２つ以上のハロゲン化銀写真乳剤層から成る多層
ハロゲン化銀写真構成層の支持体面上での接着性
が良好であり、かつ塗布性が均一なもので塗布ム
ラの認められないあるいは軽減された優れたハロ
ゲン化銀写真材料を製造工程上の障害や不利をも
たらすこと無く製造する方法を提供することであ
る。更に、本発明の別種の目的は、ハロゲン化銀
写真構成層の支持体面上での接着性だけでなく硬
膜性が顕著に強化されており、かつ塗布性が均一
なもので塗布ムラの認められないあるいは軽減さ
れた天然パルプを主成分とする紙を基質としたポ
リエチレン樹脂被覆紙を支持体として有する優れ
たハロゲン化銀写真材料を製造工程上の障害や不
利をもたらすこと無く製造する方法を提供するこ
とである。
本発明者らが鋭意検討の結果、本発明の目的
は、天然パルプを主成分とする紙を基質としてポ
リオレフイン樹脂で被覆したポリオレフイン樹脂
被覆紙を支持体として有し、該支持体上にハロゲ
ン化銀写真構成層を設けたハロゲン化銀写真材料
の製造に際し、天然パルプとして光散乱係数が
400cm2/ｇ以上の天然パルプを全使用パルプ当り乾
燥重量で40％以上用い、かつ支持体のポリオレフ
イン樹脂面上に電子衝撃を施した後30分以内にハ
ロゲン化銀写真構成層を塗設することに達成され
ることがわかつた。ここで、天然パルプの光散乱
係数は以下に記載の方法で測定されるものであ
る。即ち、天然パルプをJIS Ｐ−8210「製紙用パ
ルプの強さ試験方法」のビーダーを用いる方法に
準じて、JIS Ｐ−8121「パルプの濾水度試験方
法」のカナダ標準形により300mlまで叩解し、JIS
Ｐ−8209「パルプ試験用手すき紙調整方法」に準
じた手すき機により、80ｇ/m2の手抄紙を10枚調
製し、ハンドプレスにより水分を絞り、ドラムド
ライヤーによつて110℃で乾燥する。この手抄紙
をJIS Ｐ−8111「試験用紙の前処置」に準じて処
理を行い、JIS Ｐ−8138「紙の不透明度試験方法
に準じて、裏当て黒色板の上に前記手抄紙を１枚
重ねて反射率を測定し、10枚各々の反射率の平均
値をRoとする。次に裏当て黒色板を使用せずに
この手抄紙を10枚重ねて、その反射率を測定し
Rooとする。この測定に使用した手抄紙を、オー
プンドライヤーを使い105℃で３時間乾燥し、JIS
Ｐ−8124「紙のメートル法坪量測定方法」に準じ
て絶乾坪量を測定する。これをＷ（ｇ/m2）とす
る。以上によつて求めたRO、Roo、Ｗを使い次
式の光散乱係数（cm2/ｇ）を求める。
更に本発明の効果は、ポリオレフイン樹脂被覆
紙の基質たる紙（以下単に基紙という）として、
温度20℃、相対湿度65％において6.3×108Ω以上
の好ましくは1.0〜109Ω以上の表面固有抵抗を有
する紙を用いることによつて、一層よく発揮され
る。
なお、紙の表面固有抵抗は、試料を温度20℃、
相対湿度65％の恒温恒湿室に48時間保存して試料
条件を一定ならしめた後、直径５cmと直径７cmの
同心円電極ではさまれた紙の表面の抵抗を測定
し、抵抗Ｒ＝∫３．５ ２．５ρｓｄｒ／２πｒ（ρｓ；
表面固有抵抗）
の関係により算出される。
さらに述べれば、ポリオレフイン樹脂被覆紙を
支持体とするハロゲン化銀写真材料は、その製造
中あるいは取扱い中に静電気を帯びゴミを吸着す
る傾向となつて種々のトラブルの原因となると共
に、ハロゲン化銀写真乳剤層中にスタテツクマー
クと呼称される写真特性上極めて不快な部分カブ
リを生じることがある。このため基紙層中に、通
常無機の導電剤、多くはゼラチン、カルボキシ変
性ポリビニルアルコール、澱粉などの種々の親水
性ポリマーと良好な相溶性を有する塩化ナトリウ
ム、塩化カルシウムなどの水溶性塩化物をそれら
の親水性ポリマーと共にサイズプレスもしくはタ
ブサイズして含有せしめることが、従来行われて
いる。また、ある場合には、この目的のために澱
粉と共に硫酸ソーダなどの水溶性硫酸塩が用いら
れる。更に必要に応じて支持体の裏面、即ちハロ
ゲン化銀写真構成層を設ける支持体面とは反対側
の支持体面上に帯電防止性およびカール防止性の
バツクコート層と称せられる親水性コロイド層か
ら成る塗布層を設けることも知られている。しか
しながら、ポリオレフイン樹脂被覆紙の帯電防止
のために、天然パルプを主成分とする基紙層中に
導電剤を含有せしめて、基紙の表面抵抗が温度20
℃、相対湿度65％において6.3×108Ω以下に低下
すると、本発明の効果、即ちコロナ塗布ムラの改
良および接着性向上の効果は顕著なものではなく
なる。一方、基紙として、温度20℃、相対湿度65
％おいて6.3×108Ω以上好ましくは1.0×109以上
の表面抵抗を有する紙を用いることによつて、本
発明の効果は一層顕著に発揮されることが判明し
た。即ち、支持体の紙を基質とするポリオレフイ
ン樹脂被覆紙の疎水性表面上に電子衝撃を施した
30分以内にハロゲン化銀写真構成層を塗設して製
造したハロゲン化銀写真材料では、ハロゲン化銀
写真構成層の塗布性は顕著に均一なもので塗布ム
ラの認められないあるいは顕著に軽減されてお
り、また支持体面上での接着性も著しく向上する
だけでなく、ゼラチンを主成分とする親水性有機
コロイド層とゼラチンの硬膜剤とを含むハロゲン
化銀写真構成層の硬膜をも著しく強化できること
が明らかとなつた。以上のことは、本発明と基質
層中に静電防止剤を加えるのが有利であるとする
特公昭47−51905号に記載の先行技術とは主旨を
全く異にするものとして、理解される。
従つて、本発明の好ましい一実施態様は、光散
乱係数が400cm2/ｇ以上の天然パルプを全使用パル
プ当り乾燥重量で40％以上用いた天然パルプを主
成分とする紙であつて、かつ温度20℃、相対湿度
65％において6.3×108Ω以上の表面固有抵抗を有
する紙を基質とするポリオレフイン樹脂被覆紙を
支持体として用い、該支持体上の一方の面にコロ
ナ放電を施した後30分以内にハロゲン化銀写真構
成層を塗設し、支持体の他方の面（裏面）に親水
性有機コロイド層から成るバツクコート層を塗設
するものである。
また、本発明は天然パルプを主成分とする紙を
基質としたポリオレフイン樹脂被覆紙を支持体と
して有する少なくとも２つ以上のハロゲン化銀写
真乳剤層から成る多層ハロゲン化銀写真材料、特
に多層ハロゲンカラー写真材料の製造に有用であ
る。それは、支持体のポリオレフイン樹脂被覆紙
面上に電子衝撃を施した後30分以内に、支持体に
隣接して順に黄色カプラーを含む青感ハロゲン化
銀乳剤層と色混り防止層、マゼンタカプラーを含
む緑色ハロゲン化銀写真乳剤層と紫外線吸収層、
シアンカプラーを含む赤感ハロゲン化銀写真乳剤
層とその保護層を多層塗布用ホツパーから６層同
持に塗布して製造した多層ハロゲン化銀カラー写
真材料では、緑感ハロゲン化銀写真乳剤層中にコ
ロナ塗布ムラが著しく発生するが、本発明の製造
方法によつて顕著にコロナ塗布ムラを軽減するこ
とができるからである。
本発明の実施に用いられる基紙は、400cm2/ｇ以
上の光散乱係数を有する天然パルプを全使用パル
プ当り乾燥重量で40％以上用いたものであるが、
必要に応じて400cm2/ｇ以下の光散乱係数を有する
天然パルプを混抄してなる紙を用いてもよく、更
に天然パルプ以外の合成パルプ、合成繊維を混抄
してなる紙を用いてもよい。
本発明の実施に用いられる400cm2/ｇ以上の光散
乱係数を有する天然パルプとしては、光散乱係数
が400cm2/ｇ以上であれば、針葉樹漂白サルフアイ
トパルプ（NBSP）、針葉樹漂白クラフトパルプ
（NBKP）、広葉樹標白サルフアイトパルプ
（LBSP）、広葉樹漂白クラフトパルプ（LBKP）
およびそれらの混合パルプの木材パルプが有利に
用いられ、また漂白処理として、塩素、次亜塩素
酸塩、二酸化塩素漂白の通常の漂白処理並びにア
ルカリ抽出もしくは処理および必要に応じて過酸
化水素、過酢酸などによる過酸化物漂白処理など
およびそれらの組み合わせ処理を施した天然パル
プが有利に用いられ、蒸解助剤としてアントラキ
ノン化合物を用いた天然パルプなど各種のものを
使用することができるが、特に430cm2/ｇ以上の光
散乱係数を有する天然パルプが好ましい。また、
400cm2/ｇ以上の光散乱係数を有する天然パルプの
使用量としては、全使用パルプ当り乾燥重量で40
％以上であればよいが、特に50％以上用いるのが
好ましい。
本発明の実施に用いられるポリオレフイン樹脂
被覆紙の表面を電子衝撃する方法としては、例え
ば英国特許第971058号、同第1060526号などに記
載の方法がある。かかる特許の明細書に記載され
ている如く、任意の適当なコロナ放電または電子
衝撃装置（例えば、米国特許第2864755号、同第
284756号参照）を用いることができる。本発明は
支持体の疎水性ポリオレフイン樹脂表面をコロナ
放電処理または電子衝撃した後30分以内に好まし
くは30秒以内、更に好ましくは数秒以内に、該表
面にハロゲン化銀写真構成層を塗設して実施され
るのが有利である。例えば、本発明の好ましい実
施態様としては、連続的に走行する支持体のポリ
オレフイン樹脂被覆紙を第１セクシヨンに通紙
し、ここでポリオレフイン樹脂表面を電子衝撃
し、次いで第２セクシヨンに送り、そこで電子衝
撃表面にハロゲン化銀写真構成層を塗設する。か
かる方法を用いると電子衝撃とハロゲン化銀写真
構成層塗設の間の時間は、一般に数秒以下であ
り、操業速度によつては１秒の数分の１で実施可
能である。
本発明の実施に用いられる天然パルプを主成分
とする基紙に、紙料スラリー調製時に各種の高分
子化合物、添加物を含有せしめることができる。
例えば、乾燥紙力増強剤として、カチオン化澱
粉、カチオン化ポリアクリルアミド、アニオン化
ポリアクリルアミド、カルボキシ変性ポリビニル
アルコール、ゼラチンなど、サイズ剤として、脂
肪酸塩、ロジン、マレイン化ロジン等ロジン誘導
体、アルケニルまたはアルキルコハク酸およびそ
れらの塩または酸無水物、ジアルキルケテンダイ
マー乳化物、石油樹脂エマルジヨンなど填料とし
て、クレー、カオリン、炭酸カルシウム、硫酸バ
リウム、二酸化チタン、水酸化アルミニウム、水
酸化マグネシウムなど、湿潤紙力増強剤として、
メラミン樹脂、尿素樹脂、エポキシ化ポリアミド
樹脂など、定着剤として、硫酸アルミニウム、塩
化アルミニウムなどの多価金属塩、PH調節剤とし
て、苛性ソーダ、炭酸ソーダなど、そのほか染料
及び螢光増白剤などを適宜組み合わせて含有せし
めるのが有利である。また、基紙の抄造には、長
網抄紙機、丸網抄紙機など通常用いられる抄紙機
が用いられる。
本発明の実施に用いられる天然パルプを主成分
とする基紙は各種の水溶性高分子化合物、添加剤
を含有する液でスプレーあるいはタブサイズもし
くはサイズプレスされるのが有利である。かかる
水溶性高分子化合物、添加剤としては、例えば、
水溶性高分子化合物として、カチオン化澱粉、ポ
リビニルアルコール、カルボキシ変性ポリビニル
アルコール、カルボキシメチルセルロース、ヒド
ロキシエチルセルロース、ゼラチン、カゼインな
ど、サイズ剤として、石油樹脂エマルジヨン、ア
ルキルケテンダイマー乳化物など、スチレン−ブ
タジエン共重合体、エチレン−酢酸ビニル共重合
体、ポリエチレン、塩化ビニリデン共重合体など
のラテツクス、エマルジヨン類、吸湿性物質とし
て、グリセリン、ポリエチレングリコールなど、
顔料として、クレー、カオリン、タルク、硫酸バ
リウム、酸化チタンなど、PH調節剤として、塩
酸、燐酸、苛性ソーダなど、染料、螢光増白剤な
どの添加剤を組み合わせて使用するのが有利であ
る。
本発明の実施に用いられる天然パルプを主成分
とする基紙の種類および厚味に関しては特に制限
はないが、基紙を抄造後カレンダーにて圧力を印
加して圧縮するなどした密度が1.0以上の基紙が
好ましく、その坪量は40ｇ/m2〜250ｇ/m2が好ま
しい。
本発明の実施に用いられるポリオレフイン樹脂
としては、低密度ポリエチレン、高密度ポリエチ
レン、ポリプロピレン、ポリブテン、ポリペンテ
ンなどのオレフインのホモポリマーまたはエチレ
ン−プロピレン共重合体などのオレフインの２つ
以上から成る共重合体およびこれらの混合物であ
り、各種の密度および溶融粘度指数（メルトイン
デツクス；以下単にMIと略す）ものを単独にあ
るいはそれらを混合して使用できる。
本発明の実施に用いるポリオレフイン樹脂中に
は酸化チタン、酸化亜鉛、タルク、炭酸カルシウ
ムなどの白色顔料、ステアリン酸アミド、アラキ
ジン酸アミドなどの脂肪酸アミド、ステアリン酸
亜鉛、ステアリン酸カルシウム、ステアリン酸ア
ルミニウム、ステアリン酸マグネシウム、オクチ
ル酸ジルコニウム、パルミチン酸ナトリウム、パ
ルミチン酸カルシウム、ラウリン酸ナトリウムな
どの脂肪酸金属塩、テトラキス〔メチレン−３
（３・５−ジ−tert−ブチル−４−ヒドロキシフ
エニル）プロピオネート〕メタン、２・６−ジ−
tert−ブチル−４−メチルフエノールなどの酸化
防止剤、コバルトブルー、紺青、群青、セルリア
ンブルー、フタロシアニンブルーなどのブルーの
顔料や染料、コバルトバイオレツト、フアストバ
イオレツト、マンガン紫などのマゼンタの顔料や
染料、ビス（tert−ブチルベンゾオキサゾール）
チオフエン、ビス（メチルベンゾオキサゾール）
ナフタレンなどの螢光増白剤、チヌビン320、チ
ヌビン326、チヌビン328（以上チバ・ガイギー社
の商品名）などの紫外線吸収剤などの各種の添加
剤を適宜組み合わせて加えるのが好ましい。これ
らの添加剤をポリオレフイン樹脂中に添加する方
法としては、加熱練りロール、バンバリーミキサ
ー、ニーダー、混練用押出機等による溶融混合法
が最適であり、各成分をすべて最初から所望の組
成比だけ含有させたコンパウンドを作成して使用
してもよいし、各成分を高濃度に含んだマスター
バツチを各成分毎に作成して、それらを所望の割
合に混合して使用してもよい。
本発明の実施に用いられるポリオレフイン樹脂
被覆紙は、通常走行する基紙上に加熱溶融したポ
リオレフイン樹脂を流延するいわゆる押出コーテ
イング法に製造され、好ましくはその両面がポリ
オレフイン樹脂によつて被覆される。また、ポリ
オレフイン樹脂を基紙に被覆する前に、基紙にコ
ロナ放電処理もしくは電子衝撃処理、火炎処理な
どの活性化処理などを施すのが好ましい。ポリオ
レフイン樹脂被覆紙の乳剤側表面は、その用途に
応じて光沢面、マツト面、絹目面などを有し、裏
面は通常無光沢面であり、必要に応じて表面ある
いは表裏両面に、本発明でいうコロナ放電処理も
しくは電子衝撃処理とは別途に、それらによる活
性化処理を施してもよい。また、ポリオレフイン
樹脂被覆紙の樹脂層の厚さとしては特に制限はな
いが、一般に５ミクロン〜50ミクロン程度の厚さ
に押出しコーテイングされたものが有利である。
本発明の実施に用いられるハロゲン化銀写真構
成層としては、ハロゲン化銀白黒写真構成層、ハ
ロゲン化銀カラー写真構成層、多層ハロゲン化銀
カラー写真構成層、拡散転写法用のハロゲン化銀
写真構成層、直接ポジ型ハロゲン化銀写真構成
層、一般印画紙用、写植印画紙用、複写印画紙
用、印刷材料用などの各種の種類、用途のものが
使用できる。
また、本発明の実施に用いられるハロゲン化銀
写真構成層のハロゲン化銀写真乳剤としては、
種々のものが使用できる。例えば、ハロゲン化銀
組成として、例えば塩化銀、臭化銀、塩臭化銀、
塩沃臭化銀、沃塩化銀、沃臭化銀などの乳剤ある
いはそれらの混合物から成る乳剤、ハロゲン化銀
の結晶形や晶癖として、例えば立方体粒子のよう
な規則的形状粒子の乳剤または双晶構造を有する
不規則な形状の粒子群から成る乳剤や〔１、０、
０〕面、〔１、１、１〕面などを有する粒子から
成る乳剤あるいはそれらの混晶粒子、例えば
〔１、０、０〕面と〔１、１、１〕面を有する混
晶粒子から成る乳剤など、ハロゲン化銀の粒子径
や粒度分布として、微粒子性の乳剤あるいは粗粒
子性の乳剤や粒度分布の範囲の広い乳剤または単
分散乳剤のように粒度分布の範囲の狭い乳剤な
ど、乳剤中のPHとして、例えばPH4.0ないしはPH
8.0の範囲にある乳剤、乳剤中の銀イオン濃度と
して、例えばPAg6.0ないしはPAg11.0の範囲に
ある乳剤、ハロゲン化銀粒子のバインダーとし
て、ゼラチンや合成親水性バインダー、例えばポ
リビニルアルコール、ポリ−Ｎ−ビニルピロリド
ン、アクリル酸−アクリル酸エステル−アクリル
アミドの共重合体などのポリマーを用いた乳剤な
ど各種のものが使用できる。また、ネガ型ハロゲ
ン化銀写真乳剤を使用することもできるし、また
はもし必要ならば直接ポジ型ハロゲン化銀写真乳
剤を使用することもできる。更に、必要に応じて
潜像を主としてハロゲン化銀粒子表面に形成する
表面潜像型ハロゲン化銀写真乳剤でも、または内
部潜像型ハロゲン化銀写真乳剤でも使用できる。
更に、ハロゲン化銀写真乳剤の生成・分散およ
び第１熱成を種々の方法、条件で行つた乳剤を使
用できる。例えば、順混合法、逆混合法、同時混
合法（ダブルジエツト法、マルチジエツト法）、
特公昭46−7772号、米国特許第2592520号などに
記載の変換ハロゲン化銀法、アンモニア法、酸性
ないしは中性法、アルカリ法、特開昭48−65925
号記載の沃化銀核法など及びこれらの組み合わせ
の種々の方法、条件で調製された乳剤を使用でき
る。また、これらのハロゲン化銀写真乳剤の生
成・分散時あるいは第１熱成中または第１熱成後
に種々の添加剤を含有させた乳剤を特に有利に使
用できる。例えば、三塩化ロジウム、ヘキサハロ
ゲノロジウム酸塩などの水溶性ロジウム化合物、
ヘキサハロゲノイリジウム（）酸塩、ヘキサハ
ロゲノイリジウム（）酸塩などのヘキサハロゲ
ノイリジウム錯塩や塩化イリジウム（）、臭化
イリジウム（）などの水溶性イリジウム化合
物、ハロゲン化金、金酸塩、ハロゲン化金水素
酸、ハロゲン化金水素酸塩などの水溶性金化合
物、テトラクロロ白金酸塩などの水溶性白金化合
物、特開昭50−147925号、特開昭51−107129など
に記載もしくは例示のメルカプト−複素環化合
物、特開昭54−103018号に記載のヒドロキシアザ
インドリジン化合物、水溶性亜鉛、リチウム、ニ
ツケルなどの無機および有機金属塩などおよびそ
れらを適宜組み合わせて含有させた乳剤が有用で
ある。これら第１熱成を終えたハロゲン化銀写真
乳剤は、沈澱脱水し、所望の電気伝導度、銀イオ
ン濃度に達するまで水洗するのが好ましいが、不
水洗のものも使用することができる。
これらのハロゲン化銀写真乳剤は通常、種々の
化学増感を施して使用する。これらの化学増感を
施した乳剤としては、例えば、活性硫黄化合物を
含む増感型ゼラチン、チオ硫酸塩、活性硫黄化合
物による硫黄増感を施した乳剤、また、Ｎ・Ｎ−
ジメチルセレノ尿素などのセレノ化合物によるセ
レノ増感を施した乳剤、イリジウム、金、白金な
どの水溶性貴金属化合物による貴金属増感を施し
た乳剤、ポリエチレンオキサイド誘導体を用いて
増感した乳剤などが有用である。また、シアニ
ン、メロシアニン、カルボシアニン等のポリメチ
ン増感色素類の単独あるいは組み合わせ使用、ま
たはそれらとスチリル染料との組み合わせ使用に
よつて分光増感や強色増感を化学増感と合わせて
施した乳剤が有利に使用できる。
また、本発明は、ハロゲン化銀カラー写真乳剤
を有利に使用できる。即ち現像主薬の酸化生成物
と反応して染料を形成する化合物（カプラー）を
添加した乳剤を有利に使用できる。この目的のた
めに使用し得る代表的なカプラーとしては、ビバ
ロイルアセトアニリド型あるいはベンゾイルアセ
トアニリド型の開鎖ケトメチレンイエローカプラ
ー、ピラゾロン系マゼンタカプラー、フエノール
系あるいはナフトール系シアンカプラーおよびそ
れらの混合物あるいは複色カプラー、黒色カプラ
ーなどがあげられ、これらのカプラーの構造に合
わせて、現像抑制剤放出型カプラー（DIRカプラ
ー）、カプラーの活性点にそれぞれ−Ｏ−アリル
置換、−Ｏ−アシル置換、ヒダントイン化合物置
換、ウラゾール化合物置換、コハク酸イミド化合
物置換、モノオキソイミド化合物置換、ビリダゾ
ン化合物置換などがなされている２当量カプラー
などがあげられる。
本発明の実施に用いられるハロゲン化銀写真構
成層中のバインダーあるいは保護コロイドとして
は各種のものが使用できる。即ち石灰処理ゼラチ
ン、酸処理ゼラチン、ゼラチン誘導体、例えばフ
タール化ゼラチン、アシル化ゼラチンなど、澱分
およびその誘導体、カルボキシメチルセルロー
ス、ヒドロキシエチルセルロース等のセルロース
化合物、ポリビニルアルコール、ポリ−Ｎ−ビニ
ルピロリドン、アクリル酸−アクリル酸エステル
の共重合体、アクリル酸−アクリルアミド共重合
体、アクリル酸−アクリル酸エステル−アクリル
アミド共重合体などの合成親水性バインダー、ま
たゼラチンおよびゼラチン誘導体の増粘剤とし
て、例えばセルロース、デキストラン、デキスト
リン、アルギン酸、澱粉、ポリビニルアルコール
などの水酸基を有する天然または合成の高分子物
質、好ましくは多糖類の硫酸エステル化合物、ス
チレン−マレイン酸共重合体、アルキルビニルエ
ーテル−マレイン酸共重合体などのポリマーを単
独にまたはそれらを組み合わせて使用できる。
本発明の実施に用いられるハロゲン化銀写真構
成層中、特に好ましくはハロゲン化銀写真乳剤層
中には、各種のカブリ防止剤もしくは安定剤を含
有せしめるのが有利である。例えば、米国特許第
2716062号、同第2944900号などに記載されている
ようなヒドロキシ−アザインドリジン化合物、特
開昭48−102621号、同第51−107129号などにも記
載もしくは例示のメルカプト−複素環化合物、２
−チオン複素環化合物、ベンズイミダゾール、ベ
ンズトリアゾール、１−フエニル−テトラゾー
ル、ベンズオキサゾール、グアナゾール化合物な
どのメルカプト基を含まない複素環化合物などお
よびそれらを組み合わせて含有せしめるのが有利
である。
また、本発明の実施に用いられるハロゲン化銀
写真構成層中には、各種の添加剤を含有せしめる
ことができる。例えば硬膜剤として、ホルマリ
ン、ホルムアルデヒドと尿素あるいはメラミンな
どとの反応生成物、ハロゲンカルボン酸類、ビニ
ルスルフオン化合物、アジリジン化合物、エポキ
シ化合物、活性ハロゲン化合物、アクリロイル化
合物、イソシアネート化合物などの有機硬膜剤、
クロム明ばん、炭酸ジルコニウム等の無機硬膜
剤、界面活性剤として、アルキルベンゼンスルフ
オン酸塩、スルフオコハク酸エステル塩などのア
ニオン界面活性剤、サポニン、アルキレンオキサ
イド化合物等のノニオン界面活性剤、アミノ酸
類、アミノスルフオン酸類、アミノアルコールの
エステル類等の両性界面活性剤など、紫外線吸収
剤として、ヒドロキシ−ジアルキル−フエニル基
を２位に有するベンゾトリアゾール化合物など、
螢光増白剤として、特公昭45−24068号、特開昭
54−94318号などに記載もしくは例示の化合物、
鮮鋭度向上色素として、食用赤色２号、特開昭47
−14721号などに例示の酸性染料など、金属イオ
ン封鎖剤として、エチレンジアミンテトラ酢酸な
ど、媒染剤として、Ｎ−グアニルヒドラゾン系化
合物、４級オニウム塩化合物など、帯電防止剤と
して、繊維素系帯電防止剤、ポリスチレンスルフ
オン酸のアルカリ塩、重合せるアクリル酸類およ
びアクリル酸共重合体類のアルカリ塩など、マツ
ト剤として、ポリメタアクリル酸メチル、ポリス
チレン、メタアクリル酸−メタアクリレート共重
合体コロイド状酸化珪素など、膜物性改良剤とし
て、アクリル酸エステル、メタアクリル酸エステ
ルなどと他のメチレン基を持つ単量体との共重合
体からなるラテツクスなどを含有せしめることが
できる。更に、本発明に係る直接ポジハロゲン化
銀乳剤層中には、カプラセ剤、直接ポジ写真乳剤
用増感染料などの直接ポジ写真乳剤用添加剤を含
有せしめることができる。
本発明に係る帯電防止性のバツクコート層はハ
ロゲン化銀写真材料の裏面、即ちハロゲン化銀写
真構成層の設けられていない支持体面上に親水性
有機コロイド層、好ましくは帯電防止剤を含む親
水性有機コロイド層から成る塗布層を設置したも
のである。かかる帯電防止性のバツクコート層中
の親水性有機コロイド層としては各種のものが使
用できる。例えば、石灰処理ゼラチン、酸処理ゼ
ラチン、ゼラチン誘導体、たとえばフタール化ゼ
ラチン、アシル化ゼラチンなど、澱粉およびその
誘導体、カルボキシメチルセルロース、ヒドロキ
シエチルセルロース等のセルロース化合物、ポリ
ビニルアルコール、ポリアクリルアミド、これら
のカルボキシ変性ポリマー、ポリ−Ｎ−ビニルピ
ロリドン、寒天、アルギン酸ソーダなどがある。
また、本発明に係る帯電防止性のバツクコート
層中に各種の帯電防止剤を含有せしめて、該バツ
クコート層の帯電防止能を一層顕著に発揮にせし
めるのが特に好ましい。これらの帯電防止剤とし
ては、種々の無機および有機帯電防止剤が有用で
ある。好ましい無機帯電防止剤としては、例えば
コロイド状シリカがある。好ましい有機帯電防止
剤としては、例えばスチレンと無水マレイン酸共
重合体のナトリウム塩、イソブチレンと無水マレ
イン酸共重合体のナトリウム塩などの炭素数４以
上の不飽和共重合性単量体と無水マレイン酸との
共重合体のアルカリ塩、セルロース、デキストラ
ン、デキストリン、アルギン酸、澱粉、ポリビニ
ルアルコールなどの水酸基を有する天然または合
成の高分子物質、好ましくはセルロース硫酸エス
テルのアルカリ塩、ポリスチレンスルフオン酸の
アルカリ塩、ポリアクリル酸ナトリウム類（例え
ば、ポリアクリル酸、ポリメタアクリル酸、ポリ
−α−エチルアクリル酸のナトリウム塩など）、
ポリアクリル酸カリウム、アクリル酸とアクリル
酸メチル共重合体のナトリウム塩などの重合せる
アクリル酸類およびアクリル酸共重合体のアルカ
リ塩などがある。これらの親水性ポリマーのなか
で、炭素数４以上の不飽和共重合性単量体と無水
マレイン酸共重合体のアルカリ塩、セルロース硫
酸エステルのアルカリ塩などは、単独で、バツク
コート層の親水性有機コロイドとして使用するこ
とができる。
本発明に係る帯電防止性のバツクコート層中の
親水性有機コロイドの樹脂被覆紙の裏面への塗布
量は0.01ｇ/m2〜10ｇ/m2の範囲が有用であるが、
好ましくは0.1ｇ/m2〜5.0ｇ/m2の範囲である。ま
た、バツクコート層中に有利に含有せしめられる
帯電防止剤の塗布量としては、0.01ｇ/m2〜３ｇ/
m2の範囲が好ましい。更に、バツクコート層のPH
は9.0以下、好ましくは7.0以下にするのが望まし
い。
また、本発明に係るバツクコート層中には、本
明細書32頁〜33頁中で記載の硬膜剤、界面活性
剤、螢光増白剤、マツト剤、膜物性改良剤などの
種々の添加剤を含有せしめることができる。
本発明の実施に当り、電子衝撃処理したポリオ
レフイン樹脂被覆紙にハロゲン化銀写真構成層と
塗設するには、スライドホツパー（Slide
hopper）方式もしくはエクストル−ジヨンバー
（Eextrusion bar）方式またはカーテンフロー
（Curtain flow）方式で塗布した後乾燥するのが
普通である。スライドホツパー方式もしくはエク
ストル−ジヨンバー方式の塗布方法としては、米
国特許第2761417号、同第2761418号、同第
2761419号、同第2761791号、特公昭48−44925
号、特開昭49−107040号などに記載の方法、カー
テンフロー方式の塗布方法としては、米国特許第
3508947号、特公昭49−14130号、特開昭52−
69946号などに記載の方法など各種の方法で本発
明を実施することができる。また、多層ハロゲン
化銀写真構成層を塗設するには、多層塗布用ホツ
パーを用いて多層同時に塗設することができる。
本発明におけるハロゲン化銀写真材料は、その
種類、用途、目的等に応じて、「写真感光材料と
取扱法」（共立出版、宮本五郎著、写真技術講座
２）に記載されているような、露光、現像、停
止、定着、漂白、安定などの処理が行われる。例
えば、一般用白黒ハロゲン化銀写真材料は、その
露光後通常、少なくともハロゲン化銀現像主薬と
アルカリ剤とを含む溶液で処理して現像せられる
が、ある場合にはハロゲン化銀現像主薬を全くあ
るいは実質的に含まないアルカリ活性液が用いら
れることもある。現像された銀像は、例えばナト
リウムチオサルフエート、ナトリウムチオシアネ
ートの如き定着剤を少なくとも含む酸性溶液で定
着・安定化される。また、ハロゲン化銀カラー写
真材料は、通常その露光後発色現像主薬を含むあ
るいは実質的に含まないアルカリ活性浴で処理し
て発色現像され、その後アミノポリカルボン酸の
金属塩（例えば、エチレンジアミン四酢酸、プロ
ピレンジアミン四酢酸などの第２鉄錯塩、第２銅
錯塩など）とチオ硫酸塩の如き定着剤とを少なく
とも含む一浴漂白定着液で処理される。かかる一
浴漂白定着液には、脱銀促進剤、螢光増白剤など
の添加剤を含有させてもよい。
次に本発明をさらに具体的に説明するために、
実施例を述べる。
実施例 １
天然パルプの配合として、第１表記載のパルプ
試料をカナデイアン・スタンダード・フリーネス
310mlに叩解し、下記配合で160ｇ/m2の紙を抄造
した。
（配合中の数値は重量部を示す。）
パルプ 100
カチオン化澱粉 ２
アニオン性ポリアクリルアミド樹脂 0.5
ステアリン酸ナトリウム 0.5
硫酸バンド PH4.5に調節
アルキルケテンダイマー乳化物（ケテンダイマー
分として） 0.4
ポリアミドポリアミンエピクロルヒドリン樹脂
0.4
得られた湿紙を110℃の加熱プレートで乾燥し
た。
この紙に、次の処方の含浸液を20ｇ/m2含浸さ
せ、110℃の熱風恒温乾燥機で乾燥した。処方
中、食塩は温度20℃、相対湿度65％における紙の
表面固有抵抗が第１表記載の組み合わせになるよ
うに量変化して添加した。
（処方中の数値は重量部を示す。）
カルボキシ変性ポリビニルアルコール ３
ジアミノスチルベンジスルホン酸塩型螢光増白剤
0.05
青色染料 0.002
食 塩 量変化
水を加えて 100
含浸、乾燥した基紙は、線圧90Kg/cmでスーパ
ーカレンダー処理した後、その両面をコロナ放電
処理した。次にその裏面に高密度ポリエチレン
（密度0.96ｇ/cm2、メルトインデツクス５）と低密
度ポリエチレン（密度0.92ｇ/cm2、メルトインデ
ツクス５）の１：１混合物を樹脂温330℃で溶融
押出し塗布機を用いて30μの厚さにコーテイング
した。次いで表面にアナターゼ型酸化チタン12％
を含有する低密度ポリエチレン（顔料添加前のポ
リエチレンは密度0.92ｇ/cm2、メルトインデツク
ス５）を樹脂温330℃で30μの厚さにコーテイン
グした。
かくして作成したポリエチレン被覆紙の裏面
（酸化チタンを含有していないポリエチレン面）
にコロナ放電処理した後、下記のバツクコート液
を塗布乾燥した。
スチレン−無水マレイン酸共重合物（商品名マ
ロンMS大同工業(株)製）の５％水溶液60ｇ中に、
コロイド状シリカの20％水溶液（商品名スノーテ
ツクス日産化学(株)製）10ｇおよび10％ドデシルベ
ンゼンスルフオン酸ソーダ水溶液10ｇを加え、更
に下式で示される化合物〔〕
の５％メタノール溶液10ｇを加える。その後PH調
節剤によるこの液のPHを5.5に調整し、全量を100
ｇに水を加えて調整する。この液を塗布量30ｇ/
m2（湿分）でポリエチレン被覆紙の裏面に塗布す
る。
次いで酸化チタンを含有するポリエチレンの表
面をコロナ放電処理した数秒以内およびコロナ放
電処理して４日間貯蔵後、多層ハロゲン化銀カラ
ー写真構成層を支持体のポリエチレン表面の最も
近くに青感ハロゲン化銀写真乳剤層とその保護
層、その上に緑感ハロゲン化銀写真乳剤層と紫外
線吸収層、さらにその上に赤感ハロゲン化銀写真
乳剤層とその保護層が位置するように、多層塗布
用ホツパーから６層同時に塗布し乾燥した。
この場合、青感ハロゲン化銀写真乳剤層には、
AgBr／Agcl＝95／５なるハロゲン組成を有する
平均粒子径0.8μの最適感度に硫黄増感した全ア
ンモニア法ハロゲン化銀写真乳剤を用い、硝酸銀
量で9.6分当り下式で示される青感用増感色素
〔〕
9.6mgで光学増感し、黄色カプラーとしては下
式で示されるカプラー〔〕
をフタール酸ジブチルに分散せしめて用い、更に
適当量のカブリ防止剤を用い、ゼラチン1.7ｇ/
m2、銀0.38ｇ/m2、カプラー0.5ｇ/m2の割合で塗
布した。青感乳剤層の保護層には２・５−ジ−
tert−オクチルハイドロキノン（以下HQと略
す）をフタール酸ジブチルに分散せしめて用い、
ゼラチン1.2ｇ/m2、HQ0.04ｇ/m2の割合で塗布し
た。
また、緑感ハロゲン化銀写真乳剤層には、硝酸
銀量で9.6ｇ分当り、３×10-6ｇのヘキサクロロ
ジウム（）酸カリウムの存在下にハロゲン化銀
粒子を生成・分散して製造したAgBr／Agcl＝
95／５なるハロゲン組成を有する平均粒子径0.4
μの最適感度に硫黄増感した実質的に〔１、０、
０〕面から成る酸性法ハロゲン化銀写真乳剤を用
い、硝酸銀量で9.6ｇ分当り下式で示される緑感
用増感色素〔〕
9.6mgで光学増感し、マゼンタカプラーとして下
式で示されるカプラー〔〕
をHQと共にフタール酸ジブチルに分散せしめて
用い、更に適当量のカブリ防止剤、鮮鋭度向上色
素を用い、ゼラチン1.7ｇ/m2、銀0.38ｇ/m2、カ
プラー0.5ｇ/m2、HQ0.015ｇ/m2の割合で塗布し
た。紫外線吸収層には、下式で示される紫外線吸
収剤〔〕
をフタール酸ジノルマルノニールに分散せしめて
用い、ゼラチン1.4ｇ/m2、紫外線吸収剤0.4ｇ/m2
の割合で塗布した。
また、赤感ハロゲン化銀写真乳剤層には、硝酸
銀量で9.6ｇ分当り３×10-4ｇのヘキサクロロイ
リジウム（）酸カリウムの存在下にハロゲン化
銀粒子を生成・分散する以外は緑感乳剤とまつた
く同様にして製造したハロゲン化銀写真乳剤を用
い、硝酸銀量で9.6ｇ分当り下式で示される赤感
用増感色素〔〕
0.96mgで光学増感し、シアンカプラーとして下式
で示されるカプラー〔〕
をHQと共にフタール酸ジブチルに分散せしめて
用い、更に適当量のカブリ防止剤、鮮鋭度向上色
素を用い、ゼラチン1.5ｇ/m2、銀0.38ｇ/m2、カ
プラー0.3ｇ/m2、HQ0.015ｇ/m2の割合で塗布し
た。赤感乳剤層の保護層は、ゼラチン1.2ｇ/m2の
割合で塗布した。
更に、各写真構成層には、それぞれ適当量の硬
膜剤と界面活性剤としてスルホコハク酸エステル
のナトリウム塩を用いた。その場合、硬膜剤とし
ては下式で示される化合物〔〕
を対ゼラチン当り1.7重量％用いた。また、青感
ハロゲン化銀写真乳剤とその保護液および緑感ハ
ロゲン化銀写真乳剤と紫外線吸収層用塗布液は、
それぞれの粘度が25センチポイズ〜30センチポイ
ズの範囲になるように調製した。赤感ハロゲン化
銀写真乳剤とその保護液は、それぞれの粘度が30
センチポイズ〜35センチポイズの範囲になるよう
に調製した。その際、必要に応じてゼラチンの増
粘剤として、適当量のケルコ（KELCO）SCSの
MV〔米国ニユージヤージイ州のケルコ
（KELKO）社製〕を用いた。
このようにして塗布、乾燥して得られた多層ハ
ロゲン化銀カラー写真材料は、支持体たるポリエ
チレン被覆紙に隣接して下から順に青感乳剤層、
緑感乳剤層、赤感乳剤層の順に配置されている。
各試料を以下に記載の方法で評価した。その
際、ハロゲン化銀写真構成層の硬膜度の評価基準
としては数値で、また、ハロゲン化銀写真構成層
の塗布ムラおよび支持体との接着性の評価基準と
しては、◎印（非常に良好）、〇印（良好）、△
（やや良好）、×印（不良）で評価した。
〔ハロゲン化銀写真構成層のコロナ塗布ムラの評
価〕
塗布試料を35℃、常湿下に２日間保存後、各試
料に適正量のグリーン露光を与え、Ｄ−72現像液
の稀釈液で20℃にて90秒間現像後、停止、定着、
水洗、乾燥する。その後、現像塗布面を観察し、
視覚的にコロナ塗布ムラを判定する。
〔ハロゲン化銀写真構成層の支持体との接着性の
評価〕
下記の発色現像液に33℃で３分30秒間浸漬後、
ハロゲン化銀写真構成層に十字型の傷をつけてそ
の部分を指頭でこすり、剥離状態を見る。
（発色現像液）
炭酸ナトリウム（１水塩） 46.0ｇ
無水亜硫酸ナトリウム 2.0ｇ
臭化カリウム 0.5ｇ
CD− 4.5ｇ
ヘキサメタリン酸ナトリウム 0.5ｇ
塩酸ヒドロキシルアミン 2.0ｇ
螢光増白剤 0.5ｇ
ベンジルアルコール 12 c.c.
ジエチレングリコール 10 c.c.
水で全量を１に、水酸化ナトリウムでPH＝
10.2に調整する。
〔ハロゲン化銀写真構成層の硬膜度の評価〕
塗布試料を35℃で２日間保存した後、33℃の純
水に３分間浸漬し吸液量を測定し、原紙内水分量
と吸液量の関係を調べた。原紙内水分量が同じ
で、吸液量が少いほど硬膜度が強いことを示す。
得られた結果を第１表に示す。
原紙内水分量は13.6±0.1（ｇ/m2）で各試料実
質的に均一であつた。
The present invention relates to a method for producing a silver halide photographic material, and more specifically to a method for producing a silver halide photographic material, which has a polyolefin resin-coated paper coated with a polyolefin resin as a support using paper mainly composed of natural pulp as a substrate, and halogenated A method for producing a silver halide photographic material coated with a silver photographic constituent layer, more specifically, a silver halide photographic constituent layer having good adhesion on the polyolefin resin surface of the support and having uniform coating properties. The present invention relates to a method for producing a silver halide photographic material having as a support a polyolefin resin-coated paper which is of good quality and shows no uneven coating. Usually, a silver halide photographic material is composed of a support and a silver halide photographic constituent layer provided on the support. Such silver halide photographic constituent layers include a silver halide photographic emulsion layer, a protective layer, a subbing layer, an intermediate layer or color mixing prevention layer, an antihalation layer or filter layer, an ultraviolet absorbing layer, etc., and combinations thereof. It is what was done. For example, a single silver halide photographic material has a silver halide photographic emulsion layer and its protective layer on a support. In addition, multilayer silver halide color materials consist of a blue-sensitive silver halide photographic emulsion layer and an intermediate layer, a green-sensitive silver halide photographic emulsion layer and an ultraviolet absorbing layer, a red-sensitive silver halide photographic emulsion layer and a protective layer, on a support. etc. are provided in order and arranged in multiple layers. On the other hand, supports for silver halide photographic materials have conventionally been made of films such as polyethylene terephthalate film, cellulose triacetate film, and polystyrene, paper based on natural pulp, and resins capable of forming films on both sides.
Hydrophobic supports such as resin-coated papers, many coated with polyolefin resins, are well known. especially,
As a support for photographic printing paper, polyolefin resin-coated paper is increasingly being used in place of the conventionally used baryta paper. The reason for this is that polyolefin resin-coated paper used as a photographic support is hydrophobic, so processing liquids penetrate into the base paper layer during the development and fixing processes of photographic paper, compared to baryta paper. This is because the processing time for washing, drying, etc. can be shortened. By the way, when producing a silver halide photographic material by using a polyolefin resin-coated paper having a hydrophobic surface as a support and coating a silver halide photographic constituent layer on the support, the hydrophobic polyolefin resin of the support is It is well known that the surface of a hydrophobic polyolefin resin requires some kind of treatment in order to improve the adhesion between the resin surface and the silver halide photographic constituent layer. One of the most economical and effective methods to provide good adhesion is to electron bombard the hydrophobic polyolefin resin surface. Electron bombardment is also known as corona discharge treatment. The method of electron bombarding the surface of hydrophobic polyolefin resin is as follows:
For example, it is described in British Patent No. 971058, British Patent No. 1060526, etc. In addition, in order to further strengthen the adhesion between the hydrophobic polyolefin resin surface and the silver halide photographic constituent layer by subjecting the hydrophobic polyolefin resin surface of the support to electron impact treatment, it is necessary to within, preferably
It is necessary to coat the silver halide photographic constituent layer on the hydrophobic polyolefin resin surface of the electron-impact-treated support within 30 minutes, particularly preferably within several seconds. However, using a polyolefin resin-coated paper whose substrate is paper mainly composed of natural pulp as a support, a silver halide photographic constituent layer is formed within 30 minutes after electron impact is applied to the polyolefin resin surface of the support. It has become clear that silver halide photographic materials produced by coating, although good adhesion of the silver halide photographic constituent layers to the support, are produced, but suffer from certain serious drawbacks. That is, after applying electron bombardment to the polyolefin resin surface of the support
If the silver halide photographic constituent layer is applied within 30 minutes, the coatability of the silver halide photographic constituent layer to the polyolefin resin support surface will be uneven, and the silver halide of the finished silver halide photographic material will be uneven. The problem is that coating unevenness occurs in the photographic constituent layers. Since this coating unevenness is strongly influenced by the electron impact treatment, it will be simply referred to as corona coating unevenness hereinafter. In particular, corona coating unevenness occurring in the silver halide photographic emulsion layer is more clearly observed when the silver halide photographic material is subjected to development treatment after uniform exposure. Needless to say, uneven corona coating causes a significant deterioration in the performance of photographic paper. According to the studies conducted by the present inventors, it has become clear that this uneven coating of corona occurs due to the following situation. First, corona coating unevenness is noticeable when a silver halide photographic constituent layer is coated on the polyolefin resin surface of the support within a short period of time, for example, up to one hour after electron bombardment. If a long time has passed (for example, 1 to 2 days) after the electron impact treatment,
If a silver halide photographic constituent layer is coated on this electron impact polyolefin resin surface, corona coating unevenness will not be so severe. Although uneven corona coating can be avoided by holding the holding time, it becomes an obstacle in the manufacturing process of silver halide photographic materials. That is, in order to avoid uneven corona coating, the support must be stored for a sufficient period of time after electron impact, while the silver halide photographic constituent layers must be stored for about 1 hour after electron impact in order to obtain good adhesion to the support. The coating must be applied to the polyolefin resin coated paper support within ~2 days. Secondly,
Even if a silver halide photographic constituent layer is coated within 30 minutes after electron impact is applied to the polyolefin resin-coated paper surface of the support to produce a silver halide photographic material, corona coating unevenness is caused by a single problem. It is less severe in silver halide photographic materials, and is more pronounced in multilayer silver halide photographic materials comprising at least two or more silver halide photographic emulsion layers, such as multilayer silver halide color photographic materials. That is, within 30 minutes after electron impact is applied to the polyolefin resin-coated paper surface of the support, a blue-sensitive silver halide photographic emulsion layer containing a yellow coupler, a color mixing prevention layer, and a magenta coupler are sequentially applied adjacent to the support. A multilayer silver halide color photograph manufactured by simultaneously coating six layers of a green-sensitive silver halide photographic emulsion layer containing a UV absorption layer, a red-sensitivity silver halide photographic emulsion layer containing a cyan coupler, and its protective layer from a multilayer coating hopper. In materials,
Corona coating unevenness is noticeable in the green-sensitive silver halide photographic emulsion layer, less severe in the blue-sensitive silver halide photographic emulsion layer, and even milder in the red-sensitive silver halide photographic emulsion layer. However, as prior art regarding problems and improvements in producing a silver halide color photographic material by coating a silver halide color photographic constituent layer within 30 minutes after applying electron bombardment to the hydrophobic surface of the support, is described in Special Publication No. 47-51905. According to this document, the problem is that dye spots occur in silver halide color photographic materials, and this problem is to be improved by using a specific optical sensitizing dye. However, using a polyolefin resin-coated paper as a support made of paper whose main component is natural pulp and coated with a polyolefin resin, silver halide is deposited within 30 minutes after electron impact is applied to the polyolefin resin surface of the support. It was still insufficient to solve the corona coating unevenness that occurs in silver halide photographic materials manufactured by coating photographic constituent layers. Therefore, the object of the present invention is, first, to have a polyolefin resin-coated paper as a support, which is made of paper mainly composed of natural pulp and coated with a polyolefin resin, and to provide a paper coated on the support. An excellent silver halide photographic material with good adhesion of the silver halide photographic constituent layers on the support surface and uniform coating properties with no or reduced coating unevenness is a problem in the manufacturing process. The object of the present invention is to provide a method for producing the same without causing any disadvantages. Second, it has a polyolefin resin-coated paper as a support, which is made of paper whose main component is natural pulp and is coated with a polyolefin resin, and at least two coated sheets are simultaneously coated on the support from a multilayer coating hopper. The multilayer silver halide photographic constituent layer consisting of the above silver halide photographic emulsion layer has good adhesion on the support surface and has uniform coating properties, with no or reduced coating unevenness. It is an object of the present invention to provide a method for producing silver halide photographic materials without causing obstacles or disadvantages in the production process. Furthermore, another object of the present invention is to significantly enhance not only the adhesion of the silver halide photographic constituent layer on the support surface, but also the hardness thereof, and the coating property to be uniform, so that coating unevenness is not observed. A method for producing an excellent silver halide photographic material having as a support a polyethylene resin-coated paper based on a paper based on natural pulp with no or reduced natural pulp, without causing any obstacles or disadvantages in the production process. It is to provide. As a result of intensive studies, the present inventors have found that the object of the present invention is to have a polyolefin resin-coated paper as a support, which is made of a paper mainly composed of natural pulp and coated with a polyolefin resin, and to have a halogenated paper on the support. When manufacturing silver halide photographic materials with silver photographic constituent layers, the light scattering coefficient of natural pulp is
Natural pulp of 400 cm 2 /g or more is used in an amount of 40% or more by dry weight based on the total pulp used, and a silver halide photographic constituent layer is applied within 30 minutes after electron impact is applied to the polyolefin resin surface of the support. It turns out that this can be achieved to a great extent. Here, the light scattering coefficient of natural pulp is measured by the method described below. That is, natural pulp was beaten to 300 ml according to the Canadian standard form of JIS P-8121 "Pulp freeness test method" according to the method using a beader of JIS P-8210 "Method of testing the strength of paper pulp". , JIS
Ten sheets of 80 g/m 2 hand-made paper are prepared using a hand-sheeting machine according to P-8209 "Hand-sheeted paper preparation method for pulp testing", the water is squeezed out using a hand press, and the paper is dried at 110°C using a drum dryer. This hand-made paper was processed according to JIS P-8111 "Pretreatment of test paper", and one sheet of the hand-made paper was placed on a black backing board according to JIS P-8138 "Paper opacity test method". Stack them and measure their reflectance, and take the average value of the reflectance of each of the 10 sheets as Ro.Next, stack 10 sheets of this handmade paper without using a backing black board and measure its reflectance.
Let's call it Roo. The handmade paper used for this measurement was dried at 105℃ for 3 hours using an open dryer, and the JIS
Measure the absolute dry basis weight according to P-8124 “Measurement method of paper metric basis weight”. This is assumed to be W (g/m 2 ). Using RO, Roo, and W obtained above, calculate the light scattering coefficient (cm 2 /g) using the following formula. Furthermore, the effect of the present invention is that as a substrate paper for polyolefin resin-coated paper (hereinafter simply referred to as base paper),
This effect is better exhibited by using paper having a surface resistivity of 6.3×10 8 Ω or more, preferably 1.0 to 10 9 Ω or more, at a temperature of 20° C. and a relative humidity of 65%. Note that the surface resistivity of paper is determined when the sample is heated at 20°C.
After keeping the sample conditions constant by storing it in a constant temperature and humidity chamber with a relative humidity of 65% for 48 hours, the resistance of the surface of the paper sandwiched between concentric circular electrodes with a diameter of 5 cm and a diameter of 7 cm was measured, and the resistance R = ∫ 3 ．． 5 2 . 5 ρsdr/2πr(ρs;
It is calculated from the relationship of surface resistivity). Furthermore, silver halide photographic materials that use polyolefin resin-coated paper as a support tend to attract static electricity and dust during production or handling, causing various troubles. Partial fogging called static marks, which is extremely unpleasant due to photographic characteristics, may occur in the photographic emulsion layer. For this purpose, water-soluble chlorides such as sodium chloride and calcium chloride, which have good compatibility with various hydrophilic polymers such as gelatin, carboxy-modified polyvinyl alcohol, and starch, are usually added to the base paper layer. Conventionally, it has been carried out to contain these hydrophilic polymers in the form of size press or tab size. Also, in some cases, water-soluble sulfates such as sodium sulfate are used with starch for this purpose. Furthermore, if necessary, a hydrophilic colloid layer called a back coat layer with antistatic and anti-curling properties is coated on the back side of the support, that is, on the side of the support opposite to the support side on which the silver halide photographic constituent layer is provided. It is also known to provide layers. However, in order to prevent static electricity on polyolefin resin-coated paper, a conductive agent is contained in the base paper layer mainly composed of natural pulp, so that the surface resistance of the base paper increases at 200℃.
When the resistance decreases to 6.3×10 8 Ω or less at a temperature of 65% relative humidity, the effects of the present invention, that is, the effects of improving corona coating unevenness and improving adhesion are no longer significant. Meanwhile, as a base paper, temperature 20℃, relative humidity 65
It has been found that the effects of the present invention can be more significantly exhibited by using paper having a surface resistance of 6.3×10 8 Ω or more, preferably 1.0×10 9 or more. That is, electron bombardment was applied to the hydrophobic surface of a polyolefin resin-coated paper whose substrate was paper.
In silver halide photographic materials manufactured by coating the silver halide photographic constituent layer within 30 minutes, the coating properties of the silver halide photographic constituent layer are extremely uniform, and coating unevenness is not observed or is significantly reduced. Not only does it significantly improve adhesion on the support surface, but it also improves the hardening of silver halide photographic constituent layers containing a gelatin-based hydrophilic organic colloid layer and a gelatin hardener. It has become clear that it can be significantly strengthened. The above is understood to be completely different in spirit from the present invention and the prior art described in Japanese Patent Publication No. 47-51905, which states that it is advantageous to add an antistatic agent to the substrate layer. . Therefore, a preferred embodiment of the present invention is a paper whose main component is natural pulp, in which natural pulp with a light scattering coefficient of 400 cm 2 /g or more is used in an amount of 40% or more by dry weight based on the total pulp used, and Temperature 20℃, relative humidity
A polyolefin resin-coated paper with a paper substrate having a surface resistivity of 6.3×10 8 Ω or more at 65% was used as a support, and one side of the support was subjected to corona discharge, and then halogen was removed within 30 minutes. A silver oxide photographic constituent layer is coated, and a back coat layer consisting of a hydrophilic organic colloid layer is coated on the other side (back side) of the support. The present invention also relates to a multilayer silver halide photographic material comprising at least two silver halide photographic emulsion layers having as a support a polyolefin resin-coated paper whose substrate is paper mainly composed of natural pulp, particularly a multilayer halogen color photographic material. Useful in the production of photographic materials. Within 30 minutes after electron bombardment on the polyolefin resin-coated paper side of the support, a blue-sensitive silver halide emulsion layer containing a yellow coupler, a color mixing prevention layer, and a magenta coupler are sequentially applied adjacent to the support. including a green silver halide photographic emulsion layer and an ultraviolet absorbing layer,
In a multilayer silver halide color photographic material manufactured by coating six layers of a red-sensitive silver halide photographic emulsion layer containing a cyan coupler and its protective layer simultaneously from a multilayer coating hopper, in the green-sensitive silver halide photographic emulsion layer, This is because, although corona coating unevenness occurs significantly, the manufacturing method of the present invention can significantly reduce corona coating unevenness. The base paper used in the practice of the present invention is one in which natural pulp having a light scattering coefficient of 400 cm 2 /g or more is used in an amount of 40% or more by dry weight based on the total pulp used.
If necessary, paper made by mixing natural pulp with a light scattering coefficient of 400 cm 2 /g or less may be used, and paper made by mixing synthetic pulp or synthetic fiber other than natural pulp may also be used. . Natural pulps with a light scattering coefficient of 400 cm 2 / g or more used in the practice of the present invention include softwood bleached sulfite pulp (NBSP), softwood bleached kraft pulp ( NBKP), hardwood white sulfite pulp (LBSP), hardwood bleached kraft pulp (LBKP)
and their mixed pulps are advantageously used, and the bleaching treatments include conventional bleaching treatments such as chlorine, hypochlorite and chlorine dioxide bleaching as well as alkaline extraction or treatment and optionally hydrogen peroxide, peroxide and Natural pulps that have been subjected to peroxide bleaching treatment using acetic acid, etc., or a combination thereof are advantageously used, and various kinds of pulps such as natural pulps that have been treated with anthraquinone compounds as cooking aids can be used, but in particular 430 cm Natural pulps having a light scattering coefficient of 2 /g or more are preferred. Also,
The amount of natural pulp that has a light scattering coefficient of 400cm 2 /g or more is 40% by dry weight per total pulp used.
% or more, but it is particularly preferable to use 50% or more. Examples of the method of electron bombarding the surface of the polyolefin resin-coated paper used in the practice of the present invention include the methods described in British Patent No. 971058 and British Patent No. 1060526. Any suitable corona discharge or electron impact device (e.g., U.S. Pat. No. 2,864,755;
284756) can be used. In the present invention, a silver halide photographic constituent layer is coated on the surface of a hydrophobic polyolefin resin of a support within 30 minutes, preferably within 30 seconds, and more preferably within several seconds after the surface of the hydrophobic polyolefin resin is subjected to corona discharge treatment or electron bombardment. Advantageously, it is carried out. For example, in a preferred embodiment of the invention, a continuously running support of polyolefin resin-coated paper is passed through a first section where the polyolefin resin surface is bombarded with electrons, and then passed to a second section where A silver halide photographic constituent layer is applied to the electron impact surface. Using such a method, the time between electron bombardment and application of the silver halide photographic constituent layer is generally less than a few seconds, and depending on the operating speed, it can be carried out in a fraction of a second. The base paper mainly composed of natural pulp used in the practice of the present invention can contain various polymeric compounds and additives during the preparation of the paper stock slurry.
For example, dry paper strength enhancers such as cationized starch, cationized polyacrylamide, anionized polyacrylamide, carboxy-modified polyvinyl alcohol, gelatin, etc., and sizing agents such as fatty acid salts, rosin, rosin derivatives such as maleated rosin, alkenyl or alkyl Succinic acid and its salts or acid anhydrides, dialkyl ketene dimer emulsions, petroleum resin emulsions, etc. as fillers, clay, kaolin, calcium carbonate, barium sulfate, titanium dioxide, aluminum hydroxide, magnesium hydroxide, etc. for wet paper strength. As an agent,
Melamine resin, urea resin, epoxidized polyamide resin, etc. as a fixing agent, polyvalent metal salts such as aluminum sulfate and aluminum chloride, pH regulators such as caustic soda and soda carbonate, as well as dyes and fluorescent whitening agents as appropriate. It is advantageous to contain them in combination. Further, a commonly used paper machine such as a fourdrinier paper machine or a circular wire paper machine is used to make the base paper. The base paper mainly composed of natural pulp used in the practice of the present invention is advantageously sprayed or tab-sized or size-pressed with a liquid containing various water-soluble polymer compounds and additives. Examples of such water-soluble polymer compounds and additives include:
Water-soluble polymer compounds include cationized starch, polyvinyl alcohol, carboxy-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, gelatin, casein, etc. Sizing agents include petroleum resin emulsions, alkyl ketene dimer emulsions, and styrene-butadiene copolymers. latexes and emulsions such as polymers, ethylene-vinyl acetate copolymers, polyethylene and vinylidene chloride copolymers; hygroscopic substances such as glycerin and polyethylene glycol;
It is advantageous to use a combination of additives such as clay, kaolin, talc, barium sulfate, titanium oxide, etc. as pigments, hydrochloric acid, phosphoric acid, caustic soda, etc. as pH regulators, dyes, and fluorescent brighteners. There are no particular restrictions on the type and thickness of the base paper, which is mainly composed of natural pulp, used in the practice of the present invention, but the density of the base paper, which is compressed by applying pressure in a calendar after papermaking, is 1.0 or more. The base paper is preferably 40 g/m 2 to 250 g/m 2 in basis weight. Polyolefin resins used in the practice of the present invention include homopolymers of olefins such as low-density polyethylene, high-density polyethylene, polypropylene, polybutene, and polypentene, or copolymers of two or more olefins such as ethylene-propylene copolymers. and mixtures thereof, and those having various densities and melt viscosity indexes (hereinafter simply referred to as MI) can be used alone or in combination. The polyolefin resin used in the present invention includes white pigments such as titanium oxide, zinc oxide, talc, and calcium carbonate, fatty acid amides such as stearic acid amide and arachidic acid amide, zinc stearate, calcium stearate, aluminum stearate, and stearin. fatty acid metal salts such as magnesium acid, zirconium octylate, sodium palmitate, calcium palmitate, sodium laurate, tetrakis [methylene-3
(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] methane, 2,6-di-
Antioxidants such as tert-butyl-4-methylphenol; blue pigments and dyes such as cobalt blue, navy blue, ultramarine blue, cerulean blue, and phthalocyanine blue; magenta pigments such as cobalt violet, fast violet, and manganese violet; Dye, bis(tert-butylbenzoxazole)
Thiophene, bis(methylbenzoxazole)
It is preferable to add various additives in appropriate combinations, such as a fluorescent whitening agent such as naphthalene, and an ultraviolet absorber such as Tinuvin 320, Tinuvin 326, Tinuvin 328 (trade names of Ciba Geigy). The most suitable method for adding these additives to polyolefin resin is the melt mixing method using heated kneading rolls, Banbury mixers, kneaders, kneading extruders, etc., and each component is contained in the desired composition ratio from the beginning. A compound may be prepared and used, or a master batch containing each component at a high concentration may be prepared for each component and used by mixing them in a desired ratio. The polyolefin resin-coated paper used in the practice of the present invention is usually produced by a so-called extrusion coating method in which heated and molten polyolefin resin is cast onto a running base paper, and preferably both sides thereof are coated with polyolefin resin. Furthermore, before coating the base paper with the polyolefin resin, it is preferable to subject the base paper to an activation treatment such as a corona discharge treatment, an electronic impact treatment, or a flame treatment. The emulsion side surface of the polyolefin resin-coated paper has a glossy surface, a matte surface, a silky surface, etc. depending on the use, and the back surface is usually a matte surface. Separately from the corona discharge treatment or electron impact treatment mentioned above, an activation treatment may also be performed. The thickness of the resin layer of the polyolefin resin-coated paper is not particularly limited, but it is generally advantageous to extrude coat the paper to a thickness of about 5 to 50 microns. Silver halide photographic constituent layers used in the practice of the present invention include silver halide black and white photographic constituent layers, silver halide color photographic constituent layers, multilayer silver halide color photographic constituent layers, and silver halide photographic constituent layers for diffusion transfer method. Various types and applications such as constituent layers, direct positive silver halide photographic constituent layers, general photographic paper, typesetting photographic paper, copying photographic paper, and printing materials can be used. Further, the silver halide photographic emulsion of the silver halide photographic constituent layer used in the practice of the present invention includes:
Various types can be used. For example, silver halide compositions include silver chloride, silver bromide, silver chlorobromide,
Emulsions consisting of silver chloroiobromide, silver iodochloride, silver iodobromide, etc. or mixtures thereof, emulsions of regularly shaped grains such as cubic grains, or twin emulsions as the crystal form or crystal habit of silver halide. Emulsions consisting of irregularly shaped grains having a crystal structure or [1, 0,
Emulsions consisting of grains having 0] faces, [1, 1, 1] faces, or mixed crystal grains thereof, such as mixed crystal grains having [1, 0, 0] faces and [1, 1, 1] faces. The grain size and particle size distribution of silver halide may vary depending on the emulsion, such as fine-grained emulsions, coarse-grained emulsions, emulsions with a wide range of grain size distribution, or emulsions with a narrow range of grain size distribution such as monodisperse emulsions. For example, PH4.0 or PH
An emulsion with a silver ion concentration in the range of PAg 8.0, an emulsion with a silver ion concentration in the range of PAg 6.0 to PAg 11.0, and a binder for silver halide grains such as gelatin or a synthetic hydrophilic binder such as polyvinyl alcohol, poly- Various types of emulsions can be used, including emulsions using polymers such as N-vinylpyrrolidone and acrylic acid-acrylic ester-acrylamide copolymers. It is also possible to use negative-working silver halide photographic emulsions or, if desired, directly to positive-working silver halide photographic emulsions. Furthermore, if necessary, surface latent image type silver halide photographic emulsions in which latent images are mainly formed on the surfaces of silver halide grains, or internal latent image type silver halide photographic emulsions can also be used. Furthermore, it is possible to use emulsions in which the production, dispersion, and first thermal formation of silver halide photographic emulsions have been carried out by various methods and conditions. For example, forward mixing method, back mixing method, simultaneous mixing method (double jet method, multi-jet method),
Conversion silver halide method described in Japanese Patent Publication No. 46-7772, U.S. Patent No. 2,592,520, etc., ammonia method, acidic or neutral method, alkaline method, JP-A-48-65925
It is possible to use emulsions prepared by various methods and conditions such as the silver iodide nuclear method described in No. 1, and combinations thereof. Furthermore, emulsions containing various additives during the production and dispersion of these silver halide photographic emulsions, during or after the first thermal formation can be particularly advantageously used. For example, water-soluble rhodium compounds such as rhodium trichloride, hexahalogenorhodate,
Hexahalogenoiridium complex salts such as hexahalogenoiridium () acid salts, hexahalogenoiridium () acid salts, water-soluble iridium compounds such as iridium chloride (), iridium bromide (), gold halides, aurates, gold halides Hydrogen acid, water-soluble gold compounds such as halogenated gold hydroxides, water-soluble platinum compounds such as tetrachloroplatinate, mercapto as described or exemplified in JP-A-50-147925, JP-A-51-107129, etc. Emulsions containing heterocyclic compounds, hydroxyazaindolizine compounds described in JP-A-54-103018, water-soluble inorganic and organic metal salts such as zinc, lithium, and nickel, and appropriate combinations thereof are useful. The silver halide photographic emulsion that has undergone the first thermal formation is preferably subjected to precipitation dehydration and washed with water until desired electrical conductivity and silver ion concentration are achieved, but those that are not washed with water can also be used. These silver halide photographic emulsions are usually used after being subjected to various chemical sensitizations. These chemically sensitized emulsions include, for example, sensitized gelatin containing active sulfur compounds, thiosulfates, emulsions sensitized with sulfur using active sulfur compounds, and N/N-
Useful emulsions include seleno-sensitized emulsions using seleno compounds such as dimethylselenourea, noble metal sensitization using water-soluble noble metal compounds such as iridium, gold, and platinum, and emulsions sensitized using polyethylene oxide derivatives. be. In addition, spectral sensitization and superchromatic sensitization were performed together with chemical sensitization by using polymethine sensitizing dyes such as cyanine, merocyanine, and carbocyanine alone or in combination, or by using them in combination with styryl dye. Emulsions can advantageously be used. Further, the present invention can advantageously use silver halide color photographic emulsions. That is, it is possible to advantageously use an emulsion containing a compound (coupler) that reacts with the oxidation product of a developing agent to form a dye. Typical couplers that can be used for this purpose include bivaloylacetanilide- or benzoylacetanilide-type open-chain ketomethylene yellow couplers, pyrazolone-based magenta couplers, phenolic or naphthol-based cyan couplers, and mixtures thereof or multicolor couplers. , black couplers, etc. Depending on the structure of these couplers, development inhibitor releasing couplers (DIR couplers), -O-allyl substitution, -O-acyl substitution, hydantoin compound substitution, Examples include 2-equivalent couplers substituted with a urazole compound, a succinimide compound, a monooxoimide compound, a viridazone compound, and the like. Various types of binders or protective colloids can be used in the silver halide photographic constituent layers used in the practice of the present invention. Namely, lime-treated gelatin, acid-treated gelatin, gelatin derivatives such as phthalated gelatin and acylated gelatin, lees and their derivatives, cellulose compounds such as carboxymethylcellulose and hydroxyethylcellulose, polyvinyl alcohol, poly-N-vinylpyrrolidone, and acrylic acid. - Synthetic hydrophilic binders such as copolymers of acrylic esters, acrylic acid-acrylamide copolymers, acrylic acid-acrylic ester-acrylamide copolymers, and also as thickeners for gelatin and gelatin derivatives, e.g. cellulose, dextran; , natural or synthetic polymeric substances having hydroxyl groups such as dextrin, alginic acid, starch, and polyvinyl alcohol, preferably polymers such as polysaccharide sulfate ester compounds, styrene-maleic acid copolymers, alkyl vinyl ether-maleic acid copolymers, etc. can be used alone or in combination. It is advantageous to contain various antifoggants or stabilizers in the silver halide photographic constituent layers, particularly preferably in the silver halide photographic emulsion layers, used in the practice of the present invention. For example, U.S. Pat.
Hydroxy-azaindolizine compounds as described in JP-A-48-102621 and JP-A-51-107129, etc.;
It is advantageous to contain mercapto group-free heterocyclic compounds such as -thione heterocyclic compounds, benzimidazole, benztriazole, 1-phenyl-tetrazole, benzoxazole, guanazole compounds, etc., and combinations thereof. Further, various additives can be contained in the silver halide photographic constituent layers used in the practice of the present invention. For example, as a hardening agent, organic hardening agents such as formalin, reaction products of formaldehyde and urea or melamine, halogen carboxylic acids, vinyl sulfone compounds, aziridine compounds, epoxy compounds, active halogen compounds, acryloyl compounds, isocyanate compounds, etc. ,
Inorganic hardeners such as chromium alum and zirconium carbonate; as surfactants, anionic surfactants such as alkylbenzene sulfonates and sulfosuccinates; nonionic surfactants such as saponin and alkylene oxide compounds; amino acids; Ampholytic surfactants such as aminosulfonic acids and amino alcohol esters; benzotriazole compounds having a hydroxy-dialkyl-phenyl group at the 2-position as ultraviolet absorbers;
As a fluorescent whitening agent, Japanese Patent Publication No. 45-24068, Japanese Patent Publication No.
Compounds described or exemplified in No. 54-94318, etc.
As a sharpness-improving pigment, food red No. 2, JP-A-47
Acidic dyes such as those exemplified in No.-14721, sequestering agents such as ethylenediaminetetraacetic acid, mordants such as N-guanylhydrazone compounds, quaternary onium salt compounds, antistatic agents, cellulose antistatic agents, etc. , alkali salts of polystyrene sulfonic acid, alkali salts of polymerized acrylic acids and acrylic acid copolymers, etc. As matting agents, polymethyl methacrylate, polystyrene, methacrylic acid-methacrylate copolymers, colloidal silicon oxide, etc. A latex made of a copolymer of an acrylic ester, a methacrylic ester, etc. and another methylene group-containing monomer can be contained as a film property improving agent. Furthermore, the direct positive silver halide emulsion layer according to the present invention may contain additives for direct positive photographic emulsions such as caplace agents and sensitizing dyes for direct positive photographic emulsions. The antistatic back coat layer according to the present invention is a hydrophilic organic colloid layer containing a hydrophilic organic colloid layer, preferably an antistatic agent, on the back side of the silver halide photographic material, that is, on the support surface where no silver halide photographic constituent layer is provided. A coating layer made of an organic colloid layer is installed. Various types of hydrophilic organic colloid layers can be used in the antistatic back coat layer. For example, lime-treated gelatin, acid-treated gelatin, gelatin derivatives such as phthalated gelatin and acylated gelatin, starch and its derivatives, cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose, polyvinyl alcohol, polyacrylamide, carboxy-modified polymers thereof, Examples include poly-N-vinylpyrrolidone, agar, and sodium alginate. Furthermore, it is particularly preferable to incorporate various antistatic agents into the antistatic back coat layer according to the present invention so that the antistatic ability of the back coat layer can be more markedly exhibited. A variety of inorganic and organic antistatic agents are useful as these antistatic agents. Preferred inorganic antistatic agents include, for example, colloidal silica. Preferred organic antistatic agents include unsaturated copolymerizable monomers having 4 or more carbon atoms, such as sodium salts of styrene and maleic anhydride copolymers, and sodium salts of isobutylene and maleic anhydride copolymers, and maleic anhydride. Alkaline salts of copolymers with acids, natural or synthetic polymeric substances having hydroxyl groups such as cellulose, dextran, dextrin, alginic acid, starch, polyvinyl alcohol, preferably alkali salts of cellulose sulfate, alkali polystyrene sulfonic acids salts, sodium polyacrylates (e.g., sodium salts of polyacrylic acid, polymethacrylic acid, poly-α-ethyl acrylic acid, etc.),
Examples include alkali salts of polymerizable acrylic acids and acrylic acid copolymers, such as potassium polyacrylate and sodium salts of acrylic acid and methyl acrylate copolymers. Among these hydrophilic polymers, unsaturated copolymerizable monomers having 4 or more carbon atoms, alkali salts of maleic anhydride copolymers, alkali salts of cellulose sulfate, etc. alone can improve the hydrophilic properties of the back coat layer. Can be used as an organic colloid. The coating amount of the hydrophilic organic colloid in the antistatic back coat layer of the present invention on the back side of the resin-coated paper is preferably in the range of 0.01 g/m 2 to 10 g/m 2 .
Preferably it is in the range of 0.1 g/m 2 to 5.0 g/m 2 . Further, the coating amount of the antistatic agent that is advantageously contained in the back coat layer is 0.01 g/m 2 to 3 g/m 2 .
A range of m 2 is preferred. Furthermore, the PH of the back coat layer
is preferably 9.0 or less, preferably 7.0 or less. In addition, the back coat layer according to the present invention may contain various additives such as hardeners, surfactants, fluorescent whitening agents, matting agents, and film property improvers described on pages 32 to 33 of this specification. It is possible to contain an agent. In carrying out the present invention, a slide hopper (Slide
Usually, the coating is applied by a hopper method, an extrusion bar method, or a curtain flow method and then dried. Application methods using the slide hopper method or extrusion bar method include U.S. Patent Nos. 2761417, 2761418, and
No. 2761419, No. 2761791, Special Publication No. 48-44925
The curtain flow coating method is described in U.S. Patent No. 49-107040.
No. 3508947, Special Publication No. 14130, No. 14130, No. 14130, No. 14130
The present invention can be carried out in various ways, such as the method described in No. 69946. Further, in order to coat a multilayer silver halide photographic constituent layer, a multilayer coating hopper can be used to simultaneously coat multiple layers. The silver halide photographic material used in the present invention may be one such as described in "Photographic Light-sensitive Materials and Handling Methods" (Kyoritsu Shuppan, written by Goro Miyamoto, Photographic Technology Course 2) depending on its type, use, purpose, etc. Processes such as exposure, development, stopping, fixing, bleaching, and stabilization are performed. For example, after exposure, general purpose black and white silver halide photographic materials are usually developed by processing with a solution containing at least a silver halide developing agent and an alkaline agent, but in some cases no silver halide developing agent is used at all. Alternatively, a substantially alkaline activated liquid may be used. The developed silver image is fixed and stabilized with an acidic solution containing at least a fixing agent such as sodium thiosulfate or sodium thiocyanate. In addition, silver halide color photographic materials are usually color developed by processing in an alkaline active bath containing or substantially free of a color developing agent after exposure, and then color developed using a metal salt of an aminopolycarboxylic acid (e.g., ethylenediaminetetraacetic acid). , ferric complex salts such as propylene diamine tetraacetic acid, cupric complex salts, etc.) and a fixing agent such as thiosulfate. Such a one-bath bleach-fix solution may contain additives such as a desilvering accelerator and a fluorescent brightener. Next, in order to explain the present invention more specifically,
An example will be described. Example 1 As a blend of natural pulp, the pulp samples listed in Table 1 were prepared using Canadian Standard Freeness.
The mixture was beaten to 310 ml and paper with a weight of 160 g/m 2 was made using the following composition. (Numbers in the formulation indicate parts by weight.) Pulp 100 Cationized starch 2 Anionic polyacrylamide resin 0.5 Sodium stearate 0.5 Band sulfate Alkyl ketene dimer emulsion adjusted to PH4.5 (as ketene dimer component) 0.4 Polyamide polyamine epichlorohydrin resin
0.4 The obtained wet paper was dried on a heating plate at 110°C. This paper was impregnated with 20 g/m 2 of an impregnating solution having the following formulation and dried in a constant temperature hot air dryer at 110°C. During the formulation, salt was added in varying amounts so that the surface resistivity of the paper at a temperature of 20°C and a relative humidity of 65% would be the combinations listed in Table 1. (Numbers in the prescription indicate parts by weight.) Carboxy-modified polyvinyl alcohol 3 Diaminostilbendisulfonate type fluorescent brightener
0.05 Blue dye 0.002 Salt The impregnated and dried base paper with varying amounts of water was supercalendered at a linear pressure of 90Kg/cm, and then corona discharge treated on both sides. Next, on the back side, a 1:1 mixture of high density polyethylene (density 0.96 g/cm 2 , melt index 5) and low density polyethylene (density 0.92 g/cm 2 , melt index 5) was melted at a resin temperature of 330°C. Coating was performed using an extrusion coater to a thickness of 30μ. Next, 12% anatase titanium oxide is applied to the surface.
(Polyethylene before pigment addition has a density of 0.92 g/cm 2 and a melt index of 5) was coated to a thickness of 30 μm at a resin temperature of 330° C. The back side of the polyethylene-coated paper thus created (the polyethylene side that does not contain titanium oxide)
After corona discharge treatment, the following back coat solution was applied and dried. In 60 g of a 5% aqueous solution of styrene-maleic anhydride copolymer (trade name: Maron MS, manufactured by Daido Kogyo Co., Ltd.),
Add 10 g of a 20% aqueous solution of colloidal silica (trade name Snotex, manufactured by Nissan Chemical Co., Ltd.) and 10 g of a 10% aqueous solution of sodium dodecylbenzenesulfonate, and then add a compound represented by the following formula [] Add 10 g of a 5% methanol solution of Then, adjust the pH of this liquid to 5.5 using a pH regulator, and adjust the total volume to 100.
Adjust by adding water to g. Apply this liquid in an amount of 30g/
m 2 (moisture) to the back side of polyethylene-coated paper. Then, within a few seconds of corona discharge treatment on the surface of the polyethylene containing titanium oxide, and after corona discharge treatment and storage for 4 days, a multilayer silver halide color photographic constituent layer was placed closest to the polyethylene surface of the support with blue-sensitive silver halide. A multilayer coating hopper is placed so that a photographic emulsion layer and its protective layer are located, a green-sensitive silver halide photographic emulsion layer and an ultraviolet absorbing layer are located on top of the green-sensitive silver halide photographic emulsion layer, and a red-sensitive silver halide photographic emulsion layer and its protective layer are located on top of that. Six layers were applied simultaneously and dried. In this case, the blue-sensitive silver halide photographic emulsion layer contains
Using a sulfur-sensitized all-ammonia method silver halide photographic emulsion with a halogen composition of AgBr/Agcl = 95/5 and an average grain size of 0.8μ, the blue sensitivity is expressed by the formula below with silver nitrate amount per 9.6 minutes. Sensitizing dye [] Optically sensitized at 9.6 mg, the yellow coupler is a coupler shown by the following formula [] was dispersed in dibutyl phthalate, and an appropriate amount of antifoggant was used to dissolve 1.7 g of gelatin/gelatin.
m 2 , 0.38 g/m 2 of silver, and 0.5 g/m 2 of coupler. The protective layer of the blue-sensitive emulsion layer contains 2,5-di-
Using tert-octylhydroquinone (hereinafter abbreviated as HQ) dispersed in dibutyl phthalate,
It was applied at a ratio of 1.2 g/m 2 of gelatin and 0.04 g/m 2 of HQ. In addition, the green-sensitive silver halide photographic emulsion layer was produced by producing and dispersing silver halide grains in the presence of 3 x 10 -6 g of potassium hexachlorodate() per 9.6 g of silver nitrate. AgBr／Agcl＝
Average particle size 0.4 with a halogen composition of 95/5
Sulfur sensitized to an optimal sensitivity of μ substantially [1,0,
Using an acid method silver halide photographic emulsion consisting of 0] planes, a green sensitizing dye represented by the following formula per 9.6 g of silver nitrate [] A coupler optically sensitized at 9.6mg and represented by the following formula as a magenta coupler [] was dispersed in dibutyl phthalate together with HQ, and appropriate amounts of antifoggant and sharpness improving dye were used, gelatin 1.7g/m 2 , silver 0.38g/m 2 , coupler 0.5g/m 2 , HQ0. It was applied at a rate of 0.015 g/m 2 . The ultraviolet absorbing layer contains an ultraviolet absorber represented by the following formula [] Dispersed in dinormalnonyl phthalate, gelatin 1.4g/m 2 , ultraviolet absorber 0.4g/m 2
It was applied at the rate of In addition, the red-sensitive silver halide photographic emulsion layer has a green-sensitive emulsion layer except that silver halide grains are generated and dispersed in the presence of potassium hexachloroiridate() in an amount of 3 x 10 -4 g per 9.6 g of silver nitrate. Using a silver halide photographic emulsion produced in the same manner as the emulsion, the red-sensitizing dye represented by the following formula per 9.6 g of silver nitrate [] A coupler optically sensitized with 0.96mg and represented by the following formula as a cyan coupler [] was dispersed in dibutyl phthalate along with HQ, and appropriate amounts of antifoggant and sharpness improving dye were used, gelatin 1.5g/m 2 , silver 0.38g/m 2 , coupler 0.3g/m 2 , HQ0. It was applied at a rate of 0.015 g/m 2 . The protective layer of the red-sensitive emulsion layer was coated with gelatin at a rate of 1.2 g/m 2 . Furthermore, appropriate amounts of a hardening agent and a sodium salt of sulfosuccinate were used as a surfactant in each of the photographic constituent layers. In that case, the hardening agent is a compound represented by the following formula [] was used in an amount of 1.7% by weight based on gelatin. In addition, the blue-sensitive silver halide photographic emulsion and its protective solution, the green-sensitive silver halide photographic emulsion and the coating solution for the ultraviolet absorption layer,
The viscosity of each was adjusted to be in the range of 25 centipoise to 30 centipoise. The red-sensitive silver halide photographic emulsion and its protective liquid each have a viscosity of 30
It was adjusted to be in the range of centipoise to 35 centipoise. At that time, add an appropriate amount of KELCO SCS as a gelatin thickener if necessary.
MV (manufactured by KELKO, New Jersey, USA) was used. The multilayer silver halide color photographic material obtained by coating and drying in this manner consists of a blue-sensitive emulsion layer, a blue-sensitive emulsion layer, adjacent to a polyethylene-coated paper serving as a support, and a blue-sensitive emulsion layer,
A green-sensitive emulsion layer and a red-sensitive emulsion layer are arranged in this order. Each sample was evaluated by the method described below. At that time, the hardness of the silver halide photographic constituent layer is evaluated using numerical values, and the evaluation criteria for coating unevenness and adhesion to the support of the silver halide photographic constituent layer is marked ◎ (extremely good), 〇 mark (good), △
(slightly good) and x (poor). [Evaluation of corona coating unevenness of silver halide photographic constituent layers] After storing the coated samples at 35°C and under normal humidity for 2 days, each sample was exposed to an appropriate amount of green light, and then exposed to a diluted D-72 developer for 20 minutes. After developing for 90 seconds at ℃, stop, fix,
Wash with water and dry. After that, observe the development coated surface,
Visually judge the unevenness of corona application. [Evaluation of adhesion of silver halide photographic constituent layer to support] After immersion in the following color developing solution at 33°C for 3 minutes and 30 seconds,
Make a cross-shaped scratch on the silver halide photographic constituent layer and rub the scratched area with your fingertips to check for peeling. (Color developer) Sodium carbonate (monohydrate) 46.0g Anhydrous sodium sulfite 2.0g Potassium bromide 0.5g CD- 4.5g Sodium hexametaphosphate 0.5g Hydroxylamine hydrochloride 2.0g Fluorescent brightener 0.5g Benzyl alcohol 12 cc Diethylene glycol Adjust the total volume to 1 with 10 cc water, and adjust the pH to 1 with sodium hydroxide.
Adjust to 10.2. [Evaluation of hardness of silver halide photographic constituent layers] After storing the coated sample at 35°C for 2 days, it was immersed in pure water at 33°C for 3 minutes to measure the amount of liquid absorbed. We investigated the relationship between quantities. When the water content in the base paper is the same, the smaller the amount of liquid absorbed, the stronger the hardness. The results obtained are shown in Table 1. The moisture content in the base paper was 13.6±0.1 (g/m 2 ), which was substantially uniform for each sample.
【表】
第１表からわかるようにコロナ後直に乳剤塗布
しない場合（No.1）にはポリエチレンに対する
乳剤層の接着が弱く使用にも堪えない。基紙に用
いるパルプの光散乱係数が400cm2/ｇ未満の場合
（No.7、No.8）光散乱係数400cm2/ｇ以上のパルプ
使用量が40％未満の場合（No.13）はコロナ塗布
ムラが著しい。それに対して本発明を実施した場
合、塗布ムラは少なくともやゝ良好の範囲に入
る。特許請求の範囲第二項に従い基紙の表面固有
抵抗を高くして、本発明を実施すると接着力は非
常に良好となり、塗布ムラもいつそう良好とな
る。また、硬膜度は飛躍的に向上する。以上から
本発明を実施すると良好な塗布が可能となり、さ
らに第二項を実施すると非常に有利であることが
わかる。
実施例 ２
実施例１で調製したポリエチレン被覆紙の表面
をコロナ放電処理した後数秒以内に白黒ハロゲン
化銀写真乳剤層とその保護層を２層塗布用ホツパ
ーから同時に塗布乾燥し、白黒ハロゲン化銀写真
材料を作成した。
この場合、白黒ハロゲン化銀写真乳剤層には、
硝酸銀量で9.6ｇ当り３×10-6ｇのヘキサクロロ
ロジウム（）酸カリウムの存在下にハロゲン化
銀粒子を生成・分散して製造したAgBr／Agcl＝
45／55なるハロゲン組成を有する平均粒子径0.6
μの最適感度に硫黄増感した実質的に〔１、０、
０〕面から成る中性法ハロゲン化銀写真乳剤を用
い、硝酸銀量で9.6ｇ分当り下式で示される増感
色素〔〕
3.2mgで光学増感し、更に適当量のカブリ防止
剤、螢光増白剤を用い、ゼラチン６ｇ/m2、銀1.5
ｇ/m2の割合で塗布した。また、保護層はゼラチ
ン３ｇ/m2の割合で塗布した。更に、各写真構成
層には、それぞれ適当量の硬膜剤と界面活性剤と
してドデシルベンゼンスルホン酸ナトリウムを用
いた。その場合、硬膜剤として12％ホルマリン水
溶液を対ゼラチン当り33重量％用いた。
このようにして得られた白黒ハロゲン化銀写真
材料を35℃、常湿下に２日間保存後、適当量の白
光露光を与え、以下実施例１とまつたく同様にし
てコロナ塗布ムラの検定を行つた。
その結果、本発明におけるポリエチレン被覆紙
上に塗設されハロゲン化銀写真乳剤層には、コロ
ナ塗布ムラはほとんど認められなかつたが、本発
明外のポリエチレン被覆紙に塗設された場合には
明らかにコロナ塗布ムラが認められ、本発明の有
用性がよく理解される。[Table] As can be seen from Table 1, if the emulsion is not applied immediately after corona (No. 1), the adhesion of the emulsion layer to polyethylene is weak and it is unusable. When the light scattering coefficient of the pulp used for the base paper is less than 400 cm 2 /g (No. 7, No. 8) When the amount of pulp used with a light scattering coefficient of 400 cm 2 / g or more is less than 40% (No. 13) Significant unevenness in corona application. On the other hand, when the present invention is implemented, the coating unevenness is at least within a somewhat good range. If the present invention is carried out by increasing the surface resistivity of the base paper according to claim 2, the adhesive strength will be very good and the coating unevenness will be much better. Furthermore, the degree of hardness is dramatically improved. From the above, it can be seen that implementing the present invention enables good coating, and that implementing the second item is very advantageous. Example 2 Within a few seconds after the surface of the polyethylene-coated paper prepared in Example 1 was subjected to corona discharge treatment, a black-and-white silver halide photographic emulsion layer and its protective layer were simultaneously coated from a two-layer coating hopper and dried. Created photographic materials. In this case, the black and white silver halide photographic emulsion layer includes:
AgBr/Agcl produced by producing and dispersing silver halide particles in the presence of potassium hexachlororhodate() at 3 x 10 -6 g per 9.6 g of silver nitrate =
Average particle size 0.6 with a halogen composition of 45/55
Sulfur sensitized to an optimal sensitivity of μ substantially [1,0,
Using a neutral method silver halide photographic emulsion consisting of 0] planes, a sensitizing dye represented by the following formula per 9.6 g of silver nitrate [] Optically sensitized with 3.2 mg, further using appropriate amounts of antifoggant and fluorescent brightener, gelatin 6 g/m 2 and silver 1.5
It was applied at a rate of g/m 2 . The protective layer was coated with gelatin at a rate of 3 g/m 2 . Further, appropriate amounts of a hardening agent and sodium dodecylbenzenesulfonate were used as a surfactant in each of the photographic constituent layers. In that case, a 12% aqueous formalin solution was used as a hardening agent at 33% by weight based on gelatin. After storing the black-and-white silver halide photographic material thus obtained at 35°C and under normal humidity for two days, it was exposed to an appropriate amount of white light, and then the corona coating unevenness was examined in the same manner as in Example 1. I went. As a result, almost no corona coating unevenness was observed in the silver halide photographic emulsion layer coated on the polyethylene-coated paper according to the present invention, but it was clearly observed when coated on the polyethylene-coated paper other than the present invention. Unevenness in corona application was observed, and the usefulness of the present invention is clearly understood.
Claims (1)
リオレフイン樹脂で被覆したポリオレフイン樹脂
被覆紙を支持体として有し、該支持体上にハロゲ
ン化銀写真構成層を設けたハロゲン化銀写真材料
の製造に際し、天然パルプとして光散乱係数が
400cm2/ｇ以上の天然パルプを全使用パルプ当り乾
燥重量で40％以上用い、かつ支持体のポリオレフ
イン樹脂面上に電子衝撃を施した後30分以内にハ
ロゲン化銀写真構成層を塗設することを特徴とす
るハロゲン化銀写真材料の製造方法。 ２ 基質たる紙が、温度20℃、相対湿度65％にお
いて6.3×108Ω以上の表面固有抵抗を有するもの
である特許請求の範囲第１項記載のハロゲン化銀
写真材料の製造方法。 ３ ハロゲン化銀写真構成層が、少なくとも２つ
以上のハロゲン化銀写真乳剤層から成る多層ハロ
ゲン化銀写真構成層であつて、かつ該多層ハロゲ
ン化銀写真構成層を多層塗布用ホツパーから同時
に塗設するものである特許請求の範囲第１項又は
第２項記載のハロゲン化銀写真材料の製造方法。[Scope of Claims] 1. A halogenated paper having a polyolefin resin-coated paper coated with a polyolefin resin as a support using paper mainly composed of natural pulp as a substrate, and a silver halide photographic constituent layer provided on the support. When producing silver photographic materials, the light scattering coefficient is
Natural pulp of 400 cm 2 /g or more is used in an amount of 40% or more by dry weight based on the total pulp used, and a silver halide photographic constituent layer is applied within 30 minutes after electron impact is applied to the polyolefin resin surface of the support. A method for producing a silver halide photographic material, characterized in that: 2. The method for producing a silver halide photographic material according to claim 1, wherein the substrate paper has a surface resistivity of 6.3×10 8 Ω or more at a temperature of 20° C. and a relative humidity of 65%. 3. The silver halide photographic constituent layer is a multilayer silver halide photographic constituent layer consisting of at least two or more silver halide photographic emulsion layers, and the multilayer silver halide photographic constituent layers are simultaneously coated from a multilayer coating hopper. A method for producing a silver halide photographic material according to claim 1 or 2, which comprises:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12710381A JPS5828740A (en) | 1981-08-13 | 1981-08-13 | Manufacture of photographic sensitive silver halide material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12710381A JPS5828740A (en) | 1981-08-13 | 1981-08-13 | Manufacture of photographic sensitive silver halide material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5828740A JPS5828740A (en) | 1983-02-19 |
| JPS6130254B2 true JPS6130254B2 (en) | 1986-07-12 |
Family
ID=14951667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12710381A Granted JPS5828740A (en) | 1981-08-13 | 1981-08-13 | Manufacture of photographic sensitive silver halide material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5828740A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0332420U (en) * | 1989-08-07 | 1991-03-29 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6182451A (en) * | 1984-09-29 | 1986-04-26 | Fujitsu Autom Kk | Lead bending method of ic package |
| US5340616A (en) * | 1990-08-09 | 1994-08-23 | Fuji Photo Film., Ltd. | A coating method using an electrified web and increased humidity |
| JP2012016704A (en) * | 2011-09-16 | 2012-01-26 | Dow Global Technologies Llc | Method of manufacturing coated paper or cardboard |
-
1981
- 1981-08-13 JP JP12710381A patent/JPS5828740A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0332420U (en) * | 1989-08-07 | 1991-03-29 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5828740A (en) | 1983-02-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4410619A (en) | Photographic material | |
| US6190781B1 (en) | Support for imaging material | |
| US4419433A (en) | Photographic material | |
| JP2892833B2 (en) | Manufacturing method of photographic paper support | |
| JPS6130254B2 (en) | ||
| JPS62215950A (en) | Photographic sensitive material | |
| JPH0610736B2 (en) | Silver halide photographic paper | |
| JPH07234476A (en) | Photogrpahic substrate and photographic material | |
| JPH037092B2 (en) | ||
| JPS5843733B2 (en) | photographic support | |
| JP2914458B2 (en) | Photographic support | |
| JPH05273698A (en) | Photographic base | |
| JP2907601B2 (en) | Support for photosensitive material | |
| JPH07181625A (en) | Photographic printing paper capable of fixing toner | |
| JPS5828741A (en) | Photographic material | |
| JPH0234014B2 (en) | SHASHINZ AIRYO | |
| JP3573870B2 (en) | Photo material | |
| JP3343834B2 (en) | Support for imaging materials | |
| JPH027448B2 (en) | ||
| JPH01191850A (en) | Silver halide color photographic sensitive material | |
| JP3255991B2 (en) | Photographic support | |
| JP2972405B2 (en) | Photographic support | |
| JPS59166950A (en) | Photographic material | |
| JPS5843731B2 (en) | Method for manufacturing photographic supports | |
| JP3053134B2 (en) | Photographic support |