JPH0570811B2 - - Google Patents
Info
- Publication number
- JPH0570811B2 JPH0570811B2 JP60085950A JP8595085A JPH0570811B2 JP H0570811 B2 JPH0570811 B2 JP H0570811B2 JP 60085950 A JP60085950 A JP 60085950A JP 8595085 A JP8595085 A JP 8595085A JP H0570811 B2 JPH0570811 B2 JP H0570811B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- color
- general formula
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- -1 silver halide Chemical class 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 26
- 239000000463 material Substances 0.000 claims description 25
- 229910052709 silver Inorganic materials 0.000 claims description 20
- 239000004332 silver Substances 0.000 claims description 20
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 4
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 claims description 4
- 229940045105 silver iodide Drugs 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 230000008878 coupling Effects 0.000 claims description 3
- 238000010168 coupling process Methods 0.000 claims description 3
- 238000005859 coupling reaction Methods 0.000 claims description 3
- 150000001340 alkali metals Chemical group 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000018109 developmental process Effects 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000011109 contamination Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000008020 evaporation Effects 0.000 description 5
- 159000000014 iron salts Chemical class 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 125000004104 aryloxy group Chemical group 0.000 description 4
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 125000004423 acyloxy group Chemical group 0.000 description 2
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 2
- 125000004414 alkyl thio group Chemical group 0.000 description 2
- 125000005110 aryl thio group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000005921 isopentoxy group Chemical group 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- YCMLQMDWSXFTIF-UHFFFAOYSA-N 2-methylbenzenesulfonimidic acid Chemical group CC1=CC=CC=C1S(N)(=O)=O YCMLQMDWSXFTIF-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical group NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005115 alkyl carbamoyl group Chemical group 0.000 description 1
- 125000005153 alkyl sulfamoyl group Chemical group 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 125000004422 alkyl sulphonamide group Chemical group 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 125000004421 aryl sulphonamide group Chemical group 0.000 description 1
- 125000001231 benzoyloxy group Chemical group C(C1=CC=CC=C1)(=O)O* 0.000 description 1
- 125000000051 benzyloxy group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])O* 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HNQIVZYLYMDVSB-UHFFFAOYSA-N methanesulfonimidic acid Chemical group CS(N)(=O)=O HNQIVZYLYMDVSB-UHFFFAOYSA-N 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001148 pentyloxycarbonyl group Chemical group 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- 125000005420 sulfonamido group Chemical group S(=O)(=O)(N*)* 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/44—Regeneration; Replenishers
-
- 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/32—Colour coupling substances
- G03C7/36—Couplers containing compounds with active methylene groups
- G03C7/38—Couplers containing compounds with active methylene groups in rings
- G03C7/384—Couplers containing compounds with active methylene groups in rings in pyrazolone rings
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Description
（産業上の利用分野）
本発明はハロゲン化銀カラー写真感光材料の処
理方法に関し、更に詳しくは発色現像処理時の処
理変動が大巾に改良され、しかも低公害化を実現
しうるハロゲン化銀カラー写真感光材料の処理方
法に関する。
(Industrial Application Field) The present invention relates to a method for processing silver halide color photographic light-sensitive materials, and more specifically, to a method for processing silver halide color photographic materials, and more specifically, to a method for processing silver halide color photographic materials, and more specifically, to a method for processing silver halide color photographic materials, which greatly improves processing fluctuations during color development processing and which can realize low pollution. This invention relates to a method for processing color photographic materials.
一般にカラー写真感光材料は露光後パラフエニ
レンジアミン系発色現像主薬を含有する現像液で
処理する発色現像と漂白、定着又は漂白定着及び
水洗を含む処理工程を経て写真画像が出来る。
上記発色現像処理工程では発色現像主薬の酸化
体とカラーカプラーとのカンプリング反応によつ
て色画像を形成し、同時に該写真工程で金属銀が
生成される。この金属銀は引続く脱銀工程におい
て、漂白剤により酸化され、定着剤によつて可溶
性の銀錯体を形成し、溶解し去る。
近年、環境保護上の問題及びコスト上の問題か
ら低公害化の為の研究が行なわれ一部の処理工程
で実用化されている。特に発色現像処理工程にお
いてはその公害性の大きさから従来から様々な低
公害化技術が提案されている。例えば特開昭54−
37731号、同56−1048号、同56−1049号、同56−
27142号、同56−33644号、同56−149036号等に記
載の電気透析による再生法、特公昭55−1571号、
特開昭58−14831号による活性炭による再生法、
特開昭52−105820号記載のイオン交換膜法、更に
は特開昭53−132343号、同55−144240号、同57−
146249号、米国特許4348475号記載のイオン交換
樹脂による方法等が開示されている。しかしなが
ら前記方法は再生装置が大きく高価であること、
更には現像レベルを一定水準に保つ為に再生液を
分析する熱練者が必要であることから、ほんの一
部がラボ以外では全く行なわれていないのが実状
である。一方、再生法によらず発色現像液の補充
液を減少させることによつて排液を減少させる方
法が最近行なわれるようになつてきた。この方法
は前述した方法と違い、大がかりで高価な装置や
熟練した分析者を必要とせずに低公害化を達成す
る上で好ましい方法と言える。しかしながらこの
方法によつてある程度の低補充化は可能である
が、蒸発による発色現像液の濃縮化及びベルトや
バツクコンタミネーシヨンによる鉄塩やチオ硫酸
塩等の混入、乳剤からの溶出物例えば活性剤や抑
制成分の流出等による処理変動や処理ステインが
大きくなるという重大な欠点がある。特にこの傾
向は低補充化がすすみ更に高温処理や低処理量の
場合特に、顕著になる。低補充化に伴う発色現像
液中への鉄塩やチオ硫酸塩等の混入による処理変
動を防止する技術としては種々のキレート剤や特
開昭57−150847号、同58−120250号、同58−
121036号に記載されているが如く、ポリビニルピ
ロリドン系化合物やポエリチレングリコール系化
合物が開示されているが、もつぱらこれらの技術
は少量の鉄塩やチオ硫酸塩の混入に効果があるだ
けであり、低補充化が更に進み鉄塩やチオ硫酸塩
の発色現像液中へ混入比率が高くなつた場合は余
り効果が認められない。又、前記キレート剤やポ
リビニルピロリドン、ポリエチレングリコール系
高分子化合物を多量に添加せしめた場合、感光材
料の写真特性に大きな影響を与える為に好ましく
ない。
Generally, after exposure, color photographic materials undergo processing steps including color development using a developer containing a paraphenylenediamine color developing agent, bleaching, fixing, or bleach-fixing and washing to produce a photographic image. In the color development processing step, a color image is formed by a compres- sion reaction between the oxidized color developing agent and the color coupler, and at the same time, metallic silver is produced in the photographic step. In a subsequent desilvering step, this metallic silver is oxidized by a bleaching agent, forms a soluble silver complex by a fixing agent, and is dissolved away. In recent years, due to environmental protection and cost issues, research has been conducted to reduce pollution, and this has been put into practical use in some treatment processes. Particularly in the color development process, various low-pollution techniques have been proposed in the past due to the high level of pollution caused by the process. For example, JP-A-54-
No. 37731, No. 56-1048, No. 56-1049, No. 56-
Regeneration method by electrodialysis described in No. 27142, No. 56-33644, No. 56-149036, etc., Japanese Patent Publication No. 55-1571,
Regeneration method using activated carbon according to JP-A No. 58-14831,
The ion exchange membrane method described in JP-A-52-105820, as well as JP-A-53-132343, JP-A-55-144240, and JP-A-57-
146249, a method using an ion exchange resin described in US Pat. No. 4,348,475, etc. are disclosed. However, in the above method, the reproducing equipment is large and expensive;
Furthermore, in order to maintain the development level at a certain level, a skilled person is required to analyze the regenerating solution, so the reality is that only a small portion of this process is carried out at all outside of laboratories. On the other hand, a method has recently come into use in which the amount of waste liquid is reduced by reducing the amount of replenisher for the color developing solution without using the regeneration method. Unlike the methods described above, this method can be said to be a preferable method for achieving low pollution without requiring large-scale, expensive equipment or skilled analysts. However, although it is possible to reduce replenishment to a certain extent by this method, concentration of the color developing solution due to evaporation, contamination of iron salts, thiosulfates, etc. due to belt and back contamination, and eluates from the emulsion, such as active This method has serious disadvantages in that processing fluctuations and processing stains increase due to outflow of agents and inhibitory components. This tendency becomes particularly noticeable when low replenishment progresses and high temperature treatment and low throughput are performed. Various chelating agents and JP-A-57-150847, JP-A-58-120-250, and JP-A-58 are used to prevent processing fluctuations due to the contamination of iron salts, thiosulfates, etc. into the color developing solution due to low replenishment. −
As described in No. 121036, polyvinylpyrrolidone-based compounds and polyethylene glycol-based compounds have been disclosed, but these techniques are only effective against the contamination of small amounts of iron salts and thiosulfates. However, if the reduction in replenishment progresses further and the ratio of iron salts or thiosulfates mixed into the color developing solution increases, little effect will be observed. Further, it is not preferable to add a large amount of the chelating agent, polyvinylpyrrolidone, or polyethylene glycol-based polymer compound, since this greatly affects the photographic properties of the light-sensitive material.
本発明は低補充化に伴うハロゲン化銀写真感光
材料の処理変動を大幅に改良することにあり、第
２に大幅な低公害化を簡易でしかも安価な方法で
達成することにある。更にまた他の目的として高
感度で画質が優れたカラー写真画像を形成しうる
処理方法を提供することにある。
The purpose of the present invention is to significantly improve the processing fluctuations of silver halide photographic materials due to low replenishment, and secondly, to achieve a significant reduction in pollution using a simple and inexpensive method. Still another object of the present invention is to provide a processing method capable of forming color photographic images with high sensitivity and excellent image quality.
本発明者等は鋭意研究を重ねた結果、３モル％
以上の沃化銀を含むコアシエル乳剤を少なくとも
１層有しかつ下記一般式〔〕で表されるマゼン
タカプラーを含有するハロゲン化銀カラー写真感
光材料を臭化物3.0×10-3モル／以下含有した
発色現像補充液をハロゲン化銀カラー写真感光材
料100cm2当たり９ml以下の補充液を補充し、処理
することによつて達成されることを本発明者等は
見出した。
一般式〔〕
As a result of intensive research, the present inventors found that 3 mol%
A coloring material containing at least one layer of a core-shell emulsion containing the above silver iodide and a magenta coupler represented by the following general formula [] containing 3.0 x 10 -3 mol/or less of bromide. The present inventors have found that this can be achieved by replenishing the developer replenisher in an amount of 9 ml or less per 100 cm 2 of the silver halide color photographic light-sensitive material. General formula []
【式】
式中Arはフエニル基であり、特に置換された
フエニル基である。Ｙは芳香族第１級アミン発色
現像主薬の酸化体とカツプリングして色素が形成
されるときに離脱する基を表す。Ｘはハロゲン原
子、アルコキシ基、アルキル基である。Ｒはベン
ゼン環に置換可能な基を表し、ｎは１又は２を表
す。ｎが２のときＲは同じでも異なつてていもよ
い。
更に本発明に実施態様として下記一般式〔〕
〜〔〕で示されるキレート剤を含有し、更に又
発色現像補充液中の臭化物が3.0×10-3モル／
以下含有し、かつハロゲン化銀カラー写真感光材
料100cm2当り前記発色現像補充液を7.5ml以下補充
し、処理することによつて本発明の効果が顕著に
なる。
一般式〔〕 Ａ−COOM
一般式〔〕 Ｂ−PO3M2
一般式〔〕[Formula] In the formula, Ar is a phenyl group, especially a substituted phenyl group. Y represents a group that leaves when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent. X is a halogen atom, an alkoxy group, or an alkyl group. R represents a group that can be substituted on the benzene ring, and n represents 1 or 2. When n is 2, R may be the same or different. Further, as an embodiment of the present invention, the following general formula []
~ Contains a chelating agent shown in [], and furthermore, the bromide content in the color developer replenisher is 3.0×10 -3 mol/
The effect of the present invention becomes remarkable when the above-mentioned color development replenisher is added to 7.5 ml or less per 100 cm 2 of a silver halide color photographic light-sensitive material and processed. General formula [] A-COOM General formula [] B-PO 3 M 2 General formula []
【式】
式中Ａ、及びＢは各々一価の基もしくは原子を
表し、無機物であつてもよいし、有機物であつて
もよい。Ｄは置換基を有してもよい芳香族環又は
複素環を形成するに必要な非金属原子群を表し、
Ｍは水素原子又はアルカリ金属原子を表す。
以下本発明について詳細に説明すると本発明は
低公害化及び低コストを実現する為に低補充化を
行つた場合カラー写真感光材料の処理変動や処理
ステインが大きくなり、特に発色現像補充液がハ
ロゲン化銀カラー写真感光材料100cm2当たり９ml
以下の補充を行つて処理した際に顕著に処理変動
が大きくなることを見出だした。一般に沃化銀を
含むカラー写真感光材料例えば撮影用カラー写真
感光材料の如きカラーネガテイブフイルムは発色
現像補充量は100cm2当たり約15ml補充されている
が、この場合、補充量が多い為鉄塩やチオ硫酸塩
の如き前浴成分の混入以外余り問題とならない
が、補充量が減少して９ml以下になつた場合前記
したように蒸発による発色現像液の濃縮及び乳剤
溶出物の蓄積が問題となり、特に緑感性層の濃度
変動やステイン発生しやすくなることを本発明者
等は見出した。従つて蒸発による発色現像液の濃
縮を防止すること又は濃縮しても余りカラー写真
感光材料に影響しないこと、更には乳剤溶出物、
特にハロゲン化アルカリ塩の蓄積を防止又は一定
にコントロールする必要がある。
従来は上記問題に対し殆ど解決方法を見出だせ
ない為に更なる低補充化が不可能であつたが、ハ
ロゲン化銀カラー写真感光材料として３モル％以
上の沃化銀を含むコアシエル型ハロゲン化銀粒子
を含む乳剤層の少なくとも１層と一般式〔〕で
表されるマゼンタカプラーを含有する構成とし、
発色現像処理は発色現像補充液の臭化物を3.0×
10-3モル／以下にすることによつて支障のない
臭化物濃度に維持し、９ml／100cm2以下の低補充
を可能にするに至つたものである。
更に本発明について詳細に説明すると、本発明
の発色現像補充液の補充量は９ml以下であるが、
蒸発量を考慮した場合好ましくは１ml以上９ml以
下、特に好ましくは３ml以上7.5ml以下で補充さ
れる。
発色現像補充液の補充方法は公知の方法によつ
て補充されるが望ましくはベローズポンプの様な
定量ポンプを用いるのが良い。本発明の発色現像
補充液中の臭化物は3.0×10-3モル／以下であ
るが、低補充化の度合によつて臭化物濃度を調整
する必要があるが、一般的には補充量が減少する
に従つて発色現像補充液中の臭化物濃度を減少さ
せる必要がある。
発色現像補充液中の臭化物濃度は発色現像液中
の臭化物濃度（主に乳剤から溶出及び蒸発によつ
て決まる）を一定に保つように調整されるが臭化
物濃度が3.0×10-3モル／以下であり、かつ発
色現像補充液量が９ml／100cm2以下だと写真特性
に影響を余り与えず処理の安定化を計ることがで
きる。
臭化物の具体的化合物としては臭化ナトリウ
ム、臭化カリウム、臭化アンモニウム等のアルカ
リ金属塩、及び臭化水素酸が挙げられる。
次に、本発明に用いられるマゼンタ色素形成カ
プラーは、下記一般式〔〕
で表すことができる。
一般式〔〕[Formula] In the formula, A and B each represent a monovalent group or atom, and may be an inorganic substance or an organic substance. D represents a nonmetallic atomic group necessary to form an aromatic ring or a heterocycle that may have a substituent,
M represents a hydrogen atom or an alkali metal atom. The present invention will be explained in detail below. When low replenishment is carried out in order to achieve low pollution and cost reduction, processing fluctuations and processing stains of color photographic light-sensitive materials become large. Silver chemical color photographic material 9ml per 100cm2
It has been found that processing fluctuations become significantly large when processing is performed with the following supplementation. In general, color negative film containing silver iodide-containing color photographic materials, such as color photographic materials for photography, is refilled with approximately 15 ml per 100 cm2 of color development, but in this case, since the amount of replenishment is large, iron salts, etc. There is not much of a problem other than the contamination of pre-bath components such as thiosulfate, but if the replenishment amount decreases to 9 ml or less, concentration of the color developing solution due to evaporation and accumulation of emulsion eluate become a problem as described above. The inventors of the present invention have found that the green-sensitive layer is particularly susceptible to density fluctuations and stains. Therefore, it is necessary to prevent concentration of the color developing solution due to evaporation, or to ensure that concentration does not affect the color photographic material too much, and furthermore, to prevent emulsion eluate,
In particular, it is necessary to prevent or control the accumulation of alkali halide salts. Conventionally, it has been impossible to further reduce the replenishment level because almost no solution has been found to the above problem, but core-shell type halogen containing 3 mol% or more of silver iodide has been used as a silver halide color photographic light-sensitive material. A structure containing at least one emulsion layer containing silver oxide grains and a magenta coupler represented by the general formula [],
For color development processing, add bromide in the color development replenisher to 3.0x.
By setting the bromide concentration to 10 -3 mol/or less, it is possible to maintain the bromide concentration without causing any problems and to make it possible to replenish as low as 9 ml/100 cm 2 or less. To further explain the present invention in detail, the replenishment amount of the color development replenisher of the present invention is 9 ml or less,
When considering the amount of evaporation, it is preferably replenished at 1 ml or more and 9 ml or less, particularly preferably 3 ml or more and 7.5 ml or less. The color developer replenisher can be replenished by any known method, but it is preferable to use a metering pump such as a bellows pump. The bromide content in the color developer replenisher of the present invention is 3.0×10 -3 mol/or less, but it is necessary to adjust the bromide concentration depending on the degree of low replenishment, but generally the amount of replenishment will decrease. Accordingly, it is necessary to reduce the bromide concentration in the color developer replenisher. The bromide concentration in the color developer replenisher is adjusted to keep the bromide concentration in the color developer (mainly determined by elution and evaporation from the emulsion) constant, but the bromide concentration is 3.0×10 -3 mol/or less. In addition, if the amount of color developing replenisher is 9 ml/100 cm 2 or less, it is possible to stabilize the processing without significantly affecting photographic properties. Specific examples of bromide include alkali metal salts such as sodium bromide, potassium bromide, and ammonium bromide, and hydrobromic acid. Next, the magenta dye-forming coupler used in the present invention can be represented by the following general formula []. General formula []
【式】
Ar：フエニル基であり、特に置換されたフエ
ニル基である。
置換基としてはハロゲン原子、アルキル基、ア
ルコキシ基、アリールオキシ基、アルコキシカル
ボニル基、シアノ基、カルバモイル基、スルフア
モイル基、スルホニル基、スルホンアミド基又は
アシルアミノ基であり、Arで表されるフエニル
基に２個以上の置換基を有してもよい。
以下に置換基の具体的な例を挙げる。
ハロゲン原子：塩素、臭素、フツ素
アルキル基：メチル基、エチル基、iso−プロ
ピル基、ブチル基、ｔ−ブチル基、ｔ−ペンチル
基等であるが特に炭素原子数１〜５のアルキル基
が特に好ましい。
アルコキシ基：メトキシ基、エトキシ基、ブト
キシ基、sec−ブトキシ基、iso−ペンチルオキシ
基等であるが、特に炭素原子数１〜５のアルコキ
シ基が好ましい。
アリールオキシ基：フエノキシ基、β−ナフト
キシ基等であるが、このアリール部分には更に
Arで示されるフエニル基に挙げていると同様な
置換基を有してもよい。
アルコキシカルボニル基：上述したアルコキシ
基の付いたカルボニル基であり、メトキシカルボ
ニル基、ペンチルオキシカルボニル基等のアルキ
ル部分の炭素原子数が１〜５のものが好ましい。
カルバモイル基：カルバモイル基、ジメチルカ
ルバモイル基等のアルキルカルバモイル基
スルフアモイル基：スルフアモイル基、メチル
スルフアモイル基、ジメチルスルフアモイル基、
エチルスルフアモイル基等のアルキルスルフアモ
イル基
スルホニル基：メタンスルホニル基、エタンス
ルホニル基、ブタンスルホニル基等のアルキルス
ルホニル基
スルホンアミド基：メタンスルホンアミド基、
トルエンスルホンアミド基等のアルキルスルホン
アミド基、アリールスルホンアミド基等
アシルアミノ基：アセトアミノ基、ピバロイル
アミノ基、ベンズアミド基等
特に好ましくはハロゲン原子であり、その中で
も塩素が最も好ましい。
Ｙ：芳香族第１級アミン発色現像主薬の酸化体
とカツプリングして色素が形成されるときに離脱
する基を表す。
具体的には例えばハロゲン原子、アルコキシ
基、アリールオキシ基、アシルオキシ基、アリー
ルチオ基、アルキルチオ基、[Formula] Ar: a phenyl group, especially a substituted phenyl group. Substituents include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a cyano group, a carbamoyl group, a sulfamoyl group, a sulfonyl group, a sulfonamido group, or an acylamino group; It may have two or more substituents. Specific examples of substituents are listed below. Halogen atoms: chlorine, bromine, fluorine Alkyl groups: Methyl group, ethyl group, iso-propyl group, butyl group, t-butyl group, t-pentyl group, etc., but especially alkyl groups having 1 to 5 carbon atoms Particularly preferred. Alkoxy group: Methoxy group, ethoxy group, butoxy group, sec-butoxy group, iso-pentyloxy group, etc., and particularly preferred is an alkoxy group having 1 to 5 carbon atoms. Aryloxy group: phenoxy group, β-naphthoxy group, etc., but this aryl part also has
It may have the same substituents as those listed for the phenyl group represented by Ar. Alkoxycarbonyl group: The above-mentioned carbonyl group having an alkoxy group attached thereto, and those having an alkyl moiety of 1 to 5 carbon atoms, such as a methoxycarbonyl group and a pentyloxycarbonyl group, are preferable. Carbamoyl group: carbamoyl group, alkylcarbamoyl group such as dimethylcarbamoyl group Sulfamoyl group: sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group,
Alkylsulfamoyl group such as ethylsulfamoyl group Sulfonyl group: Alkylsulfonyl group such as methanesulfonyl group, ethanesulfonyl group, butanesulfonyl group Sulfonamide group: methanesulfonamide group,
Alkylsulfonamide groups such as toluenesulfonamide groups, arylsulfonamide groups, etc. Acylamino groups: acetamino groups, pivaloylamino groups, benzamide groups, etc. Particularly preferred are halogen atoms, among which chlorine is most preferred. Y: represents a group that leaves when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent. Specifically, for example, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, an arylthio group, an alkylthio group,
【式】（Ｚは窒
素原子と共に炭素原子、酸素原子、窒素原子及び
イオウ原子の中から選ばれた原子と５ないし６員
環を形成するに要する原子群を表す。）
以下に具体的な例を挙げる。
ハロゲン原子：塩素、臭素、フツ素
アルコキシ基：エトキシ基、ベンジルオキシ
基、メトキシエチルカルバモイルメトキシ基、テ
トラデシルカルバモイルメトキシ基等
アリールオキシ基：フエノキシ基、４−メトキ
シフエノキシ基、４−ニトロフエノキシ基等
アシルオキシ基：アセトキシ基、ミリストイル
オキシ基、ベンゾイルオキシ基等
アリールチオ基：フエニルチオ基、２−ブトキ
シ−５−オクチルフエニルチオ基、２，５−ジヘ
キシルオクチルフエニルチオ基等
アルキルチオ基：メチルチオ基、オクチルチオ
基、ヘキサデシルチオ基、ベンジルチオ基、２−
（ジエチルアミノ）エチルチオ基、エトキシカル
ボニルメチルチオ基、エトキシエチルチオ基、フ
エノキシエチルチオ基等[Formula] (Z represents an atomic group required to form a 5- or 6-membered ring with a nitrogen atom and an atom selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms.) Specific examples are shown below. List. Halogen atoms: chlorine, bromine, fluorine Alkoxy groups: ethoxy group, benzyloxy group, methoxyethylcarbamoylmethoxy group, tetradecylcarbamoylmethoxy group, etc. Aryloxy group: phenoxy group, 4-methoxyphenoxy group, 4-nitrophenoxy group etc. Acyloxy group: acetoxy group, myristoyloxy group, benzoyloxy group, etc. Arylthio group: phenylthio group, 2-butoxy-5-octylphenylthio group, 2,5-dihexyloctylphenylthio group, etc. Alkylthio group: methylthio group, Octylthio group, hexadecylthio group, benzylthio group, 2-
(diethylamino)ethylthio group, ethoxycarbonylmethylthio group, ethoxyethylthio group, phenoxyethylthio group, etc.
【式】ピラゾリル基、イミダゾリル基、
トリアゾリル基、テトラゾリル基等
Ｘ：ハロゲン原子、アルコキシ基又はアルキル
基を表す。
具体的な例を以下に挙げる。
ハロゲン原子：塩素、臭素、フツ素
アルコキシ基：メトキシ基、エトキシ基、sec
−ブトキシ基、iso−ペンチルオキシ基等の炭素
原子数が１〜５のアルコキシ基が好ましい。
アルキル基：メチル基、エチル基、iso−プロ
ピル基、ブチル基、ｔ−ブチル基、ｔ−ペンチル
基等の炭素原子数が１〜５のアルキル基が好まし
い。
特に好ましくはハロゲン原子であり、中でも塩
素が好ましい。
Ｒ：ベンゼン環に置換可能な基を表し、ｎは１
又は２を表す。ｎが２のときＲは同じでも異なつ
てていもよい。
Ｒで表されるベンゼン環に置換可能な基として
は、ハロゲン原子、R′−，R′O，[Formula] Pyrazolyl group, imidazolyl group, triazolyl group, tetrazolyl group, etc. X: represents a halogen atom, an alkoxy group, or an alkyl group. Specific examples are listed below. Halogen atoms: chlorine, bromine, fluorine Alkoxy groups: methoxy group, ethoxy group, sec
Alkoxy groups having 1 to 5 carbon atoms such as -butoxy group and iso-pentyloxy group are preferred. Alkyl group: An alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an iso-propyl group, a butyl group, a t-butyl group, and a t-pentyl group, is preferable. Particularly preferred is a halogen atom, with chlorine being particularly preferred. R: represents a group that can be substituted on the benzene ring, n is 1
Or represents 2. When n is 2, R may be the same or different. Groups that can be substituted on the benzene ring represented by R include halogen atom, R'-, R'O,
【式】R′COO−，[Formula] R′COO−,
【式】R′O−CO−，[Formula] R′O−CO−,
【式】 等が挙げられる。 R′，R″及びＲ【formula】 etc. R′, R″ and R
Claims (1)
含有するハロゲン化銀乳剤層を少なくとも１層有
し、かつ下記一般式〔〕で示されるマゼンタカ
プラーを含有するハロゲン化銀カラー写真感光材
料を発色現像処理する際、該発色現像補充液に臭
化物を3.0×10-3モル／以下含有し、ハロゲン
化銀カラー写真感光材料100cm2当たり、前記発色
現像補充液を９ml以下補充し処理することを特徴
とするハロゲン化銀カラー写真感光材料の処理方
法。 一般式〔〕 【式】 【式中Arはフエニル基であり、特に置換され
たフエニル基である。Ｙは芳香族第１級アミン発
色現像主薬の酸化体とカツプリングして色素が形
成されるときに離脱する基を表す。Ｘはハロゲン
原子、アルコキシ基、アルキル基である。Ｒはベ
ンゼン環に置換可能な基を表し、ｎは１又は２を
表す。ｎが２のときＲは同じでも異なつてていも
よい。】 ２ 前記発色現像液中に下記一般式〔〕〜
〔〕で示されるキレート剤を含有することを特
徴とする特許請求の範囲第１項記載のハロゲン化
銀カラー写真感光材料の処理方法。 一般式〔〕 Ａ−COOM 一般式〔〕 Ｂ−PO3M2 一般式〔〕 【式】 〔式中Ａ、及びＢは各々一価の基もしくは原子
を表し、無機物であつてもよいし、有機物であつ
てもよい。Ｄは置換基を有してもよい芳香族環又
は複素環を形成するに必要な非金属原子群を表
し、Ｍは水素原子又はアルカリ金属原子を表す。〕 ３ 前記発色現像補充液の臭化物が2.0×10-3モ
ル／以下含有し、かつハロゲン化銀カラー写真
感光材料100cm2当たり前記発色現像補充液を7.5ml
以下補充し、処理することを特徴とする特許請求
の範囲第１項または第２項記載のハロゲン化銀カ
ラー写真感光材料の処理方法。[Scope of Claims] 1. A silver halide having at least one silver halide emulsion layer containing a core-shell emulsion containing 3 mol% or more of silver iodide, and containing a magenta coupler represented by the following general formula [] When a color photographic light-sensitive material is subjected to color development processing, the color developer replenisher contains not more than 3.0 x 10 -3 mole of bromide, and 9 ml or less of the color developer replenisher is replenished per 100 cm 2 of the silver halide color photographic light-sensitive material. 1. A method for processing a silver halide color photographic light-sensitive material, the method comprising processing a silver halide color photographic material. General formula [] [Formula] [In the formula, Ar is a phenyl group, especially a substituted phenyl group. Y represents a group that leaves when a dye is formed by coupling with an oxidized product of an aromatic primary amine color developing agent. X is a halogen atom, an alkoxy group, or an alkyl group. R represents a group that can be substituted on the benzene ring, and n represents 1 or 2. When n is 2, R may be the same or different. ] 2 In the color developer, the following general formula [] ~
A method for processing a silver halide color photographic light-sensitive material according to claim 1, which comprises a chelating agent represented by [ ]. General formula [] A-COOM General formula [] B-PO 3 M 2 General formula [] [Formula] [In the formula, A and B each represent a monovalent group or atom, and may be an inorganic substance, It may be an organic substance. D represents a nonmetallic atom group necessary to form an aromatic ring or a heterocycle which may have a substituent, and M represents a hydrogen atom or an alkali metal atom. ] 3 The color developer replenisher contains 2.0×10 -3 mol or less of bromide, and the color developer replenisher is contained in an amount of 7.5 ml per 100 cm 2 of the silver halide color photographic light-sensitive material.
A method for processing a silver halide color photographic light-sensitive material according to claim 1 or 2, characterized in that the material is subsequently replenished and processed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8595085A JPS61243453A (en) | 1985-04-20 | 1985-04-20 | Treatment of silver halide color photographic sensitive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8595085A JPS61243453A (en) | 1985-04-20 | 1985-04-20 | Treatment of silver halide color photographic sensitive material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61243453A JPS61243453A (en) | 1986-10-29 |
| JPH0570811B2 true JPH0570811B2 (en) | 1993-10-05 |
Family
ID=13873037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8595085A Granted JPS61243453A (en) | 1985-04-20 | 1985-04-20 | Treatment of silver halide color photographic sensitive material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61243453A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2536747B2 (en) * | 1987-02-04 | 1996-09-18 | 富士写真フイルム株式会社 | Processing method of silver halide color photographic light-sensitive material |
| JPH0219844A (en) * | 1988-07-07 | 1990-01-23 | Konica Corp | Method for processing silver halide color photographic sensitive material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5674247A (en) * | 1979-11-22 | 1981-06-19 | Konishiroku Photo Ind Co Ltd | Method for continuously processing silver halide photographic material |
| JPS56165142A (en) * | 1980-05-23 | 1981-12-18 | Konishiroku Photo Ind Co Ltd | Processing method for photographic sensitive silver halide material |
| JPS59149346A (en) * | 1983-02-16 | 1984-08-27 | Konishiroku Photo Ind Co Ltd | Silver halide photosensitive material |
-
1985
- 1985-04-20 JP JP8595085A patent/JPS61243453A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5674247A (en) * | 1979-11-22 | 1981-06-19 | Konishiroku Photo Ind Co Ltd | Method for continuously processing silver halide photographic material |
| JPS56165142A (en) * | 1980-05-23 | 1981-12-18 | Konishiroku Photo Ind Co Ltd | Processing method for photographic sensitive silver halide material |
| JPS59149346A (en) * | 1983-02-16 | 1984-08-27 | Konishiroku Photo Ind Co Ltd | Silver halide photosensitive material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61243453A (en) | 1986-10-29 |
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