JPH02207243A - Silver halide photographic sensitive material having improved electrostatic chargeability - Google Patents
Silver halide photographic sensitive material having improved electrostatic chargeabilityInfo
- Publication number
- JPH02207243A JPH02207243A JP2938889A JP2938889A JPH02207243A JP H02207243 A JPH02207243 A JP H02207243A JP 2938889 A JP2938889 A JP 2938889A JP 2938889 A JP2938889 A JP 2938889A JP H02207243 A JPH02207243 A JP H02207243A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- general formula
- silver halide
- formula
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 Silver halide Chemical class 0.000 title claims description 34
- 229910052709 silver Inorganic materials 0.000 title claims description 27
- 239000004332 silver Substances 0.000 title claims description 27
- 239000000463 material Substances 0.000 title claims description 18
- 239000000839 emulsion Substances 0.000 claims abstract description 24
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 14
- 125000003277 amino group Chemical group 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 125000005647 linker group Chemical group 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 2
- 125000000732 arylene group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims 2
- 238000011161 development Methods 0.000 abstract description 9
- 230000006866 deterioration Effects 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- 238000000034 method Methods 0.000 description 17
- 239000010410 layer Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 239000002245 particle Substances 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 206010070834 Sensitisation Diseases 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DTCCVIYSGXONHU-CJHDCQNGSA-N (z)-2-(2-phenylethenyl)but-2-enedioic acid Chemical compound OC(=O)\C=C(C(O)=O)\C=CC1=CC=CC=C1 DTCCVIYSGXONHU-CJHDCQNGSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- HCBIBCJNVBAKAB-UHFFFAOYSA-N Procaine hydrochloride Chemical compound Cl.CCN(CC)CCOC(=O)C1=CC=C(N)C=C1 HCBIBCJNVBAKAB-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 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
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- FHQNDVKBVRQZQA-UHFFFAOYSA-N butyl prop-2-enoate 5-phenylpenta-2,4-dienoic acid Chemical compound CCCCOC(=O)C=C.OC(=O)C=CC=CC1=CC=CC=C1 FHQNDVKBVRQZQA-UHFFFAOYSA-N 0.000 description 1
- QMRMTRCBDHFTIV-UHFFFAOYSA-N butyl prop-2-enoate;prop-2-enenitrile;prop-2-enoic acid Chemical compound C=CC#N.OC(=O)C=C.CCCCOC(=O)C=C QMRMTRCBDHFTIV-UHFFFAOYSA-N 0.000 description 1
- TUZBYYLVVXPEMA-UHFFFAOYSA-N butyl prop-2-enoate;styrene Chemical compound C=CC1=CC=CC=C1.CCCCOC(=O)C=C TUZBYYLVVXPEMA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 229960000878 docusate sodium Drugs 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- NMLPGTZALRWFDE-UHFFFAOYSA-N ethyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(=O)C=C.COC(=O)C(C)=C NMLPGTZALRWFDE-UHFFFAOYSA-N 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、ハロゲン化銀写真感光材料に関し、詳しくは
帯電防止能の優れたハロゲン化銀写真感光材料に関する
。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having excellent antistatic properties.
ハロゲン化銀写真感光材料においては、特に冬季の如き
低湿度において帯電し易い。最近のように高感度写真乳
剤を高速度で塗布したり、高感度の感光材料を自動プリ
ンターを通して露光処理をする場合、特に帯電防止対策
が重要である。Silver halide photographic materials are easily charged, especially at low humidity such as in winter. Antistatic measures are especially important when high-speed photographic emulsions are coated at high speeds or when high-sensitivity photosensitive materials are exposed to light using automatic printers, as has been the case recently.
感光材料か帯電すると、その放電によりスタチックマー
クがでたり、またはゴミ等の異物を付着し、これにより
ピンホールを発生させたりして著しく品質を劣化し、そ
の修正のため非常に作業性をおとしてしまう。このため
、一般に感光材料では帯電防止剤が使用され、最近では
、含フツ素界面活性剤、カチオン界面活性剤、両性界面
活性剤、ポリエチレンオキザイド基を含有する界面活性
剤ないし高分子化合物、スルホン酸またはリン酸基を分
子内に有するポリマー等か用いられている。When a photosensitive material is charged, static marks appear due to the discharge, or foreign substances such as dust adhere to it, which causes pinholes and significantly deteriorates the quality, making it extremely difficult to repair. I'll put it down. For this reason, antistatic agents are generally used in photosensitive materials, and recently, fluorine-containing surfactants, cationic surfactants, amphoteric surfactants, surfactants or polymer compounds containing polyethylene oxide groups, and sulfone Polymers having acid or phosphoric acid groups in the molecule are used.
特にフッ素系界面活性剤による帯電列調整、あるいは導
電性ポリマーによる導電性向上が多く使用されてきてお
り、例えは特開昭４９−９１１６５号および同４９−１
２１５２３号にはポリマー主鎖中に解離基を有するイオ
ン型ポリマーを適用する例が開示されている。In particular, adjusting the charge series using fluorine-based surfactants or improving conductivity using conductive polymers has been widely used.
No. 21523 discloses an example in which an ionic polymer having a dissociative group in the polymer main chain is applied.
しかしなから、これらの従来技術では、現像処理により
、帯電防止能が大幅に劣化してしまう。However, in these conventional techniques, the antistatic ability is significantly deteriorated by the development process.
これはアルカリを用いる現像工程、酸性の定着工程、水
洗等の工程を経ることにより帯電防止能が失われるもの
と思われる。したがって印刷感光材料等のように、処理
済みフィルムをさらに用し１てプリントするような場合
に、ゴミの付着によるピンホール発生等の問題を生ずる
。This is thought to be because the antistatic ability is lost through processes such as a developing process using an alkali, an acidic fixing process, and washing with water. Therefore, when a processed film is further used for printing, such as with printing photosensitive materials, problems such as pinholes occur due to adhesion of dust.
上記のような問題に対し、本発明の目的は、現像処理後
も帯電防止能の劣化の起こらないハロゲン化銀写真感光
材料を提供することである。In order to solve the above problems, an object of the present invention is to provide a silver halide photographic material whose antistatic ability does not deteriorate even after development.
本発明の上記目的は、感光性乳剤層を設けた支持体の反
対側に、下記一般式〔■〕で表される繰り返し単位を有
する水溶性ポリマーを含有する層を少なくとも１層有し
、核層よりも支持体より遠い層に、一般式〔■〕及び／
又は一般式〔ＩＩＩ〕で表される化合物を含有させたこ
とを特徴とするハロゲン化銀写真感光利料により達成さ
れる。The above object of the present invention is to have at least one layer containing a water-soluble polymer having a repeating unit represented by the following general formula [■] on the opposite side of a support provided with a photosensitive emulsion layer, The general formula [■] and /
Alternatively, it can be achieved by a silver halide photographic material containing a compound represented by the general formula [III].
般式〔■〕
（ＣＨ２Ｃ）Ｘ（Ａ）Ｖ（Ｂ）Ｚ（Ｃ）Ｗ（ＳＯ３Ｍ）
ｎ
〔式中、Ｒは水素原子、ハロゲン原子、またはアルキル
基を表し、Ａ、Ｂ、Ｃはそれぞれ共重合可能なカルボキ
シ基またはそのエステル誘導体またはハロゲン原子を含
むエチレン性不飽和モノマーを共重合した互いに異なる
七ツマー単位を表す。General formula [■] (CH2C)X(A)V(B)Z(C)W(SO3M)
n [In the formula, R represents a hydrogen atom, a halogen atom, or an alkyl group, and A, B, and C are each a copolymerizable carboxyl group or an ester derivative thereof, or a copolymerized ethylenically unsaturated monomer containing a halogen atom. Represents different seven-dimensional units.
Ｘは１０〜１００モル％、ｙは０〜９０モル％、Ｚは０
〜２０モル％、Ｗは０〜１０モル％である。X is 10 to 100 mol%, y is 0 to 90 mol%, Z is 0
-20 mol%, W is 0-10 mol%.
好ましい分子量は２００〜２００万である。The preferred molecular weight is 2 million to 2 million.
Ｄは単なる結合基または炭素、窒素、硫黄、酸素及びリ
ン原子から構成される２価の結合基を表す。Ｌはベンゼ
ン環またはへテロ環を表し、Ｍは水素原子、アンモニウ
ム陽イオンまたはアルカリ金属イオンを表す。ｎは１ま
たは２である。〕一般式［１［’ｌ
〔式中、Ｒ１、Ｒ２、Ｒ３、Ｒ２は炭素数１〜１０の非
置換または置換アルキル基を表し、Ｘは水素、アミノ基
または置換アミノ基を表す。〕
一般式〔■〕
〔式中、
Ｌはアルキレン基またはアリーレン基を■
■
表し、
Ｍは水素またはアルカリ金属、
Ｘは水素、
ホモポリマ
アミ
ノ基または置換アミン基を表す。D represents a simple bonding group or a divalent bonding group composed of carbon, nitrogen, sulfur, oxygen, and phosphorus atoms. L represents a benzene ring or a heterocycle, and M represents a hydrogen atom, an ammonium cation, or an alkali metal ion. n is 1 or 2. ] General formula [1['l [In the formula, R1, R2, R3, and R2 represent an unsubstituted or substituted alkyl group having 1 to 10 carbon atoms, and X represents hydrogen, an amino group, or a substituted amino group. ] General formula [■] [In the formula, L represents an alkylene group or an arylene group, M represents hydrogen or an alkali metal, and X represents hydrogen, a homopolymer amino group or a substituted amine group.
〕 以下、 本発明の詳細について説明する。] below, The details of the present invention will be explained.
本発明に用いられる一般式 の化合物例を挙 ｏ３Ｎａ げろ。General formula used in the present invention Examples of compounds are listed below. o3Na Gero.
■ ホモポリマ Ｓｏ ３ Ｎａ ■ ＣＨ３ ｏ３Ｎａ ■ δＵ３Ｎａ ■ ■ ＣＨ３ ＣＨ。■ homopolymer So 3 Na ■ CH3 o3Na ■ δU3Na ■ ■ CH3 CH.
０３Ｎａ ■ ■ ｃｏ。03Na ■ ■ co.
零
ＣＨ３
Ｓｏ ３Ｎａ
■
ＣＩ（３
Ｃ）１２ｃＯＯＨ
ＣＨ２ＣＯＯＨ
■
■
ＣＨ３
ｏ３Ｎａ
ｘ：ｙ：ｚ−５０：４０：１０
Ｍヒ１０万
■
■
０３Ｎａ
０３Ｎａ
■
０３Ｎａ
■
ＳＯ３Ｎａ
■
■
０３Ｎａ
■
■
■
■
■
■
Ｈ３
■
■
Ｈ３
■
Ｍ４−１万
■
ｘ：ｙ＋ｚ：ｗ＝４０：３０：２０：１０Ｍ−５万
■
Ｍ４−３万
■
Ｍｂ３万
■
Ｍ辷５万
■
ｘ：ｙ：ｚ＝８０： ５ ：１５
Ｍ丑５万
ｘ：ｙ：ｚ：ｗ＝５０：３０：１０：１０■
■
なお、上記（１）〜（３８）において、ｘ＋ＶＷはそれ
ぞれ単量体成分のモル％を、またＭ（ま平均分子量（本
明細書中、平均分子量とは数平均分子量を示す。）を表
す。Zero CH3 So 3Na ■ CI (3 C) 12cOOH CH2COOH ■ ■ CH3 o3Na x:y:z-50:40:10 Mhi 100,000■ ■ 03Na 03Na ■ 03Na ■ SO3Na ■ ■ 03Na ■ ■ ■ ■ ■ ■ ■ H3 ■ ■ H3 ■ M4-10,000■ x:y+z:w=40:30:20:10M-50,000■ M4-30,000■ Mb30,000■ M length 50,000■ x:y:z=80: 5:15 M丑50,000 (In this specification, average molecular weight indicates number average molecular weight.)
これらのポリマーは市販又は常法によって得られるモノ
マーを重合することにより合成することが出来る。これ
らの化合物の添加量はＣ１，Ｏ１ｇ〜Ｌｏｇ／ｍ２が好
ましく、特に好ましくはＯ，１ｇ〜５ｇ／ｍ２である。These polymers can be synthesized by polymerizing monomers that are commercially available or obtained by conventional methods. The amount of these compounds added is preferably C1,01g to Log/m2, particularly preferably O,1g to 5g/m2.
１に
れらの化合物は単独あるいは種々の親水性バインダーま
たは疎水性バインダーと混合させて層を形成させること
ができる。親水性バインダーとして特に有利に用いられ
るものはゼラチンまたはポリアクリルアミドであるが、
他のものとしては、コロイド状アルブミン、セルロール
アセテート、セルロースニトレート、ポリビニルアルコ
ール、加水分解されたポリビニルアルコール、フタル化
ゼラチンか挙げられる。疎水性バインダーとしては分子
量２万〜１００万以上のポリマーが含まれ、スチレンー
ブヂルアクリレートーアクリル酸３元共重合ポリマー
ブチルアクリレート−アクリロニトリル−アクリル酸３
元共重合ポリマー メヂルメタクリレート−エチルアク
リレートーアクリル酸次に一般式（ＩＩ）
で表される化合物の具体例を
■
■
挙げる。1. These compounds can be used alone or mixed with various hydrophilic binders or hydrophobic binders to form a layer. Particularly advantageously used as hydrophilic binders are gelatin or polyacrylamide;
Others include colloidal albumin, cellulose acetate, cellulose nitrate, polyvinyl alcohol, hydrolyzed polyvinyl alcohol, and phthalated gelatin. Hydrophobic binders include polymers with a molecular weight of 20,000 to 1,000,000 or more, such as styrene-butyl acrylate and acrylic acid ternary copolymer.
Butyl acrylate-acrylonitrile-acrylic acid 3
Original Copolymer Polymer Methyl Methacrylate-Ethyl Acrylate Acrylic Acid Specific examples of the compound represented by the general formula (II) are listed below.
ＩＩ−１
■
ｌ−１０
上記、一般式Ｃｌ０）で表される化合物は、水又は適当
な有機溶媒に溶かして添加し、又は高沸点溶媒とともに
分散して添加することが出来る。II-1 ■ l-10 The compound represented by the above general formula Cl0) can be added after being dissolved in water or an appropriate organic solvent, or can be added after being dispersed with a high boiling point solvent.
好ましい添加量は１０ｍｇ／ｍ２− Ｌｏｇ／ｍ２であ
り、更に好ましくは１００ｍｇ／ｍ２−５ｇ／ｍ２であ
る。The preferred addition amount is 10mg/m2-Log/m2, more preferably 100mg/m2-5g/m2.
上記化合物は、アナリテイ力ルケミストリ（Ａｎａｉ２
ｙｔｉｃａＱＣｈｅｍｉｓｔｒｙ） １９８８．６０
ｐ２０１３の記載に従って合成することができる。The above compound can be obtained from Analyte Chemistry (Anai2).
yticaQChemistry) 1988.60
It can be synthesized as described in p.2013.
次に一般式 の具体的化合物例を挙げる。Then the general formula Examples of specific compounds are given below.
■
■
■
し２１１５
■−９
■
浦
上記一般式（ＩＩＩ］は一般式〔■〕と同様に添加する
ことができ、添加量も同じである。■ ■ ■ 2115 ■-9 ■ Ura The above general formula (III) can be added in the same manner as the general formula [■], and the amount added is also the same.
上記化合物の合成はバイオケミストリー（Ｂｉ。The synthesis of the above compounds is carried out using biochemistry (Bi.
Ｃｈｅｍｉｓｔｒｙ） １９８０．１９． ｐ２３９６
の記載にしたかって行うことができる。Chemistry) 1980.19. p2396
You can do it as you wish.
本発明の感光材料に用いるハロゲン化銀乳剤には、ハロ
ゲン化銀として、臭化銀、塩化銀、沃臭化銀、塩臭化銀
、塩沃臭化銀等の通常のハロゲン化銀乳剤に使用される
任意のものを用いる事ができ、ハロゲン化銀粒子は、酸
性法、中性法及びアンモニア法のいずれで得られたもの
でもよい。The silver halide emulsion used in the light-sensitive material of the present invention includes conventional silver halide emulsions such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide. Any commonly used silver halide grains can be used, and the silver halide grains may be those obtained by any of the acid method, neutral method, and ammonia method.
ハロゲン化銀粒子は、粒子内において均一なハロゲン化
銀組成分布を有するものでも、粒子の内部と表面層とで
ハロゲン化銀組成が異なるコア／シェル粒子であっても
よく、潜像が主として表面に形成されるような粒子であ
っても、また主として粒子内部に形成されるような粒子
でもよい。Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is mainly formed inside the particle.
本発明に係るハロゲン化銀粒子の形状は任意のものを用
いることかできる。好ましい１つの例は、（１００１面
を結晶表面として有する立方体である。Any shape of the silver halide grains according to the present invention can be used. One preferable example is a cube having (1001 plane) as a crystal surface.
又、米国特許４，１８３，７５６号、同４，２２５，６
６６号、特開昭５５−２６５８９号、特公昭５５−４２
７３７号等の明細書や、ザ・ジャーナル・オブ・フォト
グラフィック・サイエンス（Ｊ 、Ｐ ｈｏｔｇｒ、Ｓ
ｃｉ） 、 ２１．３９ （１９７３）等の文献に記
載された方法により、８面体、１４面体、１２面体等の
形状を有する粒子をつくり、これを用いることもできる
。更・二、双晶面を有する粒子を用いてもよい。Also, U.S. Patent Nos. 4,183,756 and 4,225,6
No. 66, JP-A-55-26589, JP-A-55-42
737, etc., and The Journal of Photographic Science (J, Photgr, S
Particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons can be prepared by the method described in literatures such as Ci), 21.39 (1973), and used. Furthermore, particles having twin planes may be used.
本発明に係るハロゲン化銀粒子は、単一の形状からなる
粒子を用いてもよいし、種々の形状の粒子が混合された
ものでもよい。The silver halide grains according to the present invention may be of a single shape or may be a mixture of grains of various shapes.
又、いかなる粒子サイズ分布を持つものを用いてもよく
、粒子サイズ分布の広い乳剤（多分散乳剤と称する）を
用いてもよいし、粒子サイズ分布の狭い乳剤（単分散乳
剤と称する。）を単独又は数種類混合してもよい。又、
多分散乳剤と単分散乳剤を混合して用いてもよい。Also, any grain size distribution may be used, and emulsions with a wide grain size distribution (referred to as polydisperse emulsions) may be used, or emulsions with a narrow grain size distribution (referred to as monodisperse emulsions) may be used. They may be used alone or in combination. or,
A polydisperse emulsion and a monodisperse emulsion may be mixed and used.
ハロゲン化銀乳剤は、別々に形成した２種以上のハロゲ
ン化銀乳剤を混合して用いてもよい。The silver halide emulsion may be a mixture of two or more separately formed silver halide emulsions.
感光性ハロゲン化銀乳剤は、化学増感を行わないで、い
わゆる未後熟（ｐｒｉｍｉｔｉｖｅ）乳剤のまま用いる
こともできるが、通常は化学増感される。Although the photosensitive silver halide emulsion can be used as a so-called primitive emulsion without chemical sensitization, it is usually chemically sensitized.
化学増感のためには、Ｇｌａｆｋｉｄｅｓ又は、Ｚｅｌ
ｉｋｍａｎらの著書、或いはＨ，Ｆｒ１ｅｓｅｒ編デ・
グルンドラーゲン・デル・フォトグラフィジエン・プロ
ツェセ・ミド・ジルベルハロゲニーデン（Ｄｉｅ Ｇｒ
ｕｎｄｌａｇｅｎｄｅｒ Ｐｈｏｔｏｇｒａｐｈｉｓ
ｃｈｅｎ Ｐｒｏｚｅｓｓｅ ｍｉｔ ５ｉｌｂ
ｅｒｈａｌ。For chemical sensitization, Glafkides or Zel
ikman et al. or edited by H. Fr1eser.
Die Gr.
undlagender Photography
chen Prozesse mit 5ilb
erhal.
ｇｅｎ＋ｄｅｎ、Ａｋａｄｅｍｉｃｃｈｅ Ｖｅｒｌ
ａｇｓｇｅｓｅｌｌｓｃｈａｆｔ。gen+den, Akademicche Verl
agsgesellschaft.
１．９６８）に記載の方法を用いることができる。1.968) can be used.
即ち、銀イオンと４反応し得る硫黄を含む化合物や活性
ゼラチンを用いる硫黄増感法、還元性物質を用いる還元
増感法、金その他の貴金属化合物を用い、または併用す
ることかできる。That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a gold or other noble metal compound, or a combination thereof can be used.
感光性乳剤としては、前記乳剤を単独で用いてもよく、
二種以上の乳剤を混合してもよい。As the photosensitive emulsion, the above emulsion may be used alone,
Two or more emulsions may be mixed.
本発明の実施に際しては、上記のような化学増感の終了
後に、例えば、４−ヒドロキシ−６−メヂル１．３，３
ａ、７−チトラザインデン、５−メルカプト−１フエニ
ルテトラゾール、２−メルカプトベンゾチアゾール等を
始め、種々の安定剤も使用できる。In carrying out the present invention, for example, 4-hydroxy-6-methyl 1.3,3
Various stabilizers can also be used, including a, 7-titrazaindene, 5-mercapto-1 phenyltetrazole, 2-mercaptobenzothiazole, and the like.
更に必要であればチオエーテル等のハロケン化銀溶剤、
又はメルカプト基含有化合物や増感色素のような晶癖コ
ントロール剤を用いてもよい。Furthermore, if necessary, a silver halide solvent such as thioether,
Alternatively, a crystal habit control agent such as a mercapto group-containing compound or a sensitizing dye may be used.
本発明の乳剤は、ハロゲン化銀粒子の成長の終了後に不
要な可溶性塩類を除去しても良いし、あるいは含有させ
たままでもよい。該塩類を除去する場合には、リサーチ
・ディスクロジャー１７６４３号記載の方法に基づいて
行うことができる。In the emulsion of the present invention, unnecessary soluble salts may be removed after the growth of silver halide grains is completed, or they may be left contained. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.
本発明の感光材料には、更に目的に応じて種々の添加剤
を用いることができる。これらの添加剤は、より詳しく
は、リサーチディスクロージャー第１７６巻１ ｔｅｍ
１７６４３ （１９７８年１２月）及び同１８７巻■ｔ
ｅｍ１８７１６（１９７９年１１月）に記載されており
、ソノ該当個所を後掲の表にまとめて示した。The photosensitive material of the present invention may further contain various additives depending on the purpose. These additives are described in more detail in Research Disclosure Vol. 176, 1 tem.
17643 (December 1978) and volume 187■t
em18716 (November 1979), and the relevant parts are summarized in the table below.
添加剤種類
ＲＤ １７６４３
ＲＤ １８７１．６
１、化学増感剤
２３頁
６４８頁右欄
２、感度上昇剤
同上
４、増白剤
２４頁
７、スティン防止剤 ２５頁右欄 ６５０
頁左〜右欄８、色素画像安定剤 ２５頁９、
硬 膜 剤 ２６頁 ６５１頁左
欄１０、バインダー ２６頁
同上１１−可塑剤・潤滑剤 ２７頁
６５０右欄１２、塗布助剤・表面活性剤 ２６
〜２７頁 同上１３、スタチック防止剤
２７頁 同上本発明のハロゲン化銀写真感光
材料の実施において、例えば乳剤層その他の層は写真感
光材料に通常用いられている可撓性支持体の片面又は両
面に塗布して構成することができる。可撓性支持体とし
て有用なものは、硝酸セルロース、酢酸セルロース、酢
酸酪酸セルロース、ポリスチレン、ポリ塩化ビニル、ポ
リエチレンテレフタレート、ポリカーボネート等の半合
成又は合成高分子からなるフィルム、バライタ層又はα
−オレフィンポリマー（例えはポリエチレン、ポリプロ
ピレン、エチレン／ブテン共重合体）等を塗布又はラミ
ネトした紙などである。支持体は、染料や顔料を用いて
着色されてもよい。遮光の目的で黒色にしてもよい。こ
れらの支持体の表面は一般に、乳剤層等との接着をよく
するために下塗処理される。下塗処理は、特開昭５２−
１０４９１３号、同５９−１８９４９号、同５９−１９
９４０号、同５９−１８９４９号各公報に記載されてい
る処理が好ましい。Additive type RD 17643 RD 1871.6 1, Chemical sensitizer 23 pages 648 pages right column 2, Sensitivity enhancer same as above 4, Brightener 24 pages 7, Stain inhibitor 25 pages right column 650
Page left to right column 8, Dye image stabilizer 25 page 9,
Hardener page 26, page 651 left column 10, binder page 26
Same as above 11-Plasticizer/Lubricant page 27
650 right column 12, coating aid/surfactant 26
~Page 27 Same as above 13, Static inhibitor
Page 27 Same as above In carrying out the silver halide photographic light-sensitive material of the present invention, for example, the emulsion layer and other layers can be constructed by coating on one or both sides of a flexible support commonly used in photographic light-sensitive materials. . Useful flexible supports include films made of semi-synthetic or synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose acetate butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, baryta layers or α
- Paper coated or laminated with an olefin polymer (eg, polyethylene, polypropylene, ethylene/butene copolymer), etc. The support may be colored using dyes or pigments. It may be made black for the purpose of blocking light. The surface of these supports is generally treated with an undercoat to improve adhesion with emulsion layers and the like. The undercoating process is based on JP-A-52-
No. 104913, No. 59-18949, No. 59-19
The treatments described in Publications No. 940 and No. 59-18949 are preferred.
本発明に係るハロゲン化銀写真感光材料において、写真
乳剤層その他の親水性コロイド層は種々の塗布法により
支持体上又は他の層の上に塗布できる。塗布には、デイ
ツプ塗布法、ローラー塗布法、カーテン塗布法、押出し
塗布法等を用いることができる。In the silver halide photographic light-sensitive material according to the present invention, the photographic emulsion layer and other hydrophilic colloid layers can be coated on the support or on other layers by various coating methods. For coating, a dip coating method, a roller coating method, a curtain coating method, an extrusion coating method, etc. can be used.
また現像等の処理は、通常ハロゲン化銀写真感光材料の
処理に用いられる当業者公知の各種方法を用いることが
できる。Further, for processing such as development, various methods known to those skilled in the art that are normally used for processing silver halide photographic materials can be used.
以下、実施例により本発明の効果を例証する。 Hereinafter, the effects of the present invention will be illustrated by examples.
実施例１
常法にしたがって、調製されたハロゲン化銀写真感光乳
剤を塗布されたポリエチレンテレフタレート支持体の反
対側に、特開昭５９−１９９４１号の実施例１によりラ
テックス下引処理をした後、下記に示す内容のポリマー
層、ハレーション防止層、ハレーション防止保護層をこ
の順に塗布乾燥し、試料を作成した。Example 1 The opposite side of a polyethylene terephthalate support coated with a silver halide photographic emulsion prepared according to a conventional method was subjected to latex subbing treatment according to Example 1 of JP-A-59-19941. A polymer layer, an antihalation layer, and an antihalation protective layer having the contents shown below were coated in this order and dried to prepare a sample.
ポリマー層
ラテックスポリマー：ブチルアクリレートスチレン−ア
クリル酸３元重合ポリマ
０．２ ｇ／ｍ２
本発明のポリマー 表１に示す硬膜剤（
Ｈ）
ハレーション防止層
スチレン−マレイン酸共ｍ合体
クエン酸（塗布後ｐＨ５，４に調製）
サポニン
硝酸リチウム塩
バッキング染料
ＣＨ２５ｏ３Ｈ
０３Ｎａ
１００■ｇ／ｍ２
４０ｍｇ／ｍ２
２００ｍｇ／ｍ２
３０＋ｎｇ／ｍ２
アルカリ処理ゼラチン ２、Ｏｇ／ｍ”
ホルマリン １０ｍｇ／ｍ２
（ハレーション防止層保護膜）
添加剤を下記付量になるよう調製し、バッキング層上部
に塗布した。Polymer layer latex polymer: Butyl acrylate styrene-acrylic acid terpolymer polymer 0.2 g/m2 Polymer of the present invention Hardener shown in Table 1 (
H) Anti-halation layer Styrene-maleic acid co-merged citric acid (adjusted to pH 5.4 after coating) Saponin lithium nitrate salt Backing dye CH25o3H 03Na 100 g/m2 40 mg/m2 200 mg/m2 30+ng/m2 Alkali-treated gelatin 2, Og/m”
Formalin 10mg/m2
(Antihalation layer protective film) Additives were prepared in the amounts shown below and applied to the top of the backing layer.
ジオクチルスルホコハク酸エステル
２００ｍｇ／ｍ２
マット剤：ポリメタクリル酸メチル
（平均粒径４．０μｍ） ５０ｍ
ｇ／ｍ２弗素化ドテシルベンゼンスルホン酸
ナトリウム ５０ｍｇ／ｎ＋２
本発明の一般式〔■〕及び／又は一般式〔ＩＩＩ）の化
合物 表１に示す量アルカリ処
理ゼラチン １．０ｇ／ｍ２ホルマリン
１０ｍｇ／ｍ２このように
して得られた試料を、下記処方の現像液及び定着液を用
い、下記処理条件で自動現像機により処理した。尚、現
像液、定着液等の処理液の調製には通常の水道水を使用
した。Dioctylsulfosuccinate 200mg/m2 Matting agent: Polymethyl methacrylate (average particle size 4.0μm) 50m
g/m2 Sodium fluorinated dotecylbenzenesulfonate 50mg/n+2
Compound of the general formula [■] and/or general formula [III] of the present invention The amount shown in Table 1 Alkali-treated gelatin 1.0 g/m2 Formalin 10 mg/m2 The sample thus obtained was treated with a developer having the following formulation. The film was processed using an automatic processor under the following processing conditions using a fixer and a fixer. Note that ordinary tap water was used to prepare processing solutions such as a developer and a fixer.
現像液処方
ハイドロキノン
１−フェニル−４，４ジメチル−３
ピラゾリドン
臭化ナトリウム
５−メチルベンゾトリアゾール
５−ニトロインダゾール
ジエチルアミノプロパン−１，２−ジオール亜硫酸カリ
ウム
５−スルホサリチル酸ナトリウム
エチレンジアミン四酢酸ナトリウム
水でＩＱに仕上げた。Developer formulation Hydroquinone 1-phenyl-4,4 dimethyl-3 Pyrazolidone Sodium bromide 5-Methylbenzotriazole 5-Nitroindazole Diethylaminopropane-1,2-diol Potassium sulfite 5-Sodium sulfosalicylate Ethylenediamine Sodium tetraacetate Add to IQ with water Finished.
ｐＨは、苛性ソータで１１．５とした。The pH was adjusted to 11.5 using a caustic sorter.
定着液処方
（組成Ａ）
チオ硫酸アンモニウム（７２，５Ｗ％水溶液）亜硫酸ナ
トリウム
酢酸ナトリウム・３水塩
硼酸
５ｇ
０．４已
３ｇ
０．３ｇ
０．０５ｇ
０ｇ
０ｇ
５ｇ
３ｇ
４０ｖ２
７ｇ
６．５ｇ
３ｇ
クエン酸ナトリウム・２水塩 ２ｇ酢酸
（９０ｗ％水溶液） ］、３３．
６ｍｆｆ組成り）
純水（イオン交換水） １７ｍ４
硫酸（５０ｗ％の水溶液） ４．７
ｇ硫酸アルミニウム （ｉ２０３換算含量が８．１ｗ％
の水溶液） ２６．５ｇ定着液の
使用時に水５００ｍ４中に上記組成Ａ１組成りの順に溶
かし、１ρに仕上げて用いた。この定着液のｐＨは約４
．３であった。Fixer formulation (composition A) Ammonium thiosulfate (72.5W% aqueous solution) Sodium sulfite Sodium acetate trihydrate Boric acid 5g 0.4g 3g 0.3g 0.05g 0g 0g 5g 3g 40v2 7g 6.5g 3g Sodium citrate・Dihydrate 2g acetic acid (90w% aqueous solution) ], 33.
6mff composition) Pure water (ion exchange water) 17m4
Sulfuric acid (50w% aqueous solution) 4.7
g Aluminum sulfate (I203 equivalent content is 8.1w%
When using a 26.5 g fixer solution, the above composition A1 was dissolved in the order of composition A1 in the order of 500 m4 of water and used after finishing to 1ρ. The pH of this fixer is approximately 4.
．． It was 3.
〈現像処理条件〉
（工程） （温度） （時間）現像
４０°Ｏ１５秒
定着 ３５°０ １０秒水洗 常
温 １０秒
得られた結果を表−１に示す。<Development processing conditions> (Process) (Temperature) (Time) Development
Fixation at 40° O for 15 seconds Washing at 35° O for 10 seconds Room temperature 10 seconds The results obtained are shown in Table 1.
表
添加量はｇ／ｍ２、表面比抵抗はΩ／ｃｍの単位で表す
。The table addition amount is expressed in g/m2, and the surface specific resistance is expressed in Ω/cm.
表−１の結果から本発明に係る試料は、現像処理後の帯
電防止能の劣化が少なく、比較に比へて著しく改善され
ていることがわかる。From the results in Table 1, it can be seen that the samples according to the present invention showed little deterioration in antistatic ability after development, and were significantly improved compared to the comparison.
本発明により、現像等の処理後も帯電防止性能の劣化し
ないハロゲン化銀写真感光材料を提供することができた
。According to the present invention, it was possible to provide a silver halide photographic material whose antistatic performance does not deteriorate even after processing such as development.
Claims (1)
I 〕で表される繰り返し単位を有する水溶性ポリマー
を含有する層を少なくとも１層有し、該層よりも支持体
より遠い層に、一般式〔II〕及び／又は一般式〔III〕
で表される化合物を含有させたことを特徴とするハロゲ
ン化銀写真感光材料。 一般式〔 I 〕 ▲数式、化学式、表等があります▼ 〔式中、Ｒは水素原子、ハロゲン原子、またはアルキル
基を表し、Ａ、Ｂ、Ｃはそれぞれ共重合可能なカルボキ
シ基またはそのエステル誘導体またはハロゲン原子を含
むエチレン性不飽和モノマーを共重合した互いに異なる
モノマー単位を表す。ｘは１０〜１００モル％、ｙは０
〜９０モル％、ｚは０〜２０モル％、ｗは０〜１０モル
％である。 また、好ましい分子量は２００〜２００万である。 Ｄは単なる結合基または炭素、窒素、硫黄、酸素及びリ
ン原子から構成される２価の結合基を表す。Ｌはベンゼ
ン環またはヘテロ環を表し、Ｍは水素原子、アンモニウ
ム陽イオンまたはアルカリ金属イオンを表す。ｎは１ま
たは２である。〕 一般式〔II〕 ▲数式、化学式、表等があります▼ 〔式中、Ｒ＿１、Ｒ＿２、Ｒ＿３、Ｒ＿４は炭素数１〜
１０の非置換または置換アルキル基を表し、ｘは水素、
アミノ基または置換アミノ基を表す。〕 一般式〔III〕 ▲数式、化学式、表等があります▼ 〔式中、Ｌはアルキレン基またはアリーレン基を表し、
Ｍは水素またはアルカリ金属、Ｘは水素、アミノ基また
は置換アミノ基を表す。〕[Claims] On the opposite side of the support provided with the photosensitive emulsion layer, the following general formula [
I] has at least one layer containing a water-soluble polymer having a repeating unit represented by general formula [II] and/or general formula [III] in a layer farther from the support than this layer.
A silver halide photographic material containing a compound represented by: General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. Alternatively, it represents a mutually different monomer unit copolymerized with an ethylenically unsaturated monomer containing a halogen atom. x is 10 to 100 mol%, y is 0
~90 mol%, z is 0-20 mol%, and w is 0-10 mol%. Moreover, a preferable molecular weight is 2 million to 2 million. D represents a simple bonding group or a divalent bonding group composed of carbon, nitrogen, sulfur, oxygen, and phosphorus atoms. L represents a benzene ring or a heterocycle, and M represents a hydrogen atom, an ammonium cation, or an alkali metal ion. n is 1 or 2. ] General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1, R_2, R_3, R_4 have 1 to 1 carbon number
represents 10 unsubstituted or substituted alkyl groups, x is hydrogen,
Represents an amino group or a substituted amino group. ] General formula [III] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, L represents an alkylene group or an arylene group,
M represents hydrogen or an alkali metal, and X represents hydrogen, an amino group or a substituted amino group. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2938889A JPH02207243A (en) | 1989-02-07 | 1989-02-07 | Silver halide photographic sensitive material having improved electrostatic chargeability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2938889A JPH02207243A (en) | 1989-02-07 | 1989-02-07 | Silver halide photographic sensitive material having improved electrostatic chargeability |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02207243A true JPH02207243A (en) | 1990-08-16 |
Family
ID=12274755
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2938889A Pending JPH02207243A (en) | 1989-02-07 | 1989-02-07 | Silver halide photographic sensitive material having improved electrostatic chargeability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02207243A (en) |
-
1989
- 1989-02-07 JP JP2938889A patent/JPH02207243A/en active Pending
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