JPH04342250A - Base for photosensitive material - Google Patents
Base for photosensitive materialInfo
- Publication number
- JPH04342250A JPH04342250A JP14246291A JP14246291A JPH04342250A JP H04342250 A JPH04342250 A JP H04342250A JP 14246291 A JP14246291 A JP 14246291A JP 14246291 A JP14246291 A JP 14246291A JP H04342250 A JPH04342250 A JP H04342250A
- Authority
- JP
- Japan
- Prior art keywords
- pulp
- natural
- silver
- resin
- support
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 60
- 239000002655 kraft paper Substances 0.000 claims abstract description 81
- 239000000123 paper Substances 0.000 claims abstract description 81
- 229920005989 resin Polymers 0.000 claims abstract description 59
- 239000011347 resin Substances 0.000 claims abstract description 59
- 229910052709 silver Inorganic materials 0.000 claims abstract description 59
- 239000004332 silver Substances 0.000 claims abstract description 59
- 238000011282 treatment Methods 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 57
- 238000002845 discoloration Methods 0.000 claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000001301 oxygen Substances 0.000 claims abstract description 39
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 39
- 238000004061 bleaching Methods 0.000 claims abstract description 36
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 14
- 239000006260 foam Substances 0.000 claims abstract description 12
- 210000000988 bone and bone Anatomy 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- 229920005672 polyolefin resin Polymers 0.000 claims description 9
- 239000002480 mineral oil Substances 0.000 claims description 6
- 235000010446 mineral oil Nutrition 0.000 claims description 6
- 229920013716 polyethylene resin Polymers 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 2
- 239000004033 plastic Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- -1 silver halide Chemical class 0.000 abstract description 49
- 239000011248 coating agent Substances 0.000 abstract description 17
- 238000000576 coating method Methods 0.000 abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- 239000010410 layer Substances 0.000 description 40
- 239000002585 base Substances 0.000 description 31
- 239000002023 wood Substances 0.000 description 30
- 230000008569 process Effects 0.000 description 18
- 238000010411 cooking Methods 0.000 description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 235000011121 sodium hydroxide Nutrition 0.000 description 15
- 108010010803 Gelatin Proteins 0.000 description 14
- 229920000159 gelatin Polymers 0.000 description 14
- 239000008273 gelatin Substances 0.000 description 14
- 235000019322 gelatine Nutrition 0.000 description 14
- 235000011852 gelatine desserts Nutrition 0.000 description 14
- 239000002562 thickening agent Substances 0.000 description 14
- 239000000839 emulsion Substances 0.000 description 13
- 239000011121 hardwood Substances 0.000 description 13
- 239000000049 pigment Substances 0.000 description 12
- 239000000975 dye Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000000654 additive Substances 0.000 description 10
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 238000003851 corona treatment Methods 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000004848 polyfunctional curative Substances 0.000 description 7
- 239000004408 titanium dioxide Substances 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000000920 calcium hydroxide Substances 0.000 description 6
- 235000011116 calcium hydroxide Nutrition 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000011241 protective layer Substances 0.000 description 6
- 230000035945 sensitivity Effects 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000004155 Chlorine dioxide Substances 0.000 description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 5
- 239000002216 antistatic agent Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 5
- 235000019398 chlorine dioxide Nutrition 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000007765 extrusion coating Methods 0.000 description 5
- 150000004665 fatty acids Chemical class 0.000 description 5
- 229920001684 low density polyethylene Polymers 0.000 description 5
- 239000004702 low-density polyethylene Substances 0.000 description 5
- 150000002978 peroxides Chemical class 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 235000010216 calcium carbonate Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000003112 inhibitor Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 230000001235 sensitizing effect Effects 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 239000011122 softwood Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 206010070834 Sensitisation Diseases 0.000 description 3
- 238000001994 activation Methods 0.000 description 3
- 230000003254 anti-foaming effect Effects 0.000 description 3
- 238000010009 beating Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920002401 polyacrylamide Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000013055 pulp slurry Substances 0.000 description 3
- 230000008313 sensitization Effects 0.000 description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 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 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001045 blue dye Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 229920006319 cationized starch Polymers 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003623 enhancer Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 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
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- CMCWWLVWPDLCRM-UHFFFAOYSA-N phenidone Chemical compound N1C(=O)CCN1C1=CC=CC=C1 CMCWWLVWPDLCRM-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 229920002545 silicone oil Polymers 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- NRUVOKMCGYWODZ-UHFFFAOYSA-N sulfanylidenepalladium Chemical group [Pd]=S NRUVOKMCGYWODZ-UHFFFAOYSA-N 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 239000004094 surface-active agent Substances 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229920003169 water-soluble polymer Polymers 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- OMDQUFIYNPYJFM-XKDAHURESA-N (2r,3r,4s,5r,6s)-2-(hydroxymethyl)-6-[[(2r,3s,4r,5s,6r)-4,5,6-trihydroxy-3-[(2s,3s,4s,5s,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxyoxan-2-yl]methoxy]oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)O)[C@H](O)[C@H](O)[C@H](O)O1 OMDQUFIYNPYJFM-XKDAHURESA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- ODPJQZNJZWLTJH-UHFFFAOYSA-N 2,3-dihydrotriazolo[4,5-d]pyrimidin-5-one Chemical class O=C1N=CC2=NNNC2=N1 ODPJQZNJZWLTJH-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
- MKALOVJHPRAZRE-UHFFFAOYSA-N 5-phenylpenta-2,4-dienoic acid;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=CC=CC1=CC=CC=C1 MKALOVJHPRAZRE-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
- 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 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- 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 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229920000926 Galactomannan Polymers 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- FYJWGDNXYRXGSR-VHUAPCKSSA-N OC(=O)C=C.OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 Chemical compound OC(=O)C=C.OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 FYJWGDNXYRXGSR-VHUAPCKSSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 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 1
- 241000872198 Serjania polyphylla Species 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
- 229920002472 Starch Polymers 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 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
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 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
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000007864 aqueous solution 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
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 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
- 229940078456 calcium stearate Drugs 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
- 238000003490 calendering Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- HDFRDWFLWVCOGP-UHFFFAOYSA-N carbonothioic O,S-acid Chemical class OC(S)=O HDFRDWFLWVCOGP-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012459 cleaning agent 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
- 239000013065 commercial product Substances 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
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000000586 desensitisation Methods 0.000 description 1
- WASQWSOJHCZDFK-UHFFFAOYSA-N diketene Chemical compound C=C1CC(=O)O1 WASQWSOJHCZDFK-UHFFFAOYSA-N 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-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
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001227 electron beam curing Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- OOCSVLHOTKHEFZ-UHFFFAOYSA-N icosanamide Chemical compound CCCCCCCCCCCCCCCCCCCC(N)=O OOCSVLHOTKHEFZ-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 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
- 229920005610 lignin Polymers 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate 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
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- 229940057948 magnesium stearate Drugs 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012528 membrane Substances 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- NPDFXFLCEDDWEG-UHFFFAOYSA-N n-[2-(4-amino-n-ethyl-3-methylanilino)ethyl]methanesulfonamide;sulfuric acid Chemical compound OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O.CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1.CS(=O)(=O)NCCN(CC)C1=CC=C(N)C(C)=C1 NPDFXFLCEDDWEG-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000006174 pH buffer Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 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
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 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
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000009895 reductive bleaching Methods 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical class [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 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 1
- NZKWZUOYGAKOQC-UHFFFAOYSA-H tripotassium;hexachloroiridium(3-) Chemical group [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[K+].[K+].[K+].[Ir+3] NZKWZUOYGAKOQC-UHFFFAOYSA-H 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229940105125 zinc myristate Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229940012185 zinc palmitate Drugs 0.000 description 1
- 229940057977 zinc stearate Drugs 0.000 description 1
- GJAPSKMAVXDBIU-UHFFFAOYSA-L zinc;hexadecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GJAPSKMAVXDBIU-UHFFFAOYSA-L 0.000 description 1
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Paper (AREA)
Abstract
Description
【発明の詳細な説明】
【0001】
【産業上の利用分野】本発明は天然パルプを主成分とす
る紙基体(以下基紙と言う)をフィルム形成能ある樹脂
、好ましくはポリオレフィン樹脂で被覆した樹脂被覆紙
型感光材料用支持体に関するものであり、詳しくはハロ
ゲン化銀感光層に対する写真適性が良好な樹脂被覆紙型
感光材料用支持体に関するものである。
【0002】
【従来の技術】感光材料用支持体として、基体の少なく
とも一方の面がフィルム形成能ある樹脂で被覆された樹
脂被覆紙型感光材料用支持体はよく知られている。例え
ば、特公昭55−12584号には、基紙がフィルム形
成能ある樹脂、好ましくはポリオレフィン樹脂で被覆さ
れた感光材料用支持体についての技術が開示されている
。米国特許第3,501,298 号には基紙の両面が
ポリオレフィン樹脂で被覆された感光材料用支持体につ
いての技術が開示されている。また、ハロゲン化銀写真
感光材料の迅速写真現像処理方式が適用されて以来、基
紙の両面がポリエチレン系樹脂で被覆された感光材料用
支持体が、写真印画紙用として主に実用されており、必
要に応じてその一方の画像形成側の樹脂層中には鮮鋭度
を付与するために、通常二酸化チタン顔料を含有してい
る。
【0003】しかしながら、天然パルプを主成分とする
基紙をフィルム形成能ある樹脂で被覆した樹脂被覆紙型
感光材料用支持体は、依然としてハロゲン化銀感光層に
対する写真適性の点である種の重大な問題点を有してい
た。
【0004】即ち、天然パルプを主成分とする基紙をフ
ィルム形成能ある樹脂で被覆した樹脂被覆紙を支持体と
するハロゲン化銀感光材料をその製造後保存した場合、
保存が長期にわたるに従い、特に高温、高湿のもとに保
存した場合、該感光材料のハロゲン化銀が斑点状にカブ
らされてしまい、未露光部が現像処理中に斑点状に現像
可能となったり、該感光材料の感度が斑点状に低下した
り、増加したりしてしまうという問題点があった。例え
ば、該樹脂被覆紙を支持体とする、ある型のポジ用白黒
ハロゲン化銀印画紙の場合には、白地に斑点状にカブリ
が生成することである。この斑点状カブリは、時には直
径20数mmにも達することがあり、印画紙は全く商品
価値の無いものになってしまう。また、ハロゲン化銀ネ
ガ感光層の支持体として該樹脂被覆紙を有する、銀塩拡
散転写方式のある型の感光材料の場合には、ネガ側のハ
ロゲン化銀感光層で斑点状にカブリが生成するため、ポ
ジ側の画像濃度が斑点状に低下したり、銀画像が斑点状
にほとんど形成されなくなり、全く商品価値が無くなっ
てしまう。また、該樹脂被覆紙を支持体として、支持体
に隣接してイエロー発色層、マゼンタ発色層およびシア
ン発色層を順に配置した、ある型の多層ハロゲン化銀カ
ラー印画紙の場合には、斑点状カブリが発生すると共に
、特にイエロー及びマゼンタ発色層が斑点状に感度低下
を起し、斑点状に画像のカラーバランスがくずれ印画紙
の商品価値がなくなってしまう等の問題点があった。以
下、これらの現象を総称して斑点故障と称することにす
る。
【0005】これまでに、ハロゲン化銀感光材料の保存
時の写真特性の変化を防止するための種々の安定剤もし
くはカブリ抑制剤が提案されている。しかしながら、樹
脂被覆紙を支持体とするハロゲン化銀感光材料の構成層
中に、種々の安定剤もしくはカブリ抑制剤を含有させて
も、感度の低下、調子の軟調化等の少なからぬ写真的悪
影響をもたらすだけでなく、斑点故障をほとんど防止す
ることが出来なかった。
【0006】また、感光材料用支持体の写真性に関する
いくつかの提案がある。特公昭54−9844 号には
、ヒドキシ−置換−トリアゾロピリミジン化合物を含有
させたポリオレフィン樹脂で基紙を被覆した、カブリ防
止性の樹脂被覆紙型感光材料用支持体が提案されている
が、該支持体を有するハロゲン化銀感光材料の斑点故障
を防止することについては極めて不十分であった。また
、写真用紙に関して、特開昭52−65423号及び特
公昭58−43730号にそれぞれカチオン性電解質お
よび紙用添加薬品の分解による写真性への悪影響を除去
することが提案されているが、これらの写真用紙から成
る樹脂被覆紙を支持体とするハロゲン化銀感光材料では
、斑点故障は全く防止出来ず、斑点故障は、これらの明
細書に記載されている機構とは全く別の機構によって発
生する事が明らかとなった。また、特開平2−9674
1 号、特開平2−99689 号及び特開平2−99
693 号に、未晒クラフト紙の写真性を改良する技術
が提案されている。それらによれば、晒クラフト紙の写
真性は良好であるが、未晒クラフト紙の写真性は悪く、
その原因として未晒段階で用いられる消泡剤成分である
酸化プロピレンあるいは/およびシリコンが残留するた
めであり、それらの成分を含む消泡剤と冷水抽出pHを
特定化することにより未晒クラフト紙の写真性を改良す
ることが提案されている。しかしながら、該技術を応用
した晒天然パルプを主成分とする基紙から成る樹脂被覆
紙を支持体とするハロゲン化銀感光材料では、やはり斑
点故障は全く防止出来ず、斑点故障は、これらの明細書
に記載されている機構とは全く別の機構によって発生す
ることが明かとなった。更に、特公昭58−43732
号に、アルカリ性で過酸化物を用いて漂白処理された天
然パルプを主成分とする基紙から成る樹脂被覆紙により
、ハロゲン化銀写真材料の保存性を改良する技術につい
て提案されているが、該樹脂被覆紙を用いても斑点故障
を防止することは不十分であった。また更に、特公昭5
9−38575号に、酸素パルプ化法で得られた木材パ
ルプを用いた写真用紙により、ハロゲン化銀写真材料の
カブリやスポットを防止する技術について提案されてい
るが、該写真用紙を基質とする樹脂被覆紙を用いても斑
点故障を防止することは依然として不十分であった。
【0007】以上のように、天然パルプを主成分とする
基紙をフィルム形成能ある樹脂で被覆した樹脂被覆紙を
支持体とするハロゲン化銀感光材料の斑点故障を改良す
る技術および斑点故障の発生機構もしくは発生原因は、
全く知られていないし、また従来公知の技術を用いて斑
点故障を改良することは全く出来なかった。
【0008】
【発明が解決しようとする課題】従って、本発明の目的
は、ハロゲン化銀感光層に対して斑点故障の発生傾向が
顕著に抑制された、天然パルプを主成分とする基紙をフ
ィルム形成能ある樹脂で被覆した感光材料用支持体を提
供することである。本発明のその他の目的は、以下の明
細書の記載から明かとなろう。
【0009】
【課題を解決するための手段および作用】本発明者らが
前述の問題点を解決するために、鋭意検討の結果、天然
パルプを主成分とする基紙をフィルム形成能ある樹脂で
被覆した感光材料用支持体において該基紙を構成する天
然パルプの一部または全部が天然クラフトパルプであり
、該天然クラフトパルプとして、クラフト法による蒸解
後その未晒段階で消泡剤あるいは抑泡剤の存在下に洗浄
処理され、かつ洗浄処理に前後して酸素脱リグニン処理
され、その後の漂白段階で漂白処理されたものであり、
なおかつ該天然クラフトパルプの本明細書で定義される
銀変色反応による変色発生個数がA−4当り20個以下
である天然クラフトパルプを使用することによって、本
発明の目的が達成される事が判明した。本明細書で言う
銀変色反応による変色発生個数とは、Tappi スタ
ンダードT444に基づいて調製された銀面板の銀面に
天然クラフトパルプ試料(試料条件としては、坪量;7
50g/m2±150g/m2,絶乾水分量;20重量
%±5重量%,pH;Tappi スタンダードT20
5に基づいて調製された時のパルプ懸濁液のpHとして
6.0〜7.5である)を密着させて、黒ポリ袋に封入
し、A−4当り2.5kgの荷重をかけて、温度50℃
±1℃、相対湿度81%±2%の条件下で50時間加温
処理を行い、その後銀面上の銀変色反応の発生個数を計
測したものである。
【0010】本発明者らの検討によれば、天然クラフト
パルプを蒸解後その未晒段階で消泡剤あるいは抑泡剤の
存在下に洗浄処理すると、黒液成分あるいは黒液変性成
分に起因する水不溶性または水難溶性の銀変色反応発生
物質が、消泡剤あるいは抑泡剤の作用により吸蔵され、
かつ局在的に残留し、驚くべきことに該銀変色反応発生
物質は、その後の漂白段階での酸化剤あるいはアルカリ
剤の攻撃にも耐えて晒天然クラフトパルプ中に残留し、
しかも更に該晒天然クラフトパルプを叩解、抄紙した基
紙にも局在的に残留し、そして該銀変色反応発生物質が
斑点故障を発生せしめることをつきとめ、更にクラフト
法による蒸解後その未晒段階で消泡剤あるいは抑泡剤の
存在下に洗浄処理され、かつ洗浄処理に前後して酸素脱
リグニン処理され、その後の漂白段階で漂白処理された
ものであり、なおかつ銀変色反応発生物質の少ない天然
クラフトパルプを使用することにより斑点故障を改良出
来る事をつきとめ本願発明に到ったものである。
【0011】本発明の実施に用いられる天然クラフトパ
ルプとしては、針葉樹クラフトパルプ、広葉樹クラフト
パルプ、針葉樹広葉樹混合クラフトパルプの木材クラフ
トパルプが有利に用いられる。それらの木材クラフトパ
ルプとしては、木材チップが水酸化ナトリウムと硫化ナ
トリウムを化学成分として含む混液、いわゆる蒸解液で
加圧蒸煮、いわゆる蒸解されて、リグニンが除去され、
その後消泡剤あるいは抑泡剤の存在下にパルプ繊維と蒸
解残液、いわゆる黒液とに分離洗浄された後酸素脱リグ
ニン処理され、その後漂白処理されて製造されたものが
有利に用いられる。蒸解液中の化学成分として、水酸化
ナトリウム、硫化ナトリウムの他に、更に炭酸ナトリウ
ム、硫酸ナトリウム、消石灰、炭酸カルシウムなどの塩
類、水素化ホウ素ナトリウム、アントラキノン化合物な
どの蒸解助剤などを含有していてもよい。また、ポリサ
ルファイド蒸解、バッチ式蒸解、連続式蒸解など各種の
蒸解方式で製造されたものでもよく、各種の硫化度、カ
ッパー価で製造されたものでもよい。
【0012】本発明の実施に用いられる基紙は、天然パ
ルプを主成分として、その一部または全部が天然クラフ
トパルプ、好ましくは木材クラフトパルプで構成された
ものであるが、天然クラフトパルプに併用して必要に応
じて天然クラフトパルプ以外の天然パルプ、合成繊維も
しくは合成パルプで構成されたものでもよい。天然クラ
フトパルプと併用されるパルプとしては、天然パルプが
好ましく、針葉樹サルファイトパルプ、広葉樹サルファ
イトパルプ、針葉樹広葉樹混合サルファイトパルプの木
材サルファイトパルプが特に好ましい。また、木材ソー
ダパルプ、木材溶解パルプなどを用いることもできる。
【0013】本発明の実施に用いられる消泡剤あるいは
抑泡剤としては各種のものを使用出来る。例えば、特開
昭54−59404号、特開昭58−220896 号
、特開昭61−245391 号、特開昭61−245
319 号、米国特許第3,923,638 号、米国
特許第4,107,073 号等に記載もしくは例示の
高級脂肪酸アルコールエステル化合物、鉱物油もしくは
液状炭化水素油、シリコーン油などを成分とするものを
使用することができる。それらの中で、特に消泡性また
は抑泡性の点で鉱物油もしくは液状炭化水素油を成分と
する、水性ベースまたは油性ベースの消泡剤または抑泡
剤が好ましい。また、該消泡剤または該抑泡剤中には、
疎水性シリカ、エチレンビス高級アルキルアミド、シリ
コーン油などの成分を含んでいてもよい。これらの消泡
剤または抑泡剤を未晒クラフトパルプの洗浄工程中に存
在せしめる方法としては、洗浄工程中の任意の段階で未
晒クラフトパルプのスラリーまたはシックナーに消泡剤
または抑泡剤を添加するのが好ましい。
【0014】本発明の実施に用いられる天然クラフトパ
ルプ、好ましくは木材クラフトパルプとしては、その蒸
解後洗浄処理され、その後酸素脱リグニン処理された後
、好ましくは更に洗浄処理され、その後漂白処理された
ものが有利に用いられる。酸素脱リグニンの処理条件と
しては、酸素脱リグニン段階での脱リグニン度が20〜
70%、好ましくは40〜50%になるように設定する
のが好ましい。また、酸素脱リグニン処理は少なくとも
酸素及びアルカリ、好ましくは更にパルプの重合度低下
防止剤の存存下に行われる。酸素脱リグニン処理に用い
られる酸素としては、酸素ボンベから供給されるもの、
酸素富化膜により空気から製造される酸素を主成分とす
るものなどが有利に用いられる。また、酸素脱リグニン
処理には、酸素単独でもよいし、過酸化水素等の酸素系
酸化剤の併用使用やオゾン、窒素酸化物等も使用出来る
。酸素脱リグニン処理に用いられるアルカリとしては、
水酸化ナトリウム、炭酸ナトリウム、酸化白液、酸化緑
液等のアルカリ液が使用出来るが、酸素白液を使用する
のが好ましい。また、酸素脱リグニン処理に好ましく用
いられるパルプの重合度低下防止剤としては、炭酸マグ
ネシウム、硫酸マグネシウム、塩化カルシウム等をあげ
ることが出来る。酸素脱リグニン処理の具体的な条件と
しては、各種の処理条件で行うことが出来る。例えば、
具体的には、パルプ濃度としては、未晒パルプの絶乾重
量として5wt%〜35wt%の範囲、好ましくは10
wt%〜20wt%の範囲、酸素の添加量としては、未
晒パルプの絶乾重量当り0.2wt%〜4wt%の範囲
、好ましくは0.5wt%〜2wt%の範囲、アルカリ
の添加量としては、未晒パルプの絶乾重量当り苛性ソー
ダ換算で0.2wt%〜7wt%の範囲、好ましくは0
.5wt%〜3wt%の範囲である。また、酸素脱リグ
ニン処理の処理温度としては、50℃〜150℃の範囲
、処理時間としては、10分〜180分の範囲が好まし
い。また、必要に応じて用いられるパルプの重合度低下
防止剤の添加量としては、未晒パルプの絶乾重量当り0
.05wt%〜1wt%の範囲が好ましい。
【0015】本発明の実施に用いられる天然クラフトパ
ルプ、好ましくは木材クラフトパルプは、その蒸解、洗
浄、酸素脱リグニン、洗浄後の漂白段階で漂白処理が施
されたものである。該漂白処理としては、塩素処理、ア
ルカリ処理もしくは抽出あるいは精製、次亜塩素酸塩漂
白処理、二酸化塩素漂白処理およびそれらの組み合わせ
多段漂白処理が好ましく、更に必要に応じて特公昭58
−43732号に記載もしくは例示のアルカリ性での過
酸化物漂白処理、またハイドロサルファイト、水素化ホ
ウ素ナトリウムなどによる還元漂白処理を施してもよい
。なお、本明細書で言う漂白段階とは、塩素処理段階以
降の漂白段階のことである。
【0016】本発明の実施に有利に用いられる木材クラ
フトパルプの好ましい多段漂白処理方式としては、第一
段が塩素処理段階(以下記号Cと略す)、第二段がアル
カリ処理もしくは抽出段階(以下記号Eと略す)、第三
段が次亜塩素酸塩漂白段階(以下記号Hと略す)あるい
は二酸化塩素漂白段階(以下記号Dと略す)であり、必
要に応じて施されるアルカリ性での過酸化物漂白段階(
以下記号Pと略す)は、第四段以降の段階で実施する方
式が有利である。例えば、「CEHDED」、「CEH
DPD」、「CEHDEDP」、「CEHED」、「C
EHPD」、「CEHEDP」、「CEHEH」、「C
EHEHP」、「CEHPHP」、「CEDED」、「
CEDEDP」などの方式が有用である。
【0017】本発明の実施に有利に用いられる木材クラ
フトパルプの漂白処理薬品としては、塩素漂白には塩素
ガスまたは塩素水が用いられる。また、二酸化塩素を併
用してもよい。アルカリ処理もしくは抽出には苛性ソー
ダを用いるのが有利であるが、水酸化カルシウム、アン
モニアなど及びそれらの混合物を用いることができる。
次亜塩素酸塩漂白には、固体紛状の消石灰に塩素を作用
させて作った晒粉、特に工業的には塩素を石灰乳あるい
は希薄苛性ソーダ溶液に吹込んで調製された次亜塩素酸
晒液、いわゆるカルシウム−ハイポ晒液、ナトリウム−
ハイポ晒液が有利に用いられる。二酸化塩素漂白には、
マチソン法、新マチソン法、エルスト法、C.I.P法
などの亜硫酸方式、ケスティング法、日曹法、ソルベー
法などの塩酸方式で調製された二酸化塩素が有利に用い
られる。また、アルカリ性での過酸化物漂白には、過酸
化物としては、過酸化水素、過酸化ナトリウム、過酸化
物晒液(過酸化水素、苛性ソ−ダ、珪酸ソ−ダおよび必
要に応じて加えた硫酸マグネシウムから成る混合水溶液
)、過酢酸、t−ブチルヒドロペルオキシドなどの無機
または有機過酸化物およびこれらの混合物が有利に用い
られ、またアルカリとしては、苛性ソ−ダ、水酸化カリ
ウム、アンモニア水、水酸化マグネシウム、水酸化カル
シウムなどのアルカリ水酸化物またはアルカリ土類水酸
化物およびこれらの混合物が有利に用いられる。また、
漂白処理条件としては、紙・パルプ技術協会編「パルプ
処理及び漂白」(昭和43年1月27日発行)、特公昭
58−43732号に記載の条件など各種の条件で行う
ことが出来る。
【0018】本発明の実施に用いられる天然クラフトパ
ルプ、好ましくは木材クラフトパルプとしては、本明細
書で定義される銀変色反応による変色発生個数がA−4
当り20個以下のものであるが、A−4当り10個以下
のものが好ましく、A−4当り5個以下のものが更に好
ましく、A−4当り2個以下(0個を含む)のものが最
も好ましい。銀変色反応による変色発生個数がA−4当
り20個以下である天然クラフトパルプ、好ましくは木
材クラフトパルプは、具体的には、酸素脱リグニン処理
を行い、かつ例えば以下の方法を用いることにより、好
ましくは以下の方法を2つ以上、更に好ましくは3つ以
上組み合わせて用いることにより得られることが本発明
者らの検討により明らかとなった。
【0019】(1)消泡剤の使用量を、その成分(水性
ベ−スの消泡剤の場合には水を除いた成分)として未晒
パルプトン当り(以下特に指定しなければ絶乾重量とし
て)0.1〜1.5kg、好ましくは0.1〜1.0k
g、更に好ましくは0.1〜0.75kgの範囲にする
。
【0020】(2)漂白段階に入る前の未晒クラフトパ
ルプシックナ−のpHを6.0以上、好ましくは6.5
以上、更に好ましくは7.0以上になるようにする。な
お、未晒クラフトパルプシックナ−のpHとは、未晒ク
ラフトパルプシックナ−50gに蒸留水300gを添加
して1時間良く撹拌後pHメ−タ−により液温25℃±
1℃で測定したものである。
【0021】(3)漂白段階に入る前の未晒クラフトパ
ルプシックナ−の電気伝導度を50μmho/cm以上
、好ましくは100μmho/cm以上、更に好ましく
は150μmho/cm以上になるようにする。なお、
未晒クラフトパルプシックナ−の電気伝導度とは、未晒
クラフトパルプシックナ−50gに蒸留水300gを添
加して1時間良く撹拌後電気伝導度計により液温25℃
±1℃で測定したものである。
【0022】(4)漂白段階に入る前の未晒クラフトパ
ルプ中のカルシウム含有量を極力低くする。具体的には
、漂白段階に入る前の未晒クラフトパルプシックナ−で
紙を構成した場合に、該紙中のカルシウム含有量を50
00ppm以下、好ましくは4000ppm以下、更に
好ましくは3000ppm以下になるようにする。なお
、未晒クラフトパルプシックナ−での紙の調製は、使用
する水として脱イオン水を用いる以外はTappi ス
タンダ−ドT−205に準拠して行い、該紙中のカルシ
ウム含有量とは、蛍光X線法により測定したものである
。
【0023】(5)未晒白水中のカルシウム含有量を極
力低くする。そのためには、蒸解工程に由来するカルシ
ウム含有量を低くする。例えば、適切な樹種の選択、白
水中に存在する不溶性カルシウム塩、例えば水酸化カル
シウム、炭酸カルシウムなどの濾過による除去効率の向
上、未晒白水中へのキレ−ト剤、例えばEDTA−ナト
リウム塩などの添加等を行うのが好ましい。
【0024】(6)塩素段階でのクラフトパルプスラリ
−のpHとしては、pHを2.5以下、好ましくは2.
0以下、更に好ましくは1.5以下になるようにする。
【0025】(7)抄造工程に入る前の漂白クラフトパ
ルプをクリ−ナ−、好ましくは液体サイクロン方式のク
リ−ナ−を用いてクリ−ンにする。クリ−ナ−での最終
リジェクト率としては、絶乾パルプ当り、0.02重量
%以上、好ましくは0.05重量%以上、更に好ましく
は0.1重量%以上にするのがよい。
【0026】本発明の実施に用いられる基紙中には、紙
料スラリ−調製時に各種の添加剤を含有せしめることが
できる。サイズ剤として、脂肪酸金属塩あるいは/及び
脂肪酸、特公昭62−7534 号に記載もしくは例示
のアルキルケテンダイマー乳化物あるいはエポキシ化高
級脂肪酸アミド、アルケニルまたはアルキルコハク酸無
水物乳化物、ロジン誘導体等、乾燥紙力増強剤として、
アニオン性、カチオン性あるいは両性のポリアクリルア
ミド、ポリビニルアルコール、カチオン化澱粉、植物性
ガラクトマンナン等、湿潤紙力増強剤として、ポリアミ
ンポリアミドエピクロルヒドリン樹脂等、填料として、
クレー、カオリン、炭酸カルシウム、酸化チタン等、定
着剤として、塩化アルミニウム、硫酸バン土等の水溶性
アルミニウム塩等、pH調節剤として、苛性ソーダ、炭
酸ソーダ、硫酸等を、その他特開昭63−204251
号、特開平1−266537号等に記載もしくは例示
の着色顔料、着色染料、蛍光増白剤などを適宜組み合せ
て含有せしめるのが有利である。
【0027】また、本発明の実施に用いられる基紙中に
は、各種の水溶性ポリマー、帯電防止剤、添加剤をスプ
レーあるいはタブサイズプレスによって含有せしめるこ
とができる。水溶性ポリマーとして、特開平1−266
537号に記載もしくは例示の澱粉系ポリマー、ポリビ
ニルアルコール系ポリマー、ゼラチン系ポリマー、ポリ
アクリルアミド系ポリマー、セルローズ系ポリマーなど
、帯電防止剤として、塩化ナトリウム、塩化カリウム等
のアルカリ金属塩、塩化カルシウム、塩化バリウム等の
アルカリ土類金属塩、コロイド状シリカ等のコロイド状
金属酸化物、ポリスチレンスルホン酸塩等の有機帯電防
止剤など、ラテックス、エマルジョン類として、石油樹
脂エマルジョン、スチレン―アクリル酸―アクリル酸エ
ステル共重合体、スチレン―アクリル酸―ブタジエン共
重合体、エチレン―酢酸ビニル共重合体、スチレン―マ
イレン酸―アクリル酸エステル共重合体等のラテックス
、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、リン酸
、クエン酸、苛性ソーダなど、そのほか前記した着色顔
料、着色染料、蛍光増白剤などの添加剤を適宜組み合わ
せて含有せしめるのが有利である。
【0028】本発明の実施に用いられる基紙としては、
JIS P8119により規定されるベック平滑度が
100秒以上の平滑面を有するものが好ましく、200
秒以上の平滑面を有するものが更に好ましい。ベック平
滑度100秒以上の基紙を製造する方法としては、一般
的には、短繊維で平滑性のでやすい広葉樹パルプを多く
用い、叩解機により長繊維分がなるべく少なくなるよう
に叩解する。具体的には、パルプの叩解は叩解後のパル
プの繊維長を42メッシュ残分が20〜45%、濾水度
200〜350CSFになるようにすることが好ましい
。
ついで、内添薬品を添加した紙料スリラ−について、特
開昭58−37642号、特開昭61−260240
号、特開昭61−284762 号等に記載もしくは例
示してあるような適切な抄紙方法を採用して長網抄紙機
、丸網抄紙機など通常用いられる抄紙機により均一な地
合が得られるように抄造し、更に抄造後にマシンカレン
ダ−、ス−パ−カレンダ−、熱カレンダ−等を用いてカ
レンダ−処理を施し、ベック平滑度100秒以上の基紙
を製造することが出来る。基紙の厚みに関しては、特に
制限はないが、その坪量は40g/m2〜250g/m
2のものが好ましい。
【0029】本発明の実施に用いられるフィルム形成能
ある樹脂としては、ポリオレフィン樹脂、ポリカ−ボネ
−ト樹脂、ポリエステル樹脂、ポリアミド樹脂などの熱
可塑性樹脂が好ましく、中でも溶融押出しコ−ティング
性の点からポリオレフィン樹脂が更に好ましい。また、
特公昭60−17104号に記載もしくは例示の電子線
硬化樹脂で被膜してもよい。
【0030】本発明の実施に好ましく用いられるポリオ
レフィン樹脂としては、ポリエチレン、ポリプロピレン
、ポリブテン、ポリペンテン等のホモポリマ−、エチレ
ン−ブチレン共重合体などのα−オレフィンの2つ以上
から成る共重合体及びこれらの混合物であるが、特に溶
融押出しコーティング性および基紙との接着性の点から
ポリエチレン系樹脂が特に好ましい。それらのポリエチ
レン系樹脂としては、低密度ポリエチレン、中密度ポリ
エチレン、高密度ポリエチレン、直鎖状低密度ポリエチ
レン、エチレンとプロピレン、ブチレン等のα−オレフ
ィンとの共重合体、カルボキシ変性ポリエチレン等及び
これらの混合物であり、各種の密度、メルトフローレー
ト(以下単にMFRと略す)、分子量、分子量分布のも
のを使用できるが、通常、密度0.90〜0.97g/
cm3 の範囲、MFR0.1g/10分〜40g/1
0分、好ましくは、MFR0.3g/10分〜30g/
10分、分子量2万〜25万の範囲のものを単独にある
いは混合して有利に使用できる。また、樹脂が多層構成
の場合、最外層の樹脂として、例えばMFR5g/10
分〜20g/10分のもの、下層の樹脂として、例えば
MFR2g/10分〜10g/10分のものを使用する
など別の性質、構成の樹脂を使用することもできる。
【0031】本発明に於ける感光材料用支持体の樹脂層
中には、各種の添加剤を含有せしめることが出来る。特
公昭60−3430 号、特公昭63−11655号、
特公平1−38291 号、特公平1−38292 号
、特開平1−105245号等に記載もしくは例示の酸
化チタン、酸化亜鉛、タルク、炭酸カルシウム等の白色
顔料、ステアリン酸アミド、アラキジン酸アミド等の脂
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、パルミチン酸亜鉛、ミリスチン酸亜鉛、パルミチ
ン酸カルシウム等の脂肪酸金属塩、特開平1−1052
45号に記載もしくは例示のヒンダ−ドフェノ−ル、ヒ
ンダ−ドアミン、リン系、硫黄系等の各種酸化防止剤、
コバルトブル−、群青、セリアンブル−、フタロシアニ
ンブル−等のブル−系の顔料や染料、コバルトバイオレ
ット、ファストバイオレット、マンガンバイオレット等
のマゼンタ系の顔料や染料、特開平2−254440号
に記載もしくは例示の蛍光増白剤、紫外線吸収剤等の各
種の添加剤を適宜組み合わせて含有せしめることが出来
る。それらの添加剤はフィルム形成能ある樹脂のマスタ
ーバッチあるいはコンパウンドとして含有せしめるのが
好ましい。また、フィルム形成能ある樹脂が熱可塑性樹
脂、好ましくはポリエチレン系樹脂の場合には、樹脂層
は走行する基紙の上に溶融した樹脂を被覆する溶融押出
しコ−ティング法により製造するのが好ましい。樹脂を
基紙に被覆する前に、基紙にコロナ放電処理、火炎処理
などの活性化処理を施すのが好ましい。
【0032】本発明における感光材料用支持体の感光層
側表面は光沢面または感光材料にした場合に感光材料の
表面の光沢に影響を与えない程度の特公昭62−197
32号に記載の微粗面あるいはマット面、絹目面等を有
し、裏面は通常無光沢面であり、表面あるいは必要に応
じ表裏両面にもコロナ放電処理、火炎処理などの活性化
処理を施すことができる。更に、活性化処理後、特開昭
61−84643号に記載のような下引き処理をするこ
とができる。また、表裏の樹脂層の厚さとしては、特に
制限はないが、一般に10μ〜50μ程度の厚さのもの
が有利である。
【0033】本発明における感光材料用支持体には帯電
防止、カ−ル防止等のために、各種のバックコ−ト層を
塗設することができる。また、バックコ−ト層には、特
公昭52−18020号、特公昭57−9059 号、
特公昭57−53940号、特公昭58−56859号
、特開昭59−214849 号、特開昭58−184
144 号等に記載もしくは例示の無機帯電防止剤、有
機帯電防止剤、親水性バインダ−、ラテックス、硬化剤
、顔料、界面活性剤等を適宜組み合わせて含有せしめる
ことができる。
【0034】本発明における感光材料用支持体は、各種
の写真構成層が塗設されてカラ−写真印画紙用、白黒写
真印画紙用、写植印画紙用、複写印画紙用、反転写真材
料用、銀塩拡散転写法ネガ用、印刷材料用等各種の用途
に用いることができる。例えば、塩化銀、臭化銀、塩臭
化銀、沃臭化銀、塩沃臭化銀乳剤層を設けることができ
る。ハロゲン化銀写真乳剤層にカラ−カプラ−を含有せ
しめて、多層ハロゲン化銀カラ−写真構成層を設けるこ
とができる。また、銀塩拡散転写法用感光層を設けるこ
とができる。それらの写真構成層の結合剤としては、通
常のゼラチンの他に、ポリビニルピロリドン、ポリビニ
ルアルコ−ル、多糖類の硫酸エステル化合物などの親水
性高分子物質を用いることができる。また、上記の写真
構成層には各種の添加剤を含有せしめることができる。
例えば、増感色素として、シアニン色素、メロシアニン
色素など、化学増感剤として、水溶性金化合物、イオウ
化合物など、カブリ防止剤もしくは安定剤として、ヒド
ロキシ−トリアゾロピリミジン化合物、メルカプト−複
素環化合物など、硬膜剤としてホルマリン、ビニルスル
フォン化合物、アジリジン化合物など、塗布助剤として
、アルキルベンゼンスルフォン酸塩、スルホコハク酸エ
ステル塩など、汚染防止剤として、ジアルキルハイドロ
キノン化合物など、そのほか蛍光増白剤、鮮鋭度向上色
素、帯電防止剤、pH調製剤、カブらせ剤、更にハロゲ
ン化銀の生成・分散時に水溶性イリジウム、水溶性ロジ
ウム化合物などを適宜組み合わせて含有せしめることが
できる。
【0035】本発明に係る感光材料は、その感光材料に
合わせて「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が
、特に発色現像後一浴漂白定着処理を行う多層ハロゲン
化銀カラ−写真感光材料は、CD−III、CD−IV
(以上の2種の化合物はコダック社商品名)、ドロキシ
クロム(メイアンドベ−カ−社商品名)などいかなる主
薬のカラ−現像液でも処理することができる。かかる主
薬を含む現像液にベンジルアルコ−ル、タリウム塩、フ
ェニドンなどの現像促進剤を含有させてもよい、また、
ベンジルアルコ−ルを実質的に含まない現像液で処理す
ることもできる。また、有用な一浴漂白定着液はアミノ
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鉄錯塩など
)溶液であり、定着剤としては、チオ硫酸ソ−ダ、チオ
硫酸アンモニウムなどが有用である。かかる一浴漂白定
着液には種々の添加剤を含有させることができる。例え
ば、脱銀促進剤(例えば、米国特許第3,512,97
9 号に記載のメルカプトカルボン酸、ベルギ−特許第
682,426 号に記載のメルカプト−複素環化合物
など)、汚染防止剤、pH調節剤ないしはpH緩衝剤、
硬膜剤(例えば、硫酸マグネシウム、硫酸アルミニウム
、カリ明ばんなど)、界面活性剤などの種々の化合物を
組み合わせて含有させることができる。また、かかる一
浴漂白定着液は種々のpHで使用され得るが有用なpH
領域はpH6.0〜8.0である。
【0036】
【実施例】次に本発明を更に具体的に説明するために、
実施例を述べる。
【0037】実施例1
広葉樹クラフトパルプの製造工程において、蒸解後未晒
クラフトパルプを第1段階の洗浄工程で洗浄処理し、そ
の後下記の条件で酸素脱リグニン処理し、酸素脱リグニ
ン処理後第2段階の洗浄工程で洗浄処理し、以後の工程
で「CEHDPD」の方式で漂白処理した。一方、比較
用の広葉樹パルプの製造工程においては酸素脱リグニン
処理を省略した。酸素脱リグニン処理の条件としては、
パルプ濃度が未晒パルプ絶乾重量として15wt%、苛
性ソーダ及び酸素の添加量が未晒パルプ絶乾重量当りそ
れぞれ1.5wt%及び1.0wt%、処理温度及び処
理時間がそれぞれ110℃及び45分であった。また、
広葉樹クラフトパルプの酸素脱リグニン工程以外の工程
条件として、未晒クラフトパルプの洗浄段階での鉱油を
成分として含む油性ベースの消泡剤の合計量での存在量
が未晒パルプ絶乾重量1トン当り0.7kg、1.0k
g、1.5kgまたは2.0kg、明細書で定義される
未晒シックナ−の電気伝導度が100μmho/cm及
び液体サイクロン方式のクリ−ナ−の最終リジェクト率
が絶乾パルプに対して0.01wt%、0.02wt%
、0.05wt%または0.1wt%であり、表1に記
載の組み合わせに調節し、その他の工程条件をそれぞれ
適宜調節して、明細書で定義される銀変色反応による変
色発生個数が表1の通りである広葉樹漂白クラフトパル
プをそれぞれ得た。
【0038】次に、それぞれのパルプをカナディアン・
スタンダ−ト・フリ−ネス320mlに叩解し、更にパ
ルプ100重量部に対して、カオチン化澱粉3重量部、
アニオン化ポリアクリルアミド0.2重量部、アルキル
ケテンダイマ−乳化物(ケテンダイマ−分として)0.
4重量部、ポリアミノポリアミドエピクロルヒドリン樹
脂0.4重量部を添加し、坪量100g/m2の紙を製
造した。得られた湿紙を110℃で乾燥し、引き続きカ
ルボキシ変性ポリビニルアルコール3重量部、蛍光増白
剤0.05重量部、青色染料0.002重量部、クエン
酸0.2重量部及び水97重量部から成る含浸液を25
g/m2含浸させ、110℃の熱風で乾燥し、更に線圧
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て、感光材料用支持体の基紙を
製造した。
【0039】次に、基紙の表面に低密度ポリエチレン樹
脂(密度0.92g/cm3 、MFR=8.5g/1
0分)47.5重量%、含水酸化アルミニウム(対二酸
化チタンに対してAl2O3分として0.75重量%)
で表面処理したアナターゼ型二酸化チタン顔料50重量
%とステアリン酸亜鉛2.5重量%から成る二酸化チタ
ン顔料のマスタ−バッチ20重量部、低密度ポリエチレ
ン樹脂(密度0.92g/cm3 、MFR=4.5g
/10分)65重量部と高密度ポリエチレン樹脂(密度
0.97g/cm3 、MFR=7.0g/10分)1
5重量部から成る樹脂組成物を樹脂温度330℃で13
μの厚さに溶融押出しコ−ティングした。なお、基紙の
表面に樹脂層を塗設する前に基紙の反対側の面(裏面)
に、低密度ポリエチレン樹脂(密度0.92g/cm3
、MFR2g/10分)15重量部と高密度ポリエチレ
ン樹脂(密度0.96g/cm3、MFR20g/10
分)85重量部から成る樹脂組成物を樹脂温度330℃
で表面と同じ厚さに溶融押出しコ−ティングした。その
際このようにして製造した感光材料用支持体の二酸化チ
タン顔料を含む樹脂層の表面は微粗面に、裏の樹脂層の
面質は紙の如きマット面に加工した。
【0040】その後、感光材料用支持体の裏面にコロナ
放電処理後乾燥重量分としてコロイダルシリカ:スチレ
ンアクリル系ラテックス=1:1の組成から成るバック
コ−ト層を0.4g/m2塗設した。次いで感光材料用
支持体の二酸化チタン顔料を含む表側の樹脂面にコロナ
放電処理後乳剤層及びその保護層を設けて白黒写真印画
紙を得た。乳剤層はヘキサクロロイリジウム(III)
カリウム1.2×10−5gの存在下にゼラチン14.
4g中に硝酸銀で19.2g分のハロゲン化銀粒子を生
成・分散して製造したArBr/AgCl=65/35
なるハロゲン組成を有する平均粒子径0.6μの最高感
度に硫黄増感と金増感により併用増感した実質的に〔1
、0、0〕面からなる中性法ハロゲン化銀写真乳剤を含
み、更に成膜に必要なゼラチンの他、適量の安定剤、増
感色素、塗布助剤、硬膜剤、蛍光増白剤、増粘剤、フィ
ルタ−染料等を含み、硝酸銀で2.2g/m2、ゼラチ
ンで4.4g/m2に相当する塗布量で保護層と共に重
層塗布された。保護層は2g/m2に相当するゼラチン
の他に塗布助剤、硬膜剤を含む。
【0041】塗布、乾燥した試料は50℃、81%で4
日間保存した後白黒現像し、斑点状カブリの個数を計測
した。得られた結果を表1に示す。
【0042】
【表1】
【0043】表1からわかるように、酸素脱リグニン処
理されて明細書で定義される銀変色反応による変色発生
個数がA−4当り20個以下の木材クラフトパルプを用
いた本発明の試料は、斑点状カブリの発生が少なく、木
材クラフトパルプとしては変色発生個数がA−4当り1
0個以下が好ましく、更にA−4当り5個以下が一層好
ましいことがよくわかる。
【0044】実施例2
実施例1で用いた木材クラフトパルプの代りに、実施例
1と同様に酸素脱リグニン処理を施し、下記の工程条件
で製造したものを用いる以外は実施例1と同様に実施し
た。
【0045】広葉樹クラフトパルプの製造工程において
、工程条件として、未晒クラフトパルプの洗浄段階での
鉱油を成分として含む油性ベ−スの消泡剤の合計量での
存在量が未晒パルプ絶乾重量1トン当り0.1kg、0
.7kg、1.0kg、1.5kgまたは2.0kg、
明細書で定義される未晒シックナーの電気電導度が45
μmho/cm、100μmho/cmまたは150μ
mho/cm、及び液体サイクロン方式のクリナーの最
終リジェクト率が絶乾パルプに対して0.01wt%、
0.02wt%、0.05wt%または0.1wt%で
あり、表2に記載の組み合わせに調節し、その他の工程
条件をそれぞれ適宜調節して、明細書で定義される銀変
色反応による変色発生個数が表2の通りである広葉樹漂
白パルプをそれぞれ得た。なお、消泡剤の存在量が0.
1kg未満では発泡の防止が不十分であった。
【0046】得られた結果を表2に示す。
【0047】
【表2】
【0048】表2からわかるように、酸素脱リグニン処
理されて明細書で定義される銀変色反応による変色発生
個数がA−4当り20個以下の木材クラフトパルプを用
いた本発明の試料は、斑点状カブリの発生が少なく、木
材クラフトパルプとしては変色発生個数がA−4当り1
0個以下が好ましく、更にA−4当り5個以下が一層好
ましいことがよくわかる。
【0049】実施例3
実施例1で用いた木材クラフトパルプの代りに、実施例
1と同様に酸素脱リグニン処理を施し、下記の工程条件
で製造したものを用いる以外は実施例1と同様に実施し
た。
【0050】広葉樹クラフトパルプの製造工程において
、工程条件として、未晒クラフトパルプの洗浄段階での
鉱油を成分として含む油性ベ−スの消泡剤の合計量での
存在量が未晒パルプ絶乾重量1トン当り0.1kg、0
.7kg、1.0kg、1.5kgまたは2.0kg、
明細書で定義される未晒クラフトパルプ中のカルシウム
含有量が3000ppm、4000ppm、あるいは5
500ppm、及び塩素段階でのクラフトパルプスラリ
−のpHがpH1.5、pH2.0あるいはpH2.7
であり、表3に記載の組み合わせに調節し、その他の工
程条件をそれぞれ適宜調節して、明細書で定義される銀
変色反応による変色発生個数が表3の通りである広葉樹
漂白パルプをそれぞれ得た。
【0051】得られた結果を表3に示す。
【0052】
【表3】
【0053】表3からわかるように、酸素脱リグニン処
理されて明細書で定義される銀変色反応による変色発生
個数がA−4当り20個以下の木材クラフトパルプを用
いた本発明の試料は、斑点状カブリの発生が少なく、木
材クラフトパルプとしては、変色発生個数がA−4当り
10個以下が好ましく、更にA−4当り5個以下が好ま
しいことがよくわかる。
【0054】実施例4
実施例2で用いた銀変色反応による変色発生個数がA−
4当り2.25個および28個である木材クラフトパル
プを用いて、基紙の坪量を160g/m2、表、裏の樹
脂層の厚さをそれぞれ30μにする以外は実施例1と同
様にして感光材料用支持体を得た。
【0055】次いで感光材料用支持体の二酸化チタン顔
料を含む表側の樹脂面にコロナ放電処理後下記の乳剤層
及びその保護層を設けて印画紙を得た。乳剤層はヘキサ
クロロイリジウム(III)カリウム1.0×10−5
gの存在下に、ゼラチン4.8g中に硝酸銀量9.6g
分のハロゲン化銀粒子を生成・分散して製造したAgB
r/AgCl=95/5なるハロゲン組成を有する平均
粒子径0.8μの最高感度に硫黄増感した〔1、0、0
〕と〔1、1、1〕面との混晶から成る中性法ハロゲン
化銀写真乳剤を含み、更にイエロ−発色カプラ−及び成
膜に必要なゼラチンの他、適量の安定剤、青感用増感色
素、塗布助剤、硬膜剤、増粘剤等を含み、硝酸銀量で0
.6g/m2、ゼラチンで1.5g/m2に相当する塗
布量で、保護層と共に重層塗布された。保護層は1.5
g/m2に相当するゼラチンの他に塗布助剤、増粘剤、
硬膜剤等を含む。
【0056】塗布、乾燥した試料は50℃、81%で4
日間保存した後発色現像し、斑点状カブリの個数を計測
した。また、イエロ−発色濃度が0.4となる様に加温
保存後の試料に均一な露光を行い、その後発色現像し、
斑点状に減感している箇所の個数を計測した。
【0057】その結果、銀変色反応による変色発生個数
がA−4当り2.25個である木材クラフトパルプを用
いた本発明の試科では、斑点故障は全く認められなかっ
た。一方、銀変色反応による変色発生個数がA−4当り
28個である木材クラフトパルプを用いた本発明外の試
科では、A−4当り数個の斑点状カブリと10数個の斑
点状減感が認められた。
【0058】実施例5
実施例2で用いた銀変色発生個数がA−4当り2.25
個および28個である木材クラフトパルプを用いて、基
紙の坪量を135g/cm2にする以外は実施例1と同
様にして感光材料用支持体の基紙を製造した。
【0059】その後、基紙の両面に低密度ポリエチレン
樹脂(密度0.92g/cm3 、MFR4.5g/1
0分)を樹脂温度330℃で18μの厚さにそれぞれ溶
融押出しコ−ティングした。その際、感光材料用支持体
の両面を紙の如きマット面に加工した。
【0060】次いで、感光材料用支持体の一方の面にコ
ロナ放電処理後平均粒子径4μのシリカ粒子とゼラチン
1.0g/m2及び硬膜剤を含有するバックコ−ト層を
塗設した。次いで、バックコ−ト層とは反対側の支持体
面にコロナ放電処理後カ−ボンブラック、平均粒子径7
μのシリカ粒子及びゼラチン3.5g /m2、硬膜剤
から成る下塗り層とAgBr/AgCl=5/95なる
ハロゲン組成を有する平均粒子径0.4μの最高感度に
硫黄増感と金増感により併用増感した実質的に〔1、0
、0〕面からなる中性法ハロゲン化銀乳剤を含み、更に
成膜に必要なゼラチンの他、適量の安定剤、オルソ用増
感色素、フェニドン、塗布助剤、硬膜剤等を含む乳剤を
硝酸銀量で1.0g/m2、ゼラチン1.0g/m2に
相当する塗布量で重層塗布した。塗布、乾燥後40℃で
3日間加温した後この乳剤層の上に、アクリルアミドと
イミダゾ−ルとの共重合体、ハイドロキノン、硫化パラ
ジウム核等から成る塗布液を硫化パラジウムゾル1.0
g/m2で塗布して平板印刷版用感光材料を得た。
【0061】塗布、乾燥した試料はロ−ル状態で50℃
、81%で4日間保存した後裁断し、その後拡散転写現
像し、斑点故障の個数を計測した。
【0062】その結果、銀変色反応による変色発生個数
がA−4当り2.25個である木材クラフトパルプを用
いた本発明の試料では、斑点状故障は全く認められなか
った。一方、銀変色反応による変色発生個数がA−4当
り28個である木材クラフトパルプを用いた本発明外の
試料では、斑点状に転写銀が欠落したり、薄くなったり
するという斑点故障が多数認められた。
【0063】実施例6
実施例1に於て、酸素脱リグニン処理条件を下記条件(
1)または(2)にする以外は実施例1と同様に実施し
、実施例1と同様の結果を得た。
【0064】条件(1);パルプ濃度が未晒パルプ絶乾
重量として20wt%、苛性ソーダ及び酸素の添加量が
未晒パルプ絶乾重量当りそれぞれ3wt%及び2.1w
t%、処理温度及び処理時間がそれぞれ110℃及び3
0分である。
【0065】条件(2);パルプ濃度が未晒パルプ絶乾
重量として27wt%、苛性ソーダ及び酸素の添加量が
未晒パルプ絶乾重量当りそれぞれ2.0wt%および1
.5wt%、処理温度及び処理時間がそれぞれ98℃及
び2時間である。
【0066】実施例7
実施例1において、アルカリとして苛性ソーダの代りに
酸化白液を苛性ソーダ分として実施例1と同量用いる以
外は実施例1と同様に実施し、実施例1と同様の結果を
得た。
【0067】
【発明の効果】本発明により、ハロゲン化銀感光層に対
して斑点故障の発生傾向が顕著に抑制された、天然パル
プを主成分とする紙を基質とする優れた感光材料用支持
体が提供出来る。Detailed Description of the Invention [0001] [Industrial Application Field] The present invention provides a paper base (hereinafter referred to as base paper) mainly composed of natural pulp coated with a resin capable of forming a film, preferably a polyolefin resin. The present invention relates to a support for a resin-coated paper-type photosensitive material, and more particularly to a support for a resin-coated paper-type photosensitive material that has good photographic suitability for a silver halide photosensitive layer. 2. Description of the Related Art Resin-coated paper-type supports for photosensitive materials, in which at least one surface of the substrate is coated with a film-forming resin, are well known as supports for photosensitive materials. For example, Japanese Patent Publication No. 55-12584 discloses a technique for a support for photosensitive materials in which a base paper is coated with a resin capable of forming a film, preferably a polyolefin resin. US Pat. No. 3,501,298 discloses a technique for a support for photosensitive materials in which both sides of a base paper are coated with a polyolefin resin. Furthermore, ever since rapid photographic processing methods for silver halide photographic light-sensitive materials were applied, supports for light-sensitive materials, in which both sides of the base paper are coated with polyethylene resin, have been mainly used for photographic paper. If necessary, the resin layer on one of the image forming sides usually contains a titanium dioxide pigment in order to impart sharpness. However, resin-coated paper-type supports for photosensitive materials, in which a base paper containing natural pulp as a main component is coated with a resin capable of forming a film, still have some serious problems in terms of photographic suitability for silver halide photosensitive layers. It had some problems. That is, when a silver halide photosensitive material having a resin-coated paper as a support, which is a base paper mainly composed of natural pulp coated with a film-forming resin, is stored after its manufacture.
When stored for a long period of time, especially when stored under high temperature and high humidity, the silver halide in the photosensitive material may fog up in spots, and the unexposed areas can be developed into spots during the development process. There is a problem in that the sensitivity of the photosensitive material may decrease or increase in spots. For example, in the case of a certain type of positive black and white silver halide photographic paper that uses the resin-coated paper as a support, speckled fog appears on the white background. This speckled fog can sometimes reach a diameter of more than 20 mm, rendering the photographic paper completely worthless as a commercial product. In addition, in the case of a type of photosensitive material using the silver salt diffusion transfer method that has the resin-coated paper as a support for the silver halide negative photosensitive layer, spotty fogging occurs on the negative side silver halide photosensitive layer. As a result, the image density on the positive side decreases in spots, and the silver image is hardly formed in spots, resulting in no commercial value at all. In addition, in the case of a certain type of multilayer silver halide color photographic paper in which the resin-coated paper is used as a support and a yellow coloring layer, a magenta coloring layer, and a cyan coloring layer are sequentially arranged adjacent to the support, a speckled color is formed. In addition to fogging, the sensitivity of the yellow and magenta coloring layers in particular decreases in spots, and the color balance of the image deteriorates in spots, resulting in a loss of commercial value of the photographic paper. Hereinafter, these phenomena will be collectively referred to as spot failures. Up to now, various stabilizers or fog suppressants have been proposed for preventing changes in photographic properties of silver halide photosensitive materials during storage. However, even if various stabilizers or fog suppressants are contained in the constituent layers of a silver halide photosensitive material using resin-coated paper as a support, considerable photographic adverse effects such as a decrease in sensitivity and a softening of tone may occur. In addition to this, it was almost impossible to prevent spotty failures. There are also several proposals regarding the photographic properties of supports for light-sensitive materials. Japanese Patent Publication No. 54-9844 proposes an anti-fogging, resin-coated paper-type support for photosensitive materials in which a base paper is coated with a polyolefin resin containing a hydroxy-substituted-triazolopyrimidine compound. It was extremely insufficient to prevent spot failures in silver halide light-sensitive materials having the support. Regarding photographic paper, Japanese Patent Laid-Open No. 52-65423 and Japanese Patent Publication No. 58-43730 propose eliminating the adverse effects on photographic properties due to the decomposition of cationic electrolytes and additive chemicals for paper, respectively. In silver halide photosensitive materials that use resin-coated photographic paper as a support, spot failures cannot be prevented at all, and spot failures occur due to a mechanism completely different from that described in these specifications. It became clear that it would. Also, JP-A-2-9674
No. 1, JP-A No. 2-99689 and JP-A No. 2-99
No. 693 proposes a technique for improving the photographic properties of unbleached kraft paper. According to them, bleached kraft paper has good photographic properties, but unbleached kraft paper has poor photographic properties.
The cause of this is that propylene oxide and/or silicone, which are antifoaming components used in the unbleached stage, remain. By specifying the antifoaming agent containing these components and the cold water extraction pH, unbleached kraft paper It has been proposed to improve the photographic properties of. However, in the case of silver halide photosensitive materials using resin-coated paper as a support made of base paper mainly composed of bleached natural pulp to which this technology is applied, spot failures cannot be prevented at all; It has become clear that this phenomenon is caused by a completely different mechanism than that described in the book. Furthermore, Special Public Interest Publication No. 58-43732
No. 1, a technique was proposed to improve the shelf life of silver halide photographic materials by using a resin-coated paper consisting of a base paper based on natural pulp bleached with alkaline peroxide. Even when the resin-coated paper was used, it was insufficient to prevent spot failures. Furthermore, the special public
No. 9-38575 proposes a technique for preventing fog and spots in silver halide photographic materials by using photographic paper using wood pulp obtained by oxygen pulping method, but it is not possible to use this photographic paper as a substrate. Even with resin-coated paper, prevention of spot failure remained insufficient. As described above, techniques for improving spot failures in silver halide photosensitive materials using resin-coated paper as a support, in which a base paper containing natural pulp as a main component is coated with a resin capable of forming a film, and techniques for improving spot failures have been described. The mechanism or cause of occurrence is
This is completely unknown, and it has not been possible to improve the spot failure using conventionally known techniques. SUMMARY OF THE INVENTION Therefore, it is an object of the present invention to provide a base paper containing natural pulp as a main component, in which the tendency of spot failure to occur in a silver halide photosensitive layer is significantly suppressed. An object of the present invention is to provide a support for a photosensitive material coated with a resin capable of forming a film. Other objects of the invention will become apparent from the description below. Means and Effects for Solving the Problems In order to solve the above-mentioned problems, the inventors of the present invention, as a result of intensive studies, developed a base paper mainly composed of natural pulp with a film-forming resin. In the coated support for photosensitive materials, part or all of the natural pulp constituting the base paper is natural kraft pulp, and as the natural kraft pulp, an antifoaming agent or foam suppressor is added to the natural kraft pulp in the unbleached stage after cooking by the kraft method. washed in the presence of a cleaning agent, subjected to oxygen delignification treatment before and after the washing treatment, and bleached in the subsequent bleaching step,
Furthermore, it has been found that the object of the present invention can be achieved by using natural kraft pulp in which the number of discolorations due to the silver discoloration reaction defined herein is 20 or less per A-4. did. In this specification, the number of discolored particles due to silver discoloration reaction refers to a natural kraft pulp sample on the silver surface of a silver plate prepared based on Tappi Standard T444 (sample conditions include basis weight;
50g/m2±150g/m2, absolute dry moisture content; 20% by weight±5% by weight, pH; Tappi Standard T20
The pH of the pulp suspension when prepared based on 5) is 6.0 to 7.5), sealed in a black plastic bag, and a load of 2.5 kg per A-4 is applied. , temperature 50℃
A heating treatment was performed for 50 hours under conditions of ±1° C. and relative humidity of 81% ±2%, and then the number of silver discoloration reactions occurring on the silver surface was counted. According to the studies conducted by the present inventors, when natural kraft pulp is washed in the presence of an antifoaming agent or a foam suppressing agent in the unbleached stage after cooking, it has been found that the presence of black liquor components or black liquor modifying components Water-insoluble or poorly water-soluble silver discoloration reaction generating substances are occluded by the action of antifoaming agents or foam suppressing agents,
Surprisingly, the silver discoloration reaction product remains in the bleached natural kraft pulp even after being attacked by oxidizing agents or alkaline agents in the subsequent bleaching step.
Furthermore, it was found that the bleached natural kraft pulp remained locally on the base paper after beating and papermaking, and that the silver discoloration reaction-generating substance caused spot failures, and furthermore, it was found that the unbleached stage of the bleached natural kraft pulp after cooking by the kraft method caused spot failure. The material is washed in the presence of an antifoaming agent or foam suppressant, and is subjected to oxygen delignification treatment before and after the washing treatment, and bleached in the subsequent bleaching step, and contains fewer substances that generate silver discoloration reactions. It was discovered that spot failure could be improved by using natural kraft pulp, leading to the present invention. As the natural kraft pulp used in the practice of the present invention, wood kraft pulps such as softwood kraft pulp, hardwood kraft pulp, and mixed kraft pulp of softwood and hardwood are advantageously used. These wood craft pulps are made by removing lignin from wood chips by pressure cooking, or cooking, in a mixture containing sodium hydroxide and sodium sulfide as chemical components, known as cooking liquor.
Thereafter, the pulp fibers and the cooking residue, so-called black liquor, are separated and washed in the presence of an antifoaming agent or a foam suppressing agent, and then subjected to an oxygen delignification treatment, and then a bleaching treatment. In addition to sodium hydroxide and sodium sulfide, the chemical components in the cooking liquor include salts such as sodium carbonate, sodium sulfate, slaked lime, and calcium carbonate, and cooking aids such as sodium borohydride and anthraquinone compounds. You can. Further, it may be produced by various cooking methods such as polysulfide cooking, batch cooking, continuous cooking, etc., and may be produced with various sulfidity degrees and kappa numbers. [0012] The base paper used in the practice of the present invention has natural pulp as its main component, and part or all of it is composed of natural kraft pulp, preferably wood kraft pulp, but it can also be used in combination with natural kraft pulp. If necessary, it may be made of natural pulp other than natural kraft pulp, synthetic fiber, or synthetic pulp. As the pulp used in combination with natural kraft pulp, natural pulp is preferred, and wood sulfite pulp such as softwood sulfite pulp, hardwood sulfite pulp, and softwood hardwood mixed sulfite pulp is particularly preferred. Further, wood soda pulp, wood dissolving pulp, etc. can also be used. Various antifoaming agents or antifoaming agents can be used in the practice of the present invention. For example, JP-A-54-59404, JP-A-58-220896, JP-A-61-245391, JP-A-61-245.
319, U.S. Patent No. 3,923,638, U.S. Patent No. 4,107,073, etc., containing higher fatty acid alcohol ester compounds, mineral oil or liquid hydrocarbon oil, silicone oil, etc. as components. can be used. Among these, water-based or oil-based antifoaming agents or antifoaming agents containing mineral oil or liquid hydrocarbon oil as a component are particularly preferred from the viewpoint of antifoaming or antifoaming properties. In addition, the antifoaming agent or the foam suppressing agent includes:
It may contain components such as hydrophobic silica, ethylenebishigher alkylamide, and silicone oil. A method for making these defoamers or foam inhibitors present during the cleaning process of unbleached kraft pulp is to add the defoamer or foam inhibitor to the unbleached kraft pulp slurry or thickener at any stage during the cleaning process. It is preferable to add [0014] The natural kraft pulp, preferably wood kraft pulp, used in the practice of the present invention is prepared by washing after cooking, followed by oxygen delignification, preferably further washing, and then bleaching. something can be used to advantage. The treatment conditions for oxygen delignification include a degree of delignification at the oxygen delignification stage of 20 to
It is preferable to set it to 70%, preferably 40 to 50%. Further, the oxygen delignification treatment is carried out in the presence of at least oxygen and an alkali, preferably also an agent for inhibiting a decrease in the degree of polymerization of the pulp. The oxygen used for oxygen delignification treatment is supplied from an oxygen cylinder,
A material whose main component is oxygen produced from air using an oxygen enrichment membrane is advantageously used. Further, in the oxygen delignification treatment, oxygen may be used alone, or an oxygen-based oxidizing agent such as hydrogen peroxide may be used in combination, ozone, nitrogen oxide, etc. may be used. The alkalis used in oxygen delignification treatment include:
Although alkaline liquids such as sodium hydroxide, sodium carbonate, oxidized white liquor, and oxidized green liquor can be used, it is preferable to use oxygenated white liquor. In addition, examples of the pulp polymerization degree reduction inhibitor preferably used in the oxygen delignification treatment include magnesium carbonate, magnesium sulfate, calcium chloride, and the like. As specific conditions for the oxygen delignification treatment, various treatment conditions can be used. for example,
Specifically, the pulp concentration is in the range of 5 wt% to 35 wt%, preferably 10 wt% as the bone dry weight of unbleached pulp.
The amount of oxygen added is in the range of wt% to 20 wt%, and the amount of alkali added is in the range of 0.2 wt% to 4 wt%, preferably 0.5 wt% to 2 wt%, based on the bone dry weight of unbleached pulp. is in the range of 0.2 wt% to 7 wt% in terms of caustic soda per bone dry weight of unbleached pulp, preferably 0.
.. It is in the range of 5wt% to 3wt%. Moreover, the treatment temperature of the oxygen delignification treatment is preferably in the range of 50° C. to 150° C., and the treatment time is preferably in the range of 10 minutes to 180 minutes. In addition, the amount of the pulp polymerization degree reduction inhibitor used as necessary is 0 per absolute dry weight of unbleached pulp.
.. The range is preferably from 0.05 wt% to 1 wt%. The natural kraft pulp, preferably wood kraft pulp, used in the practice of the present invention is one that has been subjected to a bleaching process during its cooking, washing, oxygen delignification, and post-washing bleaching steps. As the bleaching treatment, chlorine treatment, alkali treatment or extraction or purification, hypochlorite bleaching treatment, chlorine dioxide bleaching treatment, and a combination thereof multistage bleaching treatment are preferable, and if necessary, Japanese Patent Publication No. 58
The alkaline peroxide bleaching treatment described or exemplified in No. 43732, or the reductive bleaching treatment using hydrosulfite, sodium borohydride, etc. may be performed. In addition, the bleaching stage mentioned in this specification is the bleaching stage after the chlorination stage. [0016] A preferred multi-stage bleaching treatment system for wood kraft pulp that is advantageously used in the practice of the present invention includes a chlorination stage (hereinafter abbreviated as C) in the first stage and an alkali treatment or extraction stage (hereinafter referred to as C) in the second stage. The third stage is a hypochlorite bleaching stage (hereinafter abbreviated as symbol H) or a chlorine dioxide bleaching stage (hereinafter abbreviated as symbol D). Oxide bleaching stage (
(hereinafter abbreviated as P) is advantageously carried out in the fourth stage or later. For example, "CEHDED", "CEH
DPD”, “CEHDEDP”, “CEHED”, “C
EHPD”, “CEHEDP”, “CEHEH”, “C
EHEHP”, “CEHPHP”, “CEDED”, “
A method such as "CEDEDP" is useful. Chlorine gas or chlorine water is used for chlorine bleaching as the wood kraft pulp bleaching chemical that is advantageously used in the practice of the present invention. Additionally, chlorine dioxide may be used in combination. Caustic soda is advantageously used for the alkaline treatment or extraction, but calcium hydroxide, ammonia, etc. and mixtures thereof can also be used. Hypochlorite bleaching involves bleaching powder made by treating solid powdered slaked lime with chlorine, and especially industrially, hypochlorous acid bleaching solution prepared by blowing chlorine into milk of lime or dilute caustic soda solution. , so-called calcium-hypo bleaching solution, sodium-
A hypo bleaching solution is advantageously used. For chlorine dioxide bleaching,
Mattison method, new Mattison method, Elst method, C. I. Chlorine dioxide prepared by a sulfite method such as the P method, a hydrochloric acid method such as the Kesting method, the Nisso method, or the Solvay method is advantageously used. For alkaline peroxide bleaching, peroxides such as hydrogen peroxide, sodium peroxide, peroxide bleaching solution (hydrogen peroxide, caustic soda, silicate soda, and Advantageously, inorganic or organic peroxides and mixtures thereof are used, such as peracetic acid, tert-butyl hydroperoxide (mixed aqueous solutions consisting of added magnesium sulfate), peracetic acid, tert-butyl hydroperoxide, and as alkalis, caustic soda, potassium hydroxide, Alkali or alkaline earth hydroxides such as aqueous ammonia, magnesium hydroxide, calcium hydroxide and mixtures thereof are advantageously used. Also,
The bleaching treatment can be carried out under various conditions, such as those described in "Pulp Treatment and Bleaching" edited by the Paper and Pulp Technology Association (published on January 27, 1961), Japanese Patent Publication No. 43732/1983. The natural kraft pulp, preferably wood kraft pulp, used in the practice of the present invention has a discoloration count of A-4 due to a silver discoloration reaction as defined herein.
20 or less pieces per A-4, preferably 10 or less pieces per A-4, more preferably 5 or less pieces per A-4, and 2 or less pieces (including 0 pieces) per A-4. is most preferred. Natural kraft pulp, preferably wood kraft pulp, in which the number of discolorations due to silver discoloration reaction is 20 or less per A-4, is specifically treated with oxygen delignification and, for example, by using the following method, Studies by the present inventors have revealed that it can be obtained preferably by using two or more of the following methods, more preferably in combination of three or more. (1) The amount of antifoaming agent to be used is expressed as its components (components excluding water in the case of an aqueous-based antifoaming agent) per unbleached pulp (hereinafter, absolute dry weight unless otherwise specified). ) 0.1-1.5kg, preferably 0.1-1.0k
g, more preferably in the range of 0.1 to 0.75 kg. (2) The pH of the unbleached kraft pulp thickener before entering the bleaching stage is 6.0 or higher, preferably 6.5.
Above, more preferably 7.0 or above. In addition, the pH of unbleached kraft pulp thickener means that 300 g of distilled water is added to 50 g of unbleached kraft pulp thickener, and after stirring well for 1 hour, the liquid temperature is adjusted to 25°C ± 25°C using a pH meter.
Measured at 1°C. (3) The electrical conductivity of the unbleached kraft pulp thickener before entering the bleaching step is adjusted to be at least 50 μmho/cm, preferably at least 100 μmho/cm, and more preferably at least 150 μmho/cm. In addition,
The electrical conductivity of unbleached kraft pulp thickener is as follows: Add 300 g of distilled water to 50 g of unbleached kraft pulp thickener, stir well for 1 hour, and then measure the liquid temperature at 25°C using an electrical conductivity meter.
Measured at ±1°C. (4) The calcium content in the unbleached kraft pulp before entering the bleaching stage is minimized. Specifically, when paper is made of unbleached kraft pulp thickener before entering the bleaching stage, the calcium content in the paper is reduced to 50%.
00 ppm or less, preferably 4000 ppm or less, more preferably 3000 ppm or less. The paper was prepared using unbleached kraft pulp thickener in accordance with Tappi Standard T-205, except that deionized water was used. It was measured using the X-ray method. (5) The calcium content in unbleached white water should be as low as possible. To this end, the calcium content derived from the cooking process is reduced. For example, selecting an appropriate tree species, improving the removal efficiency of insoluble calcium salts present in white water, such as calcium hydroxide and calcium carbonate, by filtration, and adding chelating agents, such as EDTA-sodium salt, to unbleached white water. It is preferable to add . (6) The pH of the kraft pulp slurry in the chlorine stage is 2.5 or less, preferably 2.5 or less.
The value should be 0 or less, more preferably 1.5 or less. (7) Before entering the papermaking process, the bleached kraft pulp is cleaned using a cleaner, preferably a liquid cyclone type cleaner. The final rejection rate in the cleaner is preferably 0.02% by weight or more, preferably 0.05% by weight or more, and more preferably 0.1% by weight or more, based on the bone dry pulp. [0026] The base paper used in the practice of the present invention can contain various additives at the time of preparing the paper stock slurry. Sizing agents include fatty acid metal salts and/or fatty acids, alkyl ketene dimer emulsions or epoxidized higher fatty acid amides as described or exemplified in Japanese Patent Publication No. 62-7534, alkenyl or alkyl succinic anhydride emulsions, rosin derivatives, etc. As a paper strength enhancer,
Anionic, cationic or amphoteric polyacrylamide, polyvinyl alcohol, cationized starch, vegetable galactomannan, etc., as a wet paper strength enhancer, polyamine polyamide epichlorohydrin resin, etc., as a filler,
Clay, kaolin, calcium carbonate, titanium oxide, etc.; water-soluble aluminum salts such as aluminum chloride, aluminum sulfate, etc. as fixing agents; caustic soda, soda carbonate, sulfuric acid, etc. as pH regulators; and others JP-A-63-204251
It is advantageous to contain a suitable combination of coloring pigments, coloring dyes, fluorescent brighteners, etc. described or exemplified in JP-A-1-266537 and the like. [0027] Furthermore, various water-soluble polymers, antistatic agents, and additives can be added to the base paper used in the practice of the present invention by spraying or tab size press. As a water-soluble polymer, JP-A-1-266
Starch polymers, polyvinyl alcohol polymers, gelatin polymers, polyacrylamide polymers, cellulose polymers, etc. described or exemplified in No. Alkaline earth metal salts such as barium, colloidal metal oxides such as colloidal silica, organic antistatic agents such as polystyrene sulfonates, latexes, emulsions, petroleum resin emulsions, styrene-acrylic acid-acrylic acid esters, etc. Latex such as copolymers, styrene-acrylic acid-butadiene copolymers, ethylene-vinyl acetate copolymers, styrene-maleic acid-acrylic acid ester copolymers, pigments such as clay, kaolin, talc, barium sulfate, oxidation It is advantageous to contain a pH adjusting agent such as titanium, hydrochloric acid, phosphoric acid, citric acid, caustic soda, etc., as well as an appropriate combination of additives such as the above-mentioned colored pigments, colored dyes, and optical brighteners. [0028] The base paper used in carrying out the present invention is as follows:
It is preferable to have a smooth surface with a Beck smoothness of 100 seconds or more as defined by JIS P8119, and 200 seconds or more.
It is even more preferable to have a smooth surface with a smoothness of at least 2 seconds. As a method for producing a base paper with a Bekk smoothness of 100 seconds or more, generally a large amount of hardwood pulp, which has short fibers and is easily smooth, is used, and the pulp is beaten using a beating machine to reduce the long fiber content as much as possible. Specifically, the pulp is preferably beaten so that the fiber length of the pulp after beating is such that the 42 mesh residue is 20 to 45% and the freeness is 200 to 350 CSF. Next, regarding paper stock chillers with internal additives added, JP-A No. 58-37642 and JP-A No. 61-260240
A uniform texture can be obtained using a commonly used paper machine such as a fourdrinier paper machine or a circular paper machine by adopting an appropriate paper making method as described or exemplified in JP-A No. 61-284762. A base paper having a Bekk smoothness of 100 seconds or more can be produced by papermaking as described above, and then calendering using a machine calender, a supercalender, a thermal calender, etc. after the papermaking. There are no particular restrictions on the thickness of the base paper, but its basis weight is 40 g/m2 to 250 g/m
2 is preferred. As the film-forming resin used in the practice of the present invention, thermoplastic resins such as polyolefin resins, polycarbonate resins, polyester resins, and polyamide resins are preferable, and among them, thermoplastic resins are preferable in terms of melt extrusion coating properties. More preferred are polyolefin resins. Also,
It may be coated with an electron beam curing resin described or exemplified in Japanese Patent Publication No. 60-17104. Polyolefin resins preferably used in the practice of the present invention include homopolymers such as polyethylene, polypropylene, polybutene, and polypentene, copolymers consisting of two or more α-olefins such as ethylene-butylene copolymers, and copolymers of these. Among them, polyethylene resin is particularly preferred from the viewpoint of melt extrusion coating properties and adhesion to the base paper. These polyethylene resins include low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, copolymers of ethylene and α-olefins such as propylene and butylene, carboxy-modified polyethylene, etc. It is a mixture and can have various densities, melt flow rates (hereinafter simply referred to as MFR), molecular weights, and molecular weight distributions, but usually has a density of 0.90 to 0.97 g/
cm3 range, MFR0.1g/10min~40g/1
0 minutes, preferably MFR0.3g/10 minutes to 30g/
10 minutes, those having a molecular weight in the range of 20,000 to 250,000 can be advantageously used alone or in combination. In addition, if the resin has a multilayer structure, the outermost layer resin may have a MFR of 5g/10, for example.
It is also possible to use resins with different properties and configurations, such as those with MFR of 2 g/10 minutes to 10 g/10 minutes, as the lower layer resin. [0031] Various additives can be contained in the resin layer of the support for photosensitive materials in the present invention. Special Publication No. 60-3430, Special Publication No. 63-11655,
White pigments such as titanium oxide, zinc oxide, talc, calcium carbonate, etc., stearic acid amide, arachidic acid amide, etc. described or exemplified in Japanese Patent Publication No. 1-38291, Japanese Patent Publication No. 1-38292, and Japanese Patent Publication No. 1-105245, etc. Fatty acid metal salts such as fatty acid amide, zinc stearate, calcium stearate, aluminum stearate, magnesium stearate, zinc palmitate, zinc myristate, calcium palmitate, etc., JP-A-1-1052
Various antioxidants such as hindered phenol, hindered amine, phosphorus type, and sulfur type antioxidants described or exemplified in No. 45,
Blue pigments and dyes such as cobalt blue, ultramarine blue, ceriam blue, and phthalocyanine blue; magenta pigments and dyes such as cobalt violet, fast violet, and manganese violet; Various additives such as fluorescent brighteners and ultraviolet absorbers can be contained in appropriate combinations. Preferably, these additives are included as a masterbatch or compound of a film-forming resin. In addition, when the film-forming resin is a thermoplastic resin, preferably a polyethylene resin, the resin layer is preferably manufactured by a melt extrusion coating method in which the molten resin is coated on a running base paper. . Before coating the base paper with the resin, it is preferable to subject the base paper to an activation treatment such as a corona discharge treatment or a flame treatment. In the present invention, the surface of the photosensitive layer side of the support for a photosensitive material is a glossy surface or a surface of Japanese Patent Publication No. 62-197 which does not affect the gloss of the surface of the photosensitive material when it is made into a photosensitive material.
It has a finely rough surface, matte surface, silky surface, etc. as described in No. 32, and the back surface is usually a matte surface, and if necessary, the front surface or both the front and back surfaces can be subjected to activation treatment such as corona discharge treatment or flame treatment. can be administered. Further, after the activation process, a subbing process as described in JP-A-61-84643 can be performed. Further, there is no particular restriction on the thickness of the front and back resin layers, but it is generally advantageous to have a thickness of about 10 .mu.m to 50 .mu.m. [0033] The support for the photosensitive material in the present invention can be coated with various back coat layers for antistatic purposes, anti-curling, and the like. In addition, for the back coat layer, Japanese Patent Publication No. 52-18020, Japanese Patent Publication No. 57-9059,
JP 57-53940, JP 58-56859, JP 59-214849, JP 58-184
Inorganic antistatic agents, organic antistatic agents, hydrophilic binders, latexes, curing agents, pigments, surfactants, etc. described or exemplified in No. 144 and the like may be contained in appropriate combinations. The support for photosensitive materials in the present invention is coated with various photographic constituent layers and can be used for color photographic paper, black and white photographic paper, typesetting photographic paper, copying photographic paper, and reversal photographic material. It can be used for various purposes such as silver salt diffusion transfer negatives and printing materials. For example, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide emulsion layers can be provided. A multilayer silver halide color photographic constituent layer can be provided by incorporating a color coupler in the silver halide photographic emulsion layer. Further, a photosensitive layer for silver salt diffusion transfer method can be provided. As the binder for these photographic constituent layers, in addition to ordinary gelatin, hydrophilic polymeric substances such as polyvinylpyrrolidone, polyvinyl alcohol, and polysaccharide sulfate ester compounds can be used. Further, the above-mentioned photographic constituent layer can contain various additives. For example, sensitizing dyes include cyanine dyes and merocyanine dyes, chemical sensitizers include water-soluble gold compounds and sulfur compounds, and antifoggants or stabilizers include hydroxy-triazolopyrimidine compounds and mercapto-heterocyclic compounds. Hardeners include formalin, vinyl sulfone compounds, aziridine compounds, etc. Coating aids include alkylbenzene sulfonates, sulfosuccinates, etc. Anti-staining agents include dialkylhydroquinone compounds, and other optical brighteners and sharpness improvers. A dye, an antistatic agent, a pH adjuster, a fogging agent, and further a water-soluble iridium, a water-soluble rhodium compound, etc. can be contained in an appropriate combination during the production and dispersion of silver halide. The photosensitive material of the present invention can be exposed to light as described in ``Photographic Photosensitive Materials and Handling Methods'' (Kyoritsu Shuppan, written by Goro Miyamoto, Photographic Technology Course 2), depending on the photosensitive material.
Processes such as development, stopping, fixing, bleaching, and stabilization are carried out, and multilayer silver halide color photographic light-sensitive materials that undergo one-bath bleach-fixing treatment after color development are CD-III and CD-IV.
Processing can be carried out with any color developer containing any main ingredient, such as (the above two compounds are trade names of Kodak Co.) and droxychrome (trade name of May and Baker Co.). A developer containing such a main agent may contain a development accelerator such as benzyl alcohol, thallium salt, or phenidone.
It is also possible to process with a developer substantially free of benzyl alcohol. Also, useful one-bath bleach-fix solutions are solutions of metal salts of aminopolycarboxylic acids (e.g., ferric complex salts such as ethylenediaminetetraacetic acid and propylenediaminetetraacetic acid), and the fixing agent is sodium thiosulfate. , ammonium thiosulfate, and the like are useful. Such a one-bath bleach-fix solution may contain various additives. For example, desilvering accelerators (e.g., U.S. Pat. No. 3,512,97
mercaptocarboxylic acids described in Belgian Patent No. 9, mercapto-heterocyclic compounds described in Belgian Patent No. 682,426, etc.), antifouling agents, pH adjusters or pH buffers,
Various compounds such as hardeners (for example, magnesium sulfate, aluminum sulfate, potassium alum, etc.) and surfactants can be contained in combination. Additionally, such one-bath bleach-fix solutions may be used at a variety of pHs, but at a useful pH.
The range is pH 6.0-8.0. [Example] Next, in order to explain the present invention more specifically,
An example will be described. Example 1 In the manufacturing process of hardwood kraft pulp, the unbleached kraft pulp after cooking was washed in the first stage washing process, and then subjected to oxygen delignification treatment under the following conditions. It was washed in the first washing process, and then bleached using the "CEHDPD" method in the subsequent steps. On the other hand, the oxygen delignification treatment was omitted in the manufacturing process of hardwood pulp for comparison. The conditions for oxygen delignification treatment are:
The pulp concentration was 15 wt% as the bone dry weight of unbleached pulp, the amounts of caustic soda and oxygen added were 1.5 wt% and 1.0 wt%, respectively, based on the bone dry weight of unbleached pulp, and the treatment temperature and treatment time were 110°C and 45 minutes, respectively. Met. Also,
As a process condition other than the oxygen delignification process of hardwood kraft pulp, the total amount of oil-based antifoaming agent containing mineral oil as a component in the washing stage of unbleached kraft pulp is 1 ton of absolute dry weight of unbleached pulp. 0.7kg, 1.0k per
g, 1.5 kg or 2.0 kg, the electrical conductivity of the unbleached thickener as defined in the specification is 100 μmho/cm, and the final rejection rate of the liquid cyclone type cleaner is 0.5 kg compared to bone dry pulp. 01wt%, 0.02wt%
, 0.05 wt% or 0.1 wt%, adjusted to the combinations listed in Table 1, and adjusting other process conditions appropriately, the number of discolored particles due to the silver discoloration reaction defined in the specification is as shown in Table 1. Hardwood bleached kraft pulps were obtained as follows. [0038] Next, each pulp was
Beaten to 320 ml of standard freeness, and further add 3 parts by weight of cationized starch to 100 parts by weight of pulp.
0.2 parts by weight of anionized polyacrylamide, 0.0 parts of alkyl ketene dimer emulsion (as ketene dimer content).
4 parts by weight and 0.4 parts by weight of polyaminopolyamide epichlorohydrin resin were added to produce paper with a basis weight of 100 g/m2. The obtained wet paper paper was dried at 110°C, and then mixed with 3 parts by weight of carboxy-modified polyvinyl alcohol, 0.05 parts by weight of optical brightener, 0.002 parts by weight of blue dye, 0.2 parts by weight of citric acid, and 97 parts by weight of water. An impregnating solution consisting of 25 parts
After impregnating the paper with g/m2, drying with hot air at 110°C, and supercalendering at a linear pressure of 90kg/cm, both sides of the paper were subjected to corona discharge treatment to produce a base paper for a support for a photosensitive material. Next, low density polyethylene resin (density 0.92 g/cm3, MFR=8.5 g/1
0 min) 47.5 wt%, hydrated aluminum oxide (0.75 wt% as Al2O3 min with respect to titanium dioxide)
20 parts by weight of a titanium dioxide pigment masterbatch consisting of 50% by weight of anatase-type titanium dioxide pigment and 2.5% by weight of zinc stearate, which had been surface-treated with a low-density polyethylene resin (density 0.92 g/cm3, MFR=4. 5g
/10 minutes) 65 parts by weight and high density polyethylene resin (density 0.97 g/cm3, MFR = 7.0 g/10 minutes) 1
13 parts by weight of a resin composition at a resin temperature of 330°C.
Melt extrusion coating was performed to a thickness of μ. In addition, before coating the resin layer on the surface of the base paper, the opposite side (back side) of the base paper
, low-density polyethylene resin (density 0.92 g/cm3
, MFR2g/10min) 15 parts by weight and high density polyethylene resin (density 0.96g/cm3, MFR20g/10
) 85 parts by weight of the resin composition at a resin temperature of 330°C.
Melt extrusion coating was applied to the same thickness as the surface. At this time, the surface of the resin layer containing the titanium dioxide pigment of the support for a light-sensitive material produced in this manner was processed to have a slightly rough surface, and the surface quality of the back resin layer was processed to have a paper-like matte surface. Thereafter, a back coat layer having a composition of colloidal silica: styrene acrylic latex = 1:1 was coated at 0.4 g/m 2 on the back surface of the support for photosensitive materials after corona discharge treatment. Next, a corona discharge treated emulsion layer and its protective layer were provided on the front resin surface containing the titanium dioxide pigment of the photosensitive material support to obtain a black and white photographic paper. The emulsion layer is hexachloroiridium(III)
14. gelatin in the presence of 1.2 x 10-5 g of potassium.
ArBr/AgCl = 65/35 produced by producing and dispersing 19.2g of silver halide particles with silver nitrate in 4g
Substantially [1
, 0, 0] plane, and further contains gelatin necessary for film formation, as well as appropriate amounts of stabilizers, sensitizing dyes, coating aids, hardeners, and optical brighteners. , thickener, filter dye, etc., and was coated in a multilayer together with a protective layer at a coating amount corresponding to 2.2 g/m 2 of silver nitrate and 4.4 g/m 2 of gelatin. The protective layer contains gelatin equivalent to 2 g/m 2 as well as coating aids and hardeners. [0041] The coated and dried sample had a temperature of 4 at 50°C and 81%.
After being stored for a day, it was developed in black and white and the number of speckled fogs was counted. The results obtained are shown in Table 1. [Table 1] [0043] As can be seen from Table 1, wood kraft pulp that has been subjected to oxygen delignification treatment and has a discoloration of 20 or less particles per A-4 due to a silver discoloration reaction as defined in the specification is used. The sample of the present invention, which was used as a wood kraft pulp, had less occurrence of spot fog, and the number of discoloration was 1 per A-4 as a wood craft pulp.
It is clear that the number is preferably 0 or less, and more preferably 5 or less per A-4. Example 2 The same procedure as in Example 1 was carried out, except that instead of the wood kraft pulp used in Example 1, one was subjected to oxygen delignification treatment and produced under the following process conditions. carried out. In the manufacturing process of hardwood kraft pulp, as a process condition, the total amount of oil-based antifoaming agent containing mineral oil as a component in the washing stage of unbleached kraft pulp is 0.1 kg per ton of weight, 0
.. 7kg, 1.0kg, 1.5kg or 2.0kg,
The electrical conductivity of unbleached thickener as defined in the specification is 45
μmho/cm, 100μmho/cm or 150μ
mho/cm, and the final rejection rate of the liquid cyclone type cleaner is 0.01 wt% with respect to bone dry pulp,
0.02 wt%, 0.05 wt%, or 0.1 wt%, adjusted to the combinations listed in Table 2, and other process conditions appropriately adjusted to cause discoloration due to the silver discoloration reaction defined in the specification. Hardwood bleached pulps having the numbers shown in Table 2 were obtained. Note that the amount of antifoaming agent present is 0.
When the weight was less than 1 kg, foaming was insufficiently prevented. The results obtained are shown in Table 2. [Table 2] [0048] As can be seen from Table 2, wood kraft pulp that has been subjected to oxygen delignification treatment and has a discoloration of 20 or less particles per A-4 due to a silver discoloration reaction as defined in the specification is used. The sample of the present invention, which was used as a wood kraft pulp, had less occurrence of spot fog, and the number of discoloration was 1 per A-4 as a wood craft pulp.
It is clear that the number is preferably 0 or less, and more preferably 5 or less per A-4. Example 3 The same procedure as in Example 1 was carried out, except that instead of the wood kraft pulp used in Example 1, one was subjected to oxygen delignification treatment and produced under the following process conditions. carried out. In the manufacturing process of hardwood kraft pulp, as a process condition, the total amount of oil-based antifoaming agent containing mineral oil as a component in the washing stage of unbleached kraft pulp is 0.1 kg per ton of weight, 0
.. 7kg, 1.0kg, 1.5kg or 2.0kg,
Calcium content in unbleached kraft pulp as defined in the specification is 3000 ppm, 4000 ppm, or 5
500 ppm, and the pH of the kraft pulp slurry at the chlorine stage is pH 1.5, pH 2.0 or pH 2.7.
By adjusting the combinations shown in Table 3 and adjusting other process conditions as appropriate, hardwood bleached pulps having the number of discolored particles due to the silver discoloration reaction defined in the specification as shown in Table 3 were obtained. Ta. The results obtained are shown in Table 3. [Table 3] [0053] As can be seen from Table 3, wood kraft pulp that has been subjected to oxygen delignification treatment and has a discoloration of 20 or less pieces per A-4 due to a silver discoloration reaction as defined in the specification is used. It can be clearly seen that the samples of the present invention, which were used as wood kraft pulps, have little occurrence of spotty fog, and as a wood craft pulp, the number of discolored particles is preferably 10 or less per A-4, and more preferably 5 or less per A-4. Example 4 The number of discolorations caused by the silver discoloration reaction used in Example 2 was A-
The procedure was the same as in Example 1, except that wood kraft pulp with 2.25 pieces and 28 pieces per 4 pieces was used, the basis weight of the base paper was 160 g/m2, and the thickness of the front and back resin layers were each 30 μm. A support for a photosensitive material was obtained. Next, the resin surface on the front side containing the titanium dioxide pigment of the support for a light-sensitive material was subjected to a corona discharge treatment, and then the following emulsion layer and its protective layer were provided to obtain a photographic paper. The emulsion layer is potassium hexachloroiridium(III) 1.0×10-5
In the presence of 9.6 g of silver nitrate in 4.8 g of gelatin
AgB produced by producing and dispersing silver halide grains
Sulfur-sensitized to the highest sensitivity with an average particle size of 0.8μ and a halogen composition of r/AgCl = 95/5 [1, 0, 0
Contains a neutral silver halide photographic emulsion consisting of a mixed crystal of ] and [1,1,1] planes, and further contains a yellow color-forming coupler and gelatin necessary for film formation, as well as an appropriate amount of stabilizers and blue sensitivity. Contains sensitizing dyes, coating aids, hardeners, thickeners, etc., and contains 0 silver nitrate.
.. A multilayer coating was carried out together with a protective layer at a coating weight of 6 g/m2, which corresponds to 1.5 g/m2 of gelatin. The protective layer is 1.5
In addition to gelatin equivalent to g/m2, coating aids, thickeners,
Contains hardening agents, etc. [0056] The coated and dried sample had a temperature of 4 at 50°C and 81%.
After storage for a day, color development was performed and the number of speckled fogs was counted. In addition, the sample after heating and storage was uniformly exposed to light so that the yellow color density was 0.4, and then color development was carried out.
The number of areas with spotty desensitization was measured. [0057] As a result, no spot failure was observed in the test section of the present invention using wood kraft pulp in which the number of discolorations due to silver discoloration reaction was 2.25 per A-4. On the other hand, in a test outside the present invention using wood craft pulp in which the number of discolorations due to silver discoloration reaction was 28 per A-4, there were several spots of fogging and more than 10 spots of fading per A-4. The feeling was recognized. Example 5 The number of silver discolorations used in Example 2 was 2.25 per A-4.
A base paper for a support for a photosensitive material was produced in the same manner as in Example 1, except that the basis weight of the base paper was 135 g/cm 2 using wood kraft pulps of 1 and 28. [0059] After that, low density polyethylene resin (density 0.92 g/cm3, MFR 4.5 g/1
0 minutes) were melt-extruded and coated at a resin temperature of 330 DEG C. to a thickness of 18 .mu.m. At that time, both sides of the support for a photosensitive material were processed to have a paper-like matte surface. Next, a back coat layer containing silica particles having an average particle diameter of 4 μm after corona discharge treatment, gelatin of 1.0 g/m 2 and a hardening agent was coated on one side of the support for light-sensitive materials. Next, carbon black with an average particle size of 7 after corona discharge treatment was applied to the support surface opposite to the back coat layer.
Sulfur sensitization and gold sensitization achieve the highest sensitivity with an average particle diameter of 0.4μ, which has an undercoat layer consisting of μ silica particles and gelatin 3.5g/m2, a hardener, and a halogen composition of AgBr/AgCl = 5/95. Combined sensitization substantially [1,0
, 0] planes, and further contains gelatin necessary for film formation, as well as appropriate amounts of stabilizers, ortho sensitizing dyes, phenidone, coating aids, hardeners, etc. were coated in multiple layers at a coating amount corresponding to 1.0 g/m2 of silver nitrate and 1.0 g/m2 of gelatin. After coating and drying, the emulsion layer was heated at 40°C for 3 days, and then a coating solution consisting of a copolymer of acrylamide and imidazole, hydroquinone, palladium sulfide cores, etc. was coated with palladium sulfide sol 1.0.
A light-sensitive material for a planographic printing plate was obtained by coating at a rate of g/m2. [0061] The coated and dried sample was kept in a roll at 50°C.
After storage at 81% for 4 days, the film was cut, followed by diffusion transfer development, and the number of spot defects was counted. As a result, in the sample of the present invention using wood kraft pulp in which the number of discolorations due to silver discoloration reaction was 2.25 per A-4, no spot-like failure was observed at all. On the other hand, in a sample other than the present invention using wood craft pulp in which the number of discolorations due to silver discoloration reaction was 28 per A-4, there were many spot failures in which transferred silver was missing or thinned in spots. Admitted. Example 6 In Example 1, the oxygen delignification treatment conditions were changed to the following conditions (
The same procedure as in Example 1 was carried out except for setting 1) or (2), and the same results as in Example 1 were obtained. Condition (1): The pulp concentration is 20 wt% as the bone dry weight of unbleached pulp, and the added amounts of caustic soda and oxygen are 3 wt% and 2.1 w, respectively, based on the bone dry weight of unbleached pulp.
t%, treatment temperature and treatment time were 110℃ and 3, respectively.
It is 0 minutes. Condition (2): The pulp concentration is 27 wt% based on the bone dry weight of unbleached pulp, and the amounts of caustic soda and oxygen added are 2.0 wt% and 1, respectively, based on the bone dry weight of unbleached pulp.
.. 5 wt%, treatment temperature and treatment time were 98° C. and 2 hours, respectively. Example 7 The same procedure as in Example 1 was carried out except that instead of caustic soda as the alkali, oxidized white liquor was used as the caustic soda component in the same amount as in Example 1, and the same results as in Example 1 were obtained. Obtained. Effects of the Invention The present invention provides an excellent support for a photosensitive material, which has a paper substrate mainly composed of natural pulp, in which the tendency of spot failure to occur in a silver halide photosensitive layer is significantly suppressed. The body can provide.
Claims (6)
ルム形成能ある樹脂で被覆した感光材料用支持体におい
て、該基紙を構成する天然パルプの一部または全部が天
然クラフトパルプであり、該天然クラフトパルプが、ク
ラフト法による蒸解後その未晒段階で消泡剤あるいは抑
泡剤の存在下に洗浄処理され、かつ洗浄処理に前後して
酸素脱リグニン処理され、その後の漂白段階で漂白処理
されたものであり、なおかつ該天然クラフトパルプの下
記で定義される銀変色反応による変色発生個数がA−4
当り20個以下のものであることを特徴とする感光材料
用支持体。銀変色反応による変色発生個数:Tappi
スタンダードT444に基づいて調製された銀面板の
銀面に天然クラフトパルプ試料(試料条件としては、坪
量;750g/m2±150g/m2,絶乾水分量;2
0重量%±5重量%,pH;Tappi スタンダード
T205に基づいて調製された時のパルプ懸濁液のpH
として6.0〜7.5である)を密着させて黒ポリ袋に
封入し、A−4当り2.5kgの荷重をかけて、温度5
0℃±1℃、相対湿度81%±2%で50時間加温処理
を行い、その後銀面上の銀変色反応の発生個数を計測し
たものである。1. A support for a photosensitive material comprising a base paper containing natural pulp as a main component and coated with a resin capable of forming a film, wherein part or all of the natural pulp constituting the base paper is a natural kraft pulp, After the natural kraft pulp is cooked by the kraft method, it is washed in the presence of an antifoaming agent or a foam suppressor in the unbleached stage, and is subjected to oxygen delignification treatment before and after the washing treatment, and then bleached in the subsequent bleaching stage. The number of discoloration caused by the silver discoloration reaction defined below of the natural kraft pulp is A-4.
A support for a photosensitive material, characterized in that each support has 20 or less pieces. Number of discoloration caused by silver discoloration reaction: Tappi
A natural kraft pulp sample (sample conditions include basis weight: 750 g/m2 ± 150 g/m2, bone dry moisture content: 2) on the silver surface of a silver plate prepared based on standard T444.
0% by weight ± 5% by weight, pH; pH of pulp suspension when prepared based on Tappi standard T205
6.0 to 7.5) were tightly sealed in a black plastic bag, a load of 2.5 kg was applied to each A-4, and the temperature was 5.
A heating treatment was performed at 0° C.±1° C. and a relative humidity of 81%±2% for 50 hours, and then the number of silver discoloration reactions occurring on the silver surface was counted.
ィン樹脂である請求項1記載の感光材料用支持体。2. The support for a photosensitive material according to claim 1, wherein the resin capable of forming a film is a polyolefin resin.
樹脂である請求項2記載の感光材料用支持体。3. The support for a photosensitive material according to claim 2, wherein the polyolefin resin is a polyethylene resin.
として含むものである請求項1、2または3記載の感光
材料用支持体。4. The support for a photosensitive material according to claim 1, 2 or 3, wherein the antifoaming agent or foam suppressing agent contains mineral oil as a component.
在量が、未晒パルプ絶乾重量1トン当り0.1kg〜1
.5kgである請求項1、2、3または4記載の感光材
料用支持体。5. The total amount of antifoaming agent or foam suppressing agent is 0.1 kg to 1 ton per ton of bone dry weight of unbleached pulp.
.. The support for a photosensitive material according to claim 1, 2, 3 or 4, which weighs 5 kg.
−4当り10個以下のものである請求項1、2、3、4
または5記載の感光材料用支持体。Claim 6: The number of discolored particles due to silver discoloration reaction is A
-Claims 1, 2, 3, and 4 in which the number of pieces is 10 or less per 4.
or 5. The support for a photosensitive material according to 5.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14246291A JP2871895B2 (en) | 1991-05-17 | 1991-05-17 | Support for photosensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP14246291A JP2871895B2 (en) | 1991-05-17 | 1991-05-17 | Support for photosensitive material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH04342250A true JPH04342250A (en) | 1992-11-27 |
JP2871895B2 JP2871895B2 (en) | 1999-03-17 |
Family
ID=15315882
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP14246291A Expired - Fee Related JP2871895B2 (en) | 1991-05-17 | 1991-05-17 | Support for photosensitive material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2871895B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002517622A (en) * | 1998-06-01 | 2002-06-18 | ユー.エス.ボラックス インコーポレイテッド | Partial automatic causticization of alkaline liquids for wood pulping. |
-
1991
- 1991-05-17 JP JP14246291A patent/JP2871895B2/en not_active Expired - Fee Related
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002517622A (en) * | 1998-06-01 | 2002-06-18 | ユー.エス.ボラックス インコーポレイテッド | Partial automatic causticization of alkaline liquids for wood pulping. |
Also Published As
Publication number | Publication date |
---|---|
JP2871895B2 (en) | 1999-03-17 |
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