JPS63198047A - Silver halide photographic sensitive material - Google Patents
Silver halide photographic sensitive materialInfo
- Publication number
- JPS63198047A JPS63198047A JP3073687A JP3073687A JPS63198047A JP S63198047 A JPS63198047 A JP S63198047A JP 3073687 A JP3073687 A JP 3073687A JP 3073687 A JP3073687 A JP 3073687A JP S63198047 A JPS63198047 A JP S63198047A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- copolymer
- titled material
- styrene
- aqueous dispersion
- 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 19
- -1 Silver halide Chemical class 0.000 title claims description 20
- 229910052709 silver Inorganic materials 0.000 title claims description 9
- 239000004332 silver Substances 0.000 title claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920001577 copolymer Polymers 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 150000003440 styrenes Chemical class 0.000 claims abstract description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 4
- 239000000084 colloidal system Substances 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 40
- 239000000839 emulsion Substances 0.000 abstract description 9
- 238000004031 devitrification Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000011241 protective layer Substances 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 108010010803 Gelatin Proteins 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- 230000007774 longterm Effects 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 125000005396 acrylic acid ester group Chemical group 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- 229910001864 baryta Inorganic materials 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- YOMSJEATGXXYPX-UHFFFAOYSA-N 2-methoxy-4-vinylphenol Chemical compound COC1=CC(C=C)=CC=C1O YOMSJEATGXXYPX-UHFFFAOYSA-N 0.000 description 2
- PIAOLBVUVDXHHL-UHFFFAOYSA-N 2-nitroethenylbenzene Chemical compound [O-][N+](=O)C=CC1=CC=CC=C1 PIAOLBVUVDXHHL-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 235000015110 jellies Nutrition 0.000 description 2
- 239000008274 jelly Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- HFWFAOTUXFDVBE-UHFFFAOYSA-N 1,2,2-trinitroethenylbenzene Chemical compound [O-][N+](=O)C([N+]([O-])=O)=C([N+](=O)[O-])C1=CC=CC=C1 HFWFAOTUXFDVBE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- FCTDKZOUZXYHNA-UHFFFAOYSA-N 1,4-dioxane-2,2-diol Chemical compound OC1(O)COCCO1 FCTDKZOUZXYHNA-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
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- PIOSENMMCZHTGF-UHFFFAOYSA-N 2-benzylidenebut-3-enoic acid Chemical compound OC(=O)C(C=C)=CC1=CC=CC=C1 PIOSENMMCZHTGF-UHFFFAOYSA-N 0.000 description 1
- HXLLCROMVONRRO-UHFFFAOYSA-N 2-butoxyethenylbenzene Chemical compound CCCCOC=CC1=CC=CC=C1 HXLLCROMVONRRO-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- FZHNODDFDJBMAS-UHFFFAOYSA-N 2-ethoxyethenylbenzene Chemical compound CCOC=CC1=CC=CC=C1 FZHNODDFDJBMAS-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical class NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- XLLXMBCBJGATSP-UHFFFAOYSA-N 2-phenylethenol Chemical class OC=CC1=CC=CC=C1 XLLXMBCBJGATSP-UHFFFAOYSA-N 0.000 description 1
- IFSSSYDVRQSDSG-UHFFFAOYSA-N 3-ethenylaniline Chemical compound NC1=CC=CC(C=C)=C1 IFSSSYDVRQSDSG-UHFFFAOYSA-N 0.000 description 1
- CEBRPXLXYCFYGU-UHFFFAOYSA-N 3-methylbut-1-enylbenzene Chemical compound CC(C)C=CC1=CC=CC=C1 CEBRPXLXYCFYGU-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 1
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- QPJVMBTYPHYUOC-UHFFFAOYSA-N Methyl benzoate Natural products COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 125000005586 carbonic acid group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Natural products OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SDYRIBONPHEWCT-UHFFFAOYSA-N n,n-dimethyl-2-phenylethenamine Chemical compound CN(C)C=CC1=CC=CC=C1 SDYRIBONPHEWCT-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GNHOJBNSNUXZQA-UHFFFAOYSA-J potassium aluminium sulfate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GNHOJBNSNUXZQA-UHFFFAOYSA-J 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/7614—Cover layers; Backing layers; Base or auxiliary layers characterised by means for lubricating, for rendering anti-abrasive or for preventing adhesion
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
Abstract
Description
【発明の詳細な説明】
(A) 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、特に表面光
沢の改良された写真用印画紙に関するものである。DETAILED DESCRIPTION OF THE INVENTION (A) Field of Industrial Application The present invention relates to a silver halide photographic material, and more particularly to a photographic paper with improved surface gloss.
(H) 従来技術及びその問題点
写真用印画紙は、紙、バライタ紙、ポリマーをラミネー
トした紙、不透明層を設けたポリマーフィルム等からな
る不透明支持体上に、少なくとも1層の感光性乳剤層、
表面保護層、及び必要により、中間層、フィルタ一層、
下塗層、バッキング層を有して成る。(H) Prior art and its problems Photographic paper consists of at least one light-sensitive emulsion layer on an opaque support made of paper, baryta paper, polymer-laminated paper, polymer film with an opaque layer, etc. ,
Surface protective layer, and if necessary, intermediate layer, filter layer,
It has an undercoat layer and a backing layer.
写真用印画紙は支持体上に形成された写真画像を反射光
で観察する故に、画像の反射濃度の高低により、画質の
良否が大きく左右される。Since the photographic image formed on the support of photographic paper is observed using reflected light, the quality of the image is greatly influenced by the reflection density of the image.
写真用印画紙の反射濃度を上げる為の1つの手段として
、従来から、写真用印画紙の表面光沢を上昇せしめる努
力がされて来ている。As one means for increasing the reflection density of photographic paper, efforts have been made to increase the surface gloss of photographic paper.
例えば支持体表面に、バライタ層、ポリマーラミネート
層等を設け、しかる後、その上に感光性乳剤層を塗布す
ることにより写真用印画紙表面の平滑性を同上せしめる
ことにより入射光の散乱を防ぎ、表面光沢を上昇せしめ
る方法、又は、現像処理終了後の写真用印画紙表面を鏡
面を持つ、加熱された金属板(いわゆるフェロタイプ)
に接層させて乾燥させることにより、写真印画紙表面を
鏡面状にする、いわゆるフェロタイプかけにより表置光
沢を上昇せしめる方法及び両方法の組合せによる方法等
が従来よく知られていた。For example, by providing a baryta layer, a polymer laminate layer, etc. on the surface of the support, and then coating a photosensitive emulsion layer thereon, the surface smoothness of the photographic paper is improved, thereby preventing scattering of incident light. , a method of increasing surface gloss, or a heated metal plate (so-called ferrotype) that gives the surface of photographic paper a mirror finish after development processing.
Well-known methods include a method of increasing surface gloss by so-called ferrotyping, in which the surface of a photographic paper is brought into a mirror-like finish by being brought into contact with a photographic paper and dried, and a method of combining both methods.
近年、省エネ型材料として写真用印画紙も博物化してお
り、支持体の薄層化に伴い、支持体に塗布された感光乳
剤層、表面保護層、その他の層において高湿時又は低湿
時のカールの増大を伴う関係上薄層化を必要とされ、か
かる時において保護層の薄層化は表面光沢の減少をもた
らす。In recent years, photographic paper has become a natural resource as an energy-saving material.As supports become thinner, the light-sensitive emulsion layer, surface protection layer, and other layers coated on the support become more stable under high or low humidity. Thinning is required due to increased curl, and at such times thinning of the protective layer results in a reduction in surface gloss.
史に近年現像処理の迅速化が要求されており、そのため
にも塗層の薄ノー化が必要となり表面光沢の維持向上は
その観点からも極めて1喪な課題となっている。In recent years, there has been a demand for faster development processing, and for this reason, it is necessary to make the coating layer thinner, and from that point of view, maintenance and improvement of surface gloss has become an extremely important issue.
特公昭56−24253ではゼリー強要300I以上を
有する石灰処理ゼラチンを最上層に用いる技術を開示し
ているが最上層を博くすると、その効果は少なくなり、
光沢の減少とそnに伴なう#度の低下により写真印画紙
の商品価値の低下につながる。さらに、%JIIS8−
112491にゼリー強maooy以上でしかもカルシ
ウム含有量を1000 PPM以下の脱−した石灰処理
オセインセラテン層を最上層に用いる技術を提案してい
るが、感光乳剤層、表面保護層の薄層化が進むと光沢の
低下傾向となる。Japanese Patent Publication No. 56-24253 discloses a technique in which lime-treated gelatin having a jelly strength of 300 I or more is used in the top layer, but as the top layer becomes thicker, the effect decreases.
The decrease in gloss and the accompanying decrease in # degree lead to a decrease in the commercial value of photographic paper. Furthermore, %JIIS8-
112491, we have proposed a technology that uses a lime-treated ossein-ceratene layer as the top layer, which has a jelly strength of more than 1,000 PPM and a calcium content of 1000 PPM or less, but as the light-sensitive emulsion layer and surface protective layer become thinner, The gloss tends to decrease.
一方、特公昭57−10416では最上層中にコロイド
状シリカを含有し、乳剤層中にビニル重合体を含有せし
める技術があるがこれとても光沢の効果は期待できずさ
らに最上層の薄層化と伴に効果は少くなり、しかもコロ
イド状シリカを最上層に入れると写真画像の白地部分の
光沢が下がり写真印画紙としては好ましくない。On the other hand, in Japanese Patent Publication No. 57-10416, there is a technique in which colloidal silica is contained in the top layer and vinyl polymer is contained in the emulsion layer, but this technique cannot be expected to produce much gloss, and it is necessary to make the top layer thinner. As a result, the effect decreases, and furthermore, when colloidal silica is added to the top layer, the gloss of the white background of the photographic image decreases, making it undesirable for photographic printing paper.
さらに、表面にコロイド状シリカを含有し膳出すると、
長期展示等で元、熱に長期間さらされることにより、印
画紙表面のヒビ割れが発生し易い欠点が出て、商品価値
の低下につながる。Furthermore, when the surface contains colloidal silica and is prepared,
Due to long-term exposure to heat during long-term exhibitions, the surface of photographic paper tends to crack, leading to a decline in product value.
一方、特開昭50−56931号、loJ 53−46
018号、同58−137831号、1町53−460
18号、10J54−109831号、同54−761
37号叫には写真感光材料に含有する共重合体水系分散
物の技術が開示されている。しかしながら、これらの先
行技術に用いられている共重合体水系分散物は最外層に
用いると#、感、カブリの増加、現像時の失透及び長期
展示箋で光、熱に長期間さらされることにより、印画紙
表面のヒビ割れ、光沢の低下が発生しやすい欠点が出て
商品価値の低下につながる。On the other hand, JP-A No. 50-56931, loJ 53-46
No. 018, No. 58-137831, 1-cho 53-460
No. 18, No. 10J54-109831, No. 54-761
No. 37 discloses a technology for an aqueous copolymer dispersion contained in a photographic light-sensitive material. However, when the copolymer aqueous dispersion used in these prior art is used in the outermost layer, it may cause an increase in viscosity, fog, devitrification during development, and long-term exposure to light and heat during long-term display. This causes defects such as cracks on the surface of photographic paper and a decrease in gloss, which leads to a decrease in product value.
(C) 発明の目的
本発明の目的は、第1に表面光沢を上昇させ、反射濃度
の高い写真感光材料を提供することにある。第2に現像
時に失透を生ずることなく、かつ、長期…1の展示等で
の画像の劣化がない写真感光材料を提供することにある
。(C) Object of the Invention The first object of the invention is to provide a photographic material with increased surface gloss and high reflection density. The second object is to provide a photographic material that does not cause devitrification during development and does not cause deterioration of images during long-term exhibition, etc.
(Dl 発明の構成
本発明は、支持体上に少なくとも2)vI11以上の親
水性コロイド層を有するハロゲン化像写真感元杓科に於
て、最外層の親水性コロイド層中にスチレンおよび/ま
たはスチレンhe体、アクリル酸エステル、不飽和カル
ボン酸から実質的になる共重合体水系分散物を含有する
ことを特徴とするハロゲン化嫁写真感元@料である。(Dl) Structure of the Invention The present invention provides a halogenated image photographic sensitizer having at least two hydrophilic colloid layers with a vI of 11 or more on a support, in which the outermost hydrophilic colloid layer contains styrene and/or This is a halogenated photographic material characterized by containing an aqueous copolymer dispersion consisting essentially of styrene helium, acrylic acid ester, and unsaturated carboxylic acid.
本発明に用いらnるスチレン及び/またはスチレン誘導
体は、スチレン、ならひにメチルスチレン、エチルスチ
レン、イソプロピルスチレン等のアルキルスチレン類、
クロルスチレン、ブロムスチレン、フルオルスチレン等
のハロゲン化スチレン類、メトキシスチレン、エトキシ
スチレン、ブトキシスチレン等のアルコキシスチレン類
、P−ヒドロキシスチレン、3−メトキシ−4−ヒドロ
キシスチレン等のヒドロキシスチレン類、ビニル安息香
mビニル安息査酸メチル等のカルホキシスチレン及びそ
の訪導体ニトロスチレン、トリニトロスチレン等のニト
ロ化スチレンM% m−アミノスチレン、ジメチルアミ
ノスチレン等のアミノスチレン類、P−ビニルベンゼン
スルホン酸エテル搗のイオウを含むスチレン訪纒体類及
びα位、β位のttm体か挙げられる。アクリル酸エス
テルのエステル残基としては例えばメチル、エテノペ
n−フロビル、1ao−プロピル、2−エテルヘキシノ
ペテシル等か挙けらnる。父、1.1.3トリヒドロパ
ーフルオロ70ビルの如キハロヶン原子でtrtyhさ
れていても良い。不飽和カルボン酸としては、アクリル
酸、メタアクリル酸、イタコン酸、マレイン酸等が挙げ
られる。Styrene and/or styrene derivatives used in the present invention include styrene, alkylstyrenes such as methylstyrene, ethylstyrene, and isopropylstyrene;
Halogenated styrenes such as chlorstyrene, bromustyrene, fluorostyrene, alkoxystyrenes such as methoxystyrene, ethoxystyrene, butoxystyrene, hydroxystyrenes such as P-hydroxystyrene, 3-methoxy-4-hydroxystyrene, vinyl Carboxystyrene such as m-vinyl methyl benzoate and its derivatives nitrostyrene such as nitrostyrene and trinitrostyrene M% Aminostyrenes such as m-aminostyrene and dimethylaminostyrene, P-vinylbenzenesulfonic acid Examples include styrene-containing sulfur-containing styrene derivatives and ttm-isomers at α and β positions. Ester residues of acrylic acid esters include, for example, methyl and etenopene.
Examples include n-furovir, 1ao-propyl, 2-etherhexynopetecil, and the like. The father, 1.1.3 trihydroperfluoro70vir, may be trityhed with a dihalogen atom. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, and maleic acid.
本発明に好ましく用いられるスチレンおよび/またはス
チレン誘導体とアクリル酸エステルと不飽和カルボン酸
の比は、スチレンおよび/またはスチレン!8尋体の含
有量が10〜70重量%であり、特に30〜60%であ
ることが好ましい。また、不飽和カルボン酸の含有量は
1〜10重−11%であり、特に1〜5%であることが
好ましい。また、アクリル酸エステルは任意に選ぶこと
ができ、更に本発明の効果を実質的に損なうことのない
範囲で他のモノマー成分を含んでいてよい。The ratio of styrene and/or styrene derivative, acrylic acid ester, and unsaturated carboxylic acid preferably used in the present invention is styrene and/or styrene! It is preferable that the content of 8 fathoms is 10 to 70% by weight, particularly 30 to 60%. Further, the content of unsaturated carboxylic acid is 1 to 10% by weight, particularly preferably 1 to 5%. Further, the acrylic ester can be arbitrarily selected, and may further contain other monomer components within a range that does not substantially impair the effects of the present invention.
本発明の共重合体水系分散物は乳化東合法により製造さ
nる。これを製造するためには、還流冷却器及び撹拌機
付フラスコに乳化分散剤として例えば識硫酸アンモニウ
ム及び重合促進剤として例えは酸性亜硫酸ンータを加え
て祷らnる溶准を約60℃に保持しながら撹拌中、共重
合成分上ツマ−を篩下させ1M会させると、共重合体水
系分散物が得られる。反応に用いらnる界rkU宿性剤
の添加量は共重合成分モノマーに対して5M量%以下特
に1重量%前後が最良である。得られる分散液中μ以下
のもの、特に0.05μ以下のものが好ましい0
本発明の共重合体水系分散物は感光材料の乳剤層、中間
層等に用いても効果はあるが、最外層例えば保!!1層
に添加したとき特に効果がある。The copolymer aqueous dispersion of the present invention is produced by the emulsification method. To produce this, an emulsifying dispersant such as ammonium sulfate and a polymerization promoter such as acid sulfite are added to a flask equipped with a reflux condenser and a stirrer, and the desired solubility is maintained at approximately 60°C. While stirring, the upper part of the copolymer component is sieved to obtain a 1M copolymer, thereby obtaining an aqueous copolymer dispersion. The amount of the interfacial rkU-hosting agent used in the reaction to be added is preferably 5 M% or less, particularly around 1% by weight, based on the copolymerization component monomer. The dispersion obtained preferably has a copolymer of 0.05 μ or less, especially 0.05 μ or less. The aqueous copolymer dispersion of the present invention is effective when used in the emulsion layer, intermediate layer, etc. of a light-sensitive material, but the outermost layer For example, keep! ! It is particularly effective when added to one layer.
本発明の実施態様としては、か\る物散物を他のバイン
ダーと共に使用する。その際、ゼラチンと自由な北本で
混ざるのでゼラチンに対する添加量に特に制限はないが
、ゼラチンに対し3〜100:it%程度、特に5〜7
0M′jgt%用いるのが好ましい。Embodiments of the invention use such dispersants in conjunction with other binders. At that time, there is no particular restriction on the amount added to gelatin because it mixes with gelatin in free Kitamoto, but it is about 3 to 100:it% of gelatin, especially 5 to 7
It is preferable to use 0M'jgt%.
次に本発明に使用される共重合体水系分散物に含有され
る代表的共産合体及び比較用共電合体の組成を以下に示
すが、本発明はこnに限定されるものではない。Next, the compositions of typical copolymer and comparative copolymer contained in the aqueous copolymer dispersion used in the present invention are shown below, but the present invention is not limited thereto.
本発明において、前述の如く最外層に用いた時が最も効
果を示すが、その際バインダーとして使用される親水性
コロイド物質としては、セラチン及びゼラチン肪導体で
ある。In the present invention, the effect is most effective when used in the outermost layer as described above, and the hydrophilic colloid substances used as binders in this case are ceratin and gelatin fat conductors.
また、ポリスチレン、ポリメタクリル酸メチルあるいは
シリカ等のマット剤を共重合体とバインダーからなる最
上層に必要に応じて併用することも何らさしつかえない
。Furthermore, there is nothing wrong with using a matting agent such as polystyrene, polymethyl methacrylate, or silica in the uppermost layer consisting of a copolymer and a binder, if necessary.
本発明における表面保護層は適度に硬膜剤、界面活性剤
を含んでいることが好ましい。硬1111Jの具体的な
例としては、ホルムアルデヒド、ゲルタールアルデヒド
の如きアルデヒド系化合物、ジアセチル、ミクロペンジ
オンの如きチトン化合物、ビス(2−クロロエチル尿素
)−2−ヒドロキシ−4,6−ジクロロ−1,3,5)
リアジン、米国特許第3635718号記載の如き反応
性のハロゲンを有する化合物、ジビニルスルホン、本国
特許3635718号記載の如き反応性のオレフィン化
合物、米国%iFF第2732316号記載の如きN−
メチロール化合物、米国特許第3103437号記載の
如きインシアナート類、米国特許第3017280号、
同第2983611号記載の如きアジリジリ化合物類、
米国特許第3100704号記載の如きカルポジイシド
系化合物類、米国特許第3091537号記載の如きエ
ポキシ化合物、ムコクロム酸の如きハロゲンカルボキシ
アルデヒド類、ジヒドロキシジオキサンの如きジオキサ
ンv5導体、クロム明ばん、カリ明ばん、硫酸ジルコニ
ウムの如き無機硬膜剤などがあり、これらをl′ai又
は2棟以上組合せて用いることが出来る。界面活性剤の
具体的な例としては、サポニンなどの天然界面活性剤、
アルキレンオキサイド系、グリセリン系、クリシドール
系などのノニオン界面活性剤高級アルキルアミン類、第
四級アンそニウム塩類、ピリジン、その他の楡素虫類、
スルホニウム類などのカチオン界面活性剤、カルホン酸
、燐酸、硫酸エステル基、燐酸エステル基等の酸性基を
含むアニオン界1lII]活性剤、アミノ触知、アミノ
スルホンmu、アミンアルコールの4iAtK又は燐酸
エステル類等の両性界面活性剤などがあり、これらを1
攬又は2種以上組合せて用いることが出来る。The surface protective layer in the present invention preferably contains an appropriate amount of a hardening agent and a surfactant. Specific examples of hard 1111J include aldehyde compounds such as formaldehyde and geltaraldehyde, titone compounds such as diacetyl and micropendione, and bis(2-chloroethylurea)-2-hydroxy-4,6-dichloro-1. ,3,5)
riazine, reactive halogen-bearing compounds as described in US Pat. No. 3,635,718, divinyl sulfone, reactive olefin compounds as described in US Pat. No. 3,635,718, N- as described in US %iFF No. 2,732,316.
Methylol compounds, incyanates such as those described in U.S. Pat. No. 3,103,437, U.S. Pat. No. 3,017,280;
Azirijiry compounds as described in No. 2983611,
Carposiside compounds as described in U.S. Pat. No. 3,100,704, epoxy compounds as described in U.S. Pat. No. 3,091,537, halogen carboxaldehydes such as mucochromic acid, dioxane V5 conductors such as dihydroxydioxane, chromium alum, potassium alum, sulfuric acid. There are inorganic hardeners such as zirconium, and these can be used in l'ai or in combination of two or more. Specific examples of surfactants include natural surfactants such as saponin,
Nonionic surfactants such as alkylene oxide type, glycerin type, cricidol type, higher alkyl amines, quaternary anthonium salts, pyridine, other elegans,
Cationic surfactants such as sulfoniums, anionic world containing acidic groups such as carbonic acid, phosphoric acid, sulfuric acid ester groups, phosphoric ester groups, etc. activators, amino tactile agents, amino sulfone mu, 4iAtK or phosphoric esters of amine alcohols There are amphoteric surfactants such as
It can be used alone or in combination of two or more types.
本発明の実施に用いられるハロゲン化銀乳剤は公知、慣
用の方法により調整することが出来るハロゲン化銀の生
成・分散方法、ハロゲン化銀組成(例えば、塩化鏝、臭
化銭、沃臭化銀、塩臭化鏝など)、ハロゲン化釧粒子の
サイズや晶癖ハロゲン化銀とゼラチン比率、ハロゲン化
銀乳剤のP)lやPAI化学増感剤の種類や量、その他
の添加剤の81類や量、セラチン、その他のバインダー
のat類や童などにより制限さnるものではない。The silver halide emulsion used in the practice of the present invention can be prepared by a known or commonly used method. , chlorobromide trowel, etc.), the size and crystal habit of the halide grains, the ratio of silver halide to gelatin, the type and amount of P)l of the silver halide emulsion and PAI chemical sensitizer, and other additives in Class 81. There are no limitations depending on the amount, seratin, or other binders.
本発明のハロゲン化銀写真材料に用いられる支持体とし
ては、バライタまたはポリオレフィン掬脂をラミネート
した紙、または透明フィルムに染料が酸化チタンの如き
、顔料を加えることにより不透明にしたフィルム及びセ
ールロースアセテートフィルム、ポリスチレンフィルム
、ポリエチレンテレフタレートフィルム、ボリヵーホネ
ートフイルムなどの各種フィルム類か挙げられる。Supports used in the silver halide photographic material of the present invention include paper laminated with baryta or polyolefin resin, transparent films made opaque by adding pigments such as titanium oxide, and salelose acetate. Films, polystyrene films, polyethylene terephthalate films, polycarbonate films, and various other films can be mentioned.
(綽 実施例
以下に本発明を実施例をもって詳細に説明するが、本発
明はこれらの態様に限定されるものでない0
実施例1
通常の方法で調整された塩臭化侭乳剤(Bマ:(’、I
P=60:40)をコロナ放電加工したポリエチレンラ
ミネート紺(光沢面)支持体上に鏝としてlA17m″
、セラテン411/m“となる様に、表面保禮層にセラ
チン217m″となる様にスライドホッパー型押し出し
塗布機により同時塗布した。(Example) The present invention will be explained in detail with reference to Examples below, but the present invention is not limited to these embodiments. (', I
P=60:40) as a trowel on a corona discharge machined polyethylene laminate navy blue (glossy side) support.
, Ceratin 411/m" and Ceratin 217 m" were simultaneously coated on the surface protection layer using a slide hopper type extrusion coater.
但し、表面保護層のパインターとして例示化合物の割合
(重量)が0.20%(試料1〜6とする)になるよう
にし塗布、乾燥した。次にこnらの試料とは別に比較化
合物として、アクリロニトリル・ブタジェン糸ラテック
ス、アクリレート糸ラテックス、スチレン寺ブタジェン
糸うテックスコロイタルシリカを用い、前述と同様(試
#+7〜10とする)になるようにした。However, the coating and drying were carried out in such a manner that the proportion (weight) of the exemplified compound was 0.20% (referred to as Samples 1 to 6) as a pinter of the surface protective layer. Next, apart from these samples, acrylonitrile-butadiene thread latex, acrylate thread latex, and styrene butadiene thread latex coroital silica were used as comparative compounds, and the result was the same as described above (species #+7 to 10). I did it like that.
史に1〜10の%試料の白地部及び黒地部の表面光沢度
及び最大反射画題(Dmax)を第1表に示した。これ
らの値の内、白地部の光沢の値は各々の試料を未露光の
状態で通常の写真処理を行ない又、黒地部の光沢の値は
各々の試料を適度な光で露光を行ない通常の写真処理を
行い、Dmaxは通常のセンシトメトリー及び写真処理
を行って自然放置し、乾燥された後に測定された値であ
る。Table 1 shows the surface glossiness and maximum reflection image (Dmax) of the white and black areas of the 1-10% samples. Among these values, the gloss value of the white background area is determined by performing normal photographic processing on each sample in an unexposed state, and the gloss value of the black background area is determined by exposing each sample to appropriate light and performing normal photographic processing. Photographic processing was performed, and Dmax was a value measured after normal sensitometry and photographic processing were performed, left to stand naturally, and dried.
ここでの表面光N[の値は日本電色工業製のVO−ID
型光沢計により入射角60°受光角600で測定したも
のである。同時にこれらのDmaxを同じ第1表に示し
た。ここでの反射両度の測定値はJIS−に7611に
記載の方法によるものである。The value of surface light N[ here is VO-ID manufactured by Nippon Denshoku Industries.
It was measured using a type gloss meter at an incident angle of 60° and a light receiving angle of 600°. At the same time, their Dmax are shown in the same Table 1. The measured value of the reflection power here is based on the method described in JIS-7611.
次に現像時に生じる黒地@(黒化された像部)の失透(
黒地部がくもって見える)について、視見的判断を行な
い失透のないものに○HJあるものにx印を付は同僚に
第1表に示した。Next, devitrification (devitrification) of the black background @ (blackened image area) that occurs during development
Regarding the results (the black background appears cloudy), I made a visual judgment and marked those with ○HJ with no devitrification and showed them to my colleagues in Table 1.
次に現泳さ口た試料を屋外(太陽光線が直接当たる所)
に放直し、約1ケ月後に放置していない試料と表面状態
を比較し、こnを耐秩性とし、変化がほとんどないもの
に○臼、変化のあるものに×印を付は同様に第1表に示
した。Next, the sample was swam outdoors (in a place exposed to direct sunlight).
After about one month, the surface condition was compared with the sample that had not been left for a while, and the surface condition was determined as resistance to corrosion. It is shown in Table 1.
(注)
比較用化合物
(1)n−ブチルアクリレート 100(2)
ブタジェン 3011.I アク
リロニトリル 70(3)スチレン
59ブタジエン
41(4) コロイダルシリカ
(以13余白)
第 1 表
第1表から明らかなごとく、本発明の共重合体水系分散
物(試料2〜6)は共重合体の含まれないもの(試料1
)に比較して黒地部の表面光沢度が高く、かつDmax
も高い。また、比較化合物(試料7〜10)に比較して
、黒地部の表面光沢、Dmax%埃像時の失透、耐候性
のいずnかで優nていることは明瞭である。(Note) Comparative compound (1) n-butyl acrylate 100 (2)
Butadiene 3011. I Acrylonitrile 70(3) Styrene
59 Butadiene
41 (4) Colloidal silica (13 blank spaces) Table 1 As is clear from Table 1, the copolymer aqueous dispersions of the present invention (Samples 2 to 6) are different from those containing no copolymer (Sample 1).
), the surface gloss of the black background is higher than that of Dmax
It's also expensive. Furthermore, it is clear that these compounds are superior to the comparative compounds (Samples 7 to 10) in terms of surface gloss of the black background, devitrification in Dmax% dust images, and weather resistance.
(F) 発明の効果
本発明の共重合体水系分散物を最外層に含有したハロゲ
ン化銀写真感光材料は、表面光沢を上昇させ、反射濃度
が高く、また現像時に失透させることなく、かつ、耐候
性にも優れている。(F) Effects of the Invention The silver halide photographic material containing the aqueous copolymer dispersion of the present invention in its outermost layer has increased surface gloss, high reflection density, and does not devitrify during development. , and has excellent weather resistance.
Claims (1)
するハロゲン化銀写真感光材料に於て、最外層の親水性
コロイド層中にスチレンおよび/またはスチレン誘導体
、アクリル酸エステル、不飽和カルボン酸から実質的に
なる共重合体水系分散物を含有することを特徴とするハ
ロゲン化銀写真感光材料。In a silver halide photographic light-sensitive material having at least two or more hydrophilic colloid layers on a support, the outermost hydrophilic colloid layer contains styrene and/or styrene derivatives, acrylic esters, unsaturated carboxylic acids, etc. 1. A silver halide photographic material comprising an aqueous copolymer dispersion consisting essentially of a copolymer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62030736A JPH0648353B2 (en) | 1987-02-13 | 1987-02-13 | Silver halide photographic light-sensitive material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP62030736A JPH0648353B2 (en) | 1987-02-13 | 1987-02-13 | Silver halide photographic light-sensitive material |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS63198047A true JPS63198047A (en) | 1988-08-16 |
JPH0648353B2 JPH0648353B2 (en) | 1994-06-22 |
Family
ID=12311957
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62030736A Expired - Lifetime JPH0648353B2 (en) | 1987-02-13 | 1987-02-13 | Silver halide photographic light-sensitive material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0648353B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02259636A (en) * | 1989-03-30 | 1990-10-22 | Mitsubishi Paper Mills Ltd | Silver halide photographic sensitive material for photomechanical process ensuring superior reducibility |
US5038934A (en) * | 1989-08-29 | 1991-08-13 | Brother Kogyo Kabushiki Kaisha | Microcapsule-carrying sheet storage cartridge and method of sealing the same |
EP0615158A1 (en) * | 1993-03-04 | 1994-09-14 | Konica Corporation | A silver halide photographic light-sensitive material |
EP0620481A2 (en) * | 1993-04-16 | 1994-10-19 | Konica Corporation | Silver Halide photographic light-sensitive material |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6087323A (en) * | 1983-10-19 | 1985-05-17 | Fuji Photo Film Co Ltd | Photosensitive material |
-
1987
- 1987-02-13 JP JP62030736A patent/JPH0648353B2/en not_active Expired - Lifetime
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6087323A (en) * | 1983-10-19 | 1985-05-17 | Fuji Photo Film Co Ltd | Photosensitive material |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH02259636A (en) * | 1989-03-30 | 1990-10-22 | Mitsubishi Paper Mills Ltd | Silver halide photographic sensitive material for photomechanical process ensuring superior reducibility |
US5038934A (en) * | 1989-08-29 | 1991-08-13 | Brother Kogyo Kabushiki Kaisha | Microcapsule-carrying sheet storage cartridge and method of sealing the same |
EP0615158A1 (en) * | 1993-03-04 | 1994-09-14 | Konica Corporation | A silver halide photographic light-sensitive material |
EP0620481A2 (en) * | 1993-04-16 | 1994-10-19 | Konica Corporation | Silver Halide photographic light-sensitive material |
EP0620481A3 (en) * | 1993-04-16 | 1994-11-23 | Konishiroku Photo Ind | Silver halide photographic light-sensitive material. |
US5415987A (en) * | 1993-04-16 | 1995-05-16 | Konica Corporation | Silver halide photographic light-sensitive material |
Also Published As
Publication number | Publication date |
---|---|
JPH0648353B2 (en) | 1994-06-22 |
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