JPH0374815B2 - - Google Patents
Info
- Publication number
- JPH0374815B2 JPH0374815B2 JP58227512A JP22751283A JPH0374815B2 JP H0374815 B2 JPH0374815 B2 JP H0374815B2 JP 58227512 A JP58227512 A JP 58227512A JP 22751283 A JP22751283 A JP 22751283A JP H0374815 B2 JPH0374815 B2 JP H0374815B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- general formula
- photographic
- color
- alkyl group
- 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 - Lifetime
Links
- -1 aromatic primary amine Chemical class 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 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
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 claims description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 2
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 claims 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 229910052742 iron Inorganic materials 0.000 description 12
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 11
- 229910001431 copper ion Inorganic materials 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 9
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000002738 chelating agent Substances 0.000 description 7
- 238000000354 decomposition reaction Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000003352 sequestering agent Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003755 preservative agent Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 230000005856 abnormality Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002335 preservative effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- XQRLCLUYWUNEEH-UHFFFAOYSA-N diphosphonic acid Chemical compound OP(=O)OP(O)=O XQRLCLUYWUNEEH-UHFFFAOYSA-N 0.000 description 2
- 229960001484 edetic acid Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ULZRKSDAMUWQEZ-UHFFFAOYSA-N 1-anilinoethanol Chemical compound CC(O)NC1=CC=CC=C1 ULZRKSDAMUWQEZ-UHFFFAOYSA-N 0.000 description 1
- FOUZISDNESEYLX-UHFFFAOYSA-N 2-(2-hydroxyethylazaniumyl)acetate Chemical compound OCCNCC(O)=O FOUZISDNESEYLX-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XXAXVMUWHZHZMJ-UHFFFAOYSA-L 4,5-dihydroxybenzene-1,3-disulfonate Chemical compound OC1=CC(S([O-])(=O)=O)=CC(S([O-])(=O)=O)=C1O XXAXVMUWHZHZMJ-UHFFFAOYSA-L 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PQUCIEFHOVEZAU-UHFFFAOYSA-N Diammonium sulfite Chemical compound [NH4+].[NH4+].[O-]S([O-])=O PQUCIEFHOVEZAU-UHFFFAOYSA-N 0.000 description 1
- VSNHCAURESNICA-UHFFFAOYSA-N Hydroxyurea Chemical compound NC(=O)NO VSNHCAURESNICA-UHFFFAOYSA-N 0.000 description 1
- JYXGIOKAKDAARW-UHFFFAOYSA-N N-(2-hydroxyethyl)iminodiacetic acid Chemical compound OCCN(CC(O)=O)CC(O)=O JYXGIOKAKDAARW-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000001118 alkylidene group Chemical group 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
- 239000007844 bleaching agent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229940120503 dihydroxyacetone Drugs 0.000 description 1
- 231100000676 disease causative agent Toxicity 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010186 staining Methods 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
- G03C7/407—Development processes or agents therefor
- G03C7/413—Developers
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、写真用発色現像剤組成物に関し、更
に詳細には重金属イオンの混入による有害な作用
を防止した写真用発色現像剤組成物に関する。
（従来技術）
一般にハロゲン化銀カラー写真感光材料は画像
露光の後、発色現像工程と脱銀工程とを基本工程
とする一連の写真処理により色素画像を形成す
る。
上記の発色現像工程では、発色現像主薬の酸化
体が、共存するカラーカプラーとカプリング反応
することによつて画像模様の色素画像を形成し、
同時に還元銀が生成される。ここに生成された銀
は、引続く脱銀工程において、漂白剤により酸化
され、定着剤の作用を受けて可溶性の銀錯体に変
化し、水洗によつて溶解し去る。
通常の発色現像液においては、芳香族第１級ア
ミン発色現像主薬の酸化防止のために、保恒剤と
して亜硫酸塩あるいは、亜硫酸塩とヒドロキシル
アミンの水溶性塩とが添加されている。
これらの亜硫酸塩は単独で現像液に添加したの
では、必ずしも保存性が十分ではないので、ヒド
ロキシルアミンを水溶性塩として添加することに
より効果的に保恒性が得られることは既に知られ
ている。又別には亜硫酸塩やヒドロキシルアミン
に代る保恒剤としてジヒドロキシアセトン、アニ
リノエタノール、ヒドロキシル尿素等が知られて
いる。
しかしながら、これらの保恒剤は共存する微量
の金属イオン、特に鉄イオンにより触媒作用を受
けて酸化されて保恒効果が減少し、また、ヒドロ
キシルアミン塩はアンモニアを発生し、カラー写
真感光材料にカブリや汚染を形成させたり、写真
特性を変化させたりする。
そこで金属イオンによるこのような好ましくな
い作用を防止するために各種金属キレート剤を添
加し、感光材料に含有せしめる技術が提案され、
実用化されている。例えば米国特許第3839045号
にはヒドロキシアルキリデンニホスホン酸金属イ
オン封鎖剤とリチウム塩の使用、米国特許第
3746544号にはポリヒドロキシ化合物とアミノポ
リカルボン酸金属イオン封鎖剤とを併用する技
術、また米国特許第4264716号にはポリヒドロキ
シ化合物とアミノポリホスホン酸金属イオン封鎖
剤を併用する技術がそれぞれ開示されている。こ
れら開示された技術によると現像液に混入した重
金属イオン特に鉄イオンによる影響を減少させる
ことができる。
しかしながら、本発明者等による検討の結果で
は、アミノ基上に水溶性基を有する芳香族第１級
アミノ発色現像主薬を含有する現像液でこれら前
記のキレート剤を添加したにもかかわらず自動現
像機による連続処理を行うと感光材料にカブリや
写真特性の変化、特に肩部の硬調化が起ることを
つきとめた。
特に最近の写真処理の特徴とされている公害対
策や資源保護のために現像液の補充量を低減させ
た低補充化処理やオーバーフロー液を再使用する
再生処理においては蓄積する重金属イオンが増大
するためか、この写真特性の異常が大きく発生す
ることが解つた。
本発明者等は、この原因が従来からこの現像の
原因物質とされてきた不純物として混入する鉄イ
オンによるものばかりではなく、銅イオンの混入
が増大するためであり、この銅イオンに対しては
従来のキレート剤の使用やキレート剤の組合わせ
による使用ではほとんど効果がなく、無害化する
ことが困難であることもつきとめた。
すなわち、通常の処理されている発色現像液中
の銅イオンは少くとも0.2ppmの銅イオンとして
混入されており、従来から用いられているキレー
ト剤としてのヒドロキシアルキリデンニホスホン
酸金属イオン封鎖剤は、上記の銅イオンに対して
は全く効果が無く、ポリヒドロキシ化合物とカル
ボキシ基を３つ以上有するアミノポリカルボン酸
金属イオン封鎖剤との併用またはポリヒドロキシ
化合物とアミノポリホスホン酸金属イオン封鎖剤
との併用では銅イオンの触媒作用を完全に防止す
ることはできず、保恒剤の分解を促進し、ハロゲ
ン化銀カラー写真感光材料の写真特性に異常を発
生させてしまう欠点があることが解つた。
（発明の目的）
本発明の第１の目的は、金属イオン、特に鉄イ
オンと銅イオンの作用による発色現像液中の成分
の酸化や分解が防止され長期間その効力が持続す
る写真用発色現像剤組成物を提供することにあ
り、第２の目的は金属イオン特に鉄イオンと銅イ
オンの作用によるカラー感光材料の写真特性上の
異常発生を防止した写真用発色現像剤組成物を提
供することにあり、また第３の目的は金属イオン
の存在による沈澱やスラツジの発生が防止された
安定な発色現像液が得られる写真用発色現像剤組
成物を提供することにある。
（発明の構成）
上記本発明の目的は、下記(a)、(b)および(c)を含
有する写真用発色現像剤組成物により達成するこ
とができる。
(a) 少なくとも１つの水溶性基をアミノ基上に有
する芳香族第１級アミン発色現像主薬。
(b) 下記一般式〔〕で表わされる化合物。
一般式〔〕
式中、R1は水素原子またはヒドロキシ基、
アミノ基、ホスホノ基もしくはスルホ基で置換
されていてもよい炭素原子数１〜６のアルキル
基、アリル基またはフエニル基を表す。
(c) 下記一般式〔〕又は〔〕で表される化合
物。
一般式〔〕
一般式〔〕
式中、R2、R3、R4およびR5はそれぞれ水素
原子、ハロゲン原子、スルホン酸基、置換また
は未置換の炭素原子数１〜７のアルキル基、−
OR6、
(Industrial Field of Application) The present invention relates to a photographic color developer composition, and more particularly to a photographic color developer composition which prevents harmful effects due to the contamination of heavy metal ions. (Prior Art) Generally, in silver halide color photographic materials, after image exposure, a dye image is formed by a series of photographic processes whose basic steps are a color development step and a desilvering step. In the above color development step, the oxidized color developing agent forms a dye image with an image pattern by a coupling reaction with the coexisting color coupler,
At the same time, reduced silver is produced. In the subsequent desilvering step, the silver produced here is oxidized by a bleaching agent, transformed into a soluble silver complex by the action of a fixing agent, and dissolved away by washing with water. In ordinary color developing solutions, sulfite or a water-soluble salt of sulfite and hydroxylamine is added as a preservative to prevent oxidation of the aromatic primary amine color developing agent. It is already known that preservability is not necessarily sufficient when these sulfites are added alone to the developer, and that preservability can be effectively obtained by adding hydroxylamine as a water-soluble salt. There is. Additionally, dihydroxyacetone, anilinoethanol, hydroxylurea, etc. are known as preservatives in place of sulfites and hydroxylamine. However, these preservatives are catalyzed by small amounts of coexisting metal ions, especially iron ions, and are oxidized, reducing their preservative effect.Additionally, hydroxylamine salts generate ammonia, which is harmful to color photographic materials. Form fog, contamination, or change photographic properties. Therefore, in order to prevent such undesirable effects caused by metal ions, a technology has been proposed in which various metal chelating agents are added and incorporated into photosensitive materials.
It has been put into practical use. For example, U.S. Pat.
No. 3,746,544 discloses a technology that uses a polyhydroxy compound and an aminopolycarboxylic acid sequestrant in combination, and US Pat. No. 4,264,716 discloses a technology that uses a polyhydroxy compound and an aminopolyphosphonic acid sequestrant in combination. ing. According to these disclosed techniques, it is possible to reduce the influence of heavy metal ions, particularly iron ions, mixed into the developer. However, as a result of studies conducted by the present inventors, it was found that automatic development was possible despite the addition of these chelating agents in a developer containing an aromatic primary amino color developing agent having a water-soluble group on the amino group. It was discovered that continuous processing using a machine causes fogging and changes in photographic characteristics of photosensitive materials, especially hard contrast in the shoulder areas. In particular, the accumulation of heavy metal ions increases in low-replenishment processing that reduces the amount of developer replenishment and reuse processing that reuses overflow solution, which are characteristics of recent photographic processing in order to prevent pollution and conserve resources. It turns out that this abnormality in photographic characteristics occurs to a large extent, perhaps because of this. The inventors believe that this is not only due to iron ions mixed in as an impurity, which has traditionally been thought to be the causative agent of this development, but also due to an increase in the amount of copper ions mixed in. It has also been found that the use of conventional chelating agents or combinations of chelating agents has little effect and is difficult to render harmless. In other words, the copper ions in color developing solutions that are normally processed are mixed in as copper ions of at least 0.2 ppm, and the hydroxyalkylidene diphosphonic acid sequestering agent, which has been used as a chelating agent, It has no effect on the copper ions mentioned above, and the combination of a polyhydroxy compound and an aminopolycarboxylic acid sequestering agent having three or more carboxy groups or a combination of a polyhydroxy compound and an aminopolyphosphonic acid sequestering agent It has been found that when used in combination, the catalytic action of copper ions cannot be completely prevented, and the decomposition of the preservative is accelerated, causing abnormalities in the photographic properties of silver halide color photographic materials. . (Objective of the Invention) The first object of the present invention is to develop a photographic color developer which prevents oxidation and decomposition of components in a color developer due to the action of metal ions, particularly iron ions and copper ions, and which maintains its effectiveness for a long period of time. The second object is to provide a photographic color developer composition which prevents abnormalities in the photographic properties of color light-sensitive materials caused by the action of metal ions, particularly iron ions and copper ions. A third object of the present invention is to provide a photographic color developer composition capable of producing a stable color developer in which precipitation and sludge are prevented from occurring due to the presence of metal ions. (Structure of the Invention) The above object of the present invention can be achieved by a photographic color developer composition containing the following (a), (b) and (c). (a) An aromatic primary amine color developing agent having at least one water-soluble group on an amino group. (b) A compound represented by the following general formula []. General formula [] In the formula, R 1 is a hydrogen atom or a hydroxy group,
Represents an alkyl group having 1 to 6 carbon atoms, an allyl group, or a phenyl group that may be substituted with an amino group, a phosphono group, or a sulfo group. (c) A compound represented by the following general formula [] or []. General formula [] General formula [] In the formula, R 2 , R 3 , R 4 and R 5 each represent a hydrogen atom, a halogen atom, a sulfonic acid group, a substituted or unsubstituted alkyl group having 1 to 7 carbon atoms, -
OR 6 ,
温度(℃) 時間(分)
発色現像 38 3.5
漂白定着 33 1.5
水 洗 30〜36 3.0
乾 燥 75〜85
使用した漂白定着液と安定溶の組成は下記の通
りである。
（漂白定着液）
エチレンジアミン−四酢酸 40ｇ
亜硫酸アンモニウム（50％溶液） 30ml
チオ硫酸アンモニウム（70％溶液） 140ml
アンモニア水（28％溶液） 30ml
エチレンジアミン−四酢酸鉄（）ナトリウム
70ｇ
水にて １
上記により現像処理を行なつた各試料につい
て、更に光電濃度計PDA−65型（小西六写真工
業株式会社製）を用いてイエロー、マゼンタ、シ
アンの各色の反射濃度をそれぞれ測定し示性曲線
を作成した。それぞれの反射濃度1.3〜1.8までの
傾斜（ガンマ値）を計算して下記第２表に示し
た。
（実験−３）
発色現像液試料No.１〜No.17について実験−２で
使用後それぞれについて室温で６週間保存し、保
存中の沈澱の発生状況を目視で観察した。その結
果を下記第２表に示した。
Temperature (°C) Time (min) Color development 38 3.5 Bleach-fixing 33 1.5 Water Washing 30-36 3.0 Drying 75-85 The compositions of the bleach-fix solution and stable solution used are as follows. (Bleach-fix solution) Ethylenediamine-tetraacetic acid 40g Ammonium sulfite (50% solution) 30ml Ammonium thiosulfate (70% solution) 140ml Aqueous ammonia (28% solution) 30ml Ethylenediamine-sodium iron()tetraacetate
With 70g water 1 For each sample developed as above, the reflection density of each color of yellow, magenta, and cyan was measured using a photoelectric densitometer PDA-65 model (manufactured by Konishiroku Photo Industry Co., Ltd.). A characteristic curve was created. The slope (gamma value) of each reflection density from 1.3 to 1.8 was calculated and shown in Table 2 below. (Experiment-3) Color developer samples No. 1 to No. 17 were stored at room temperature for 6 weeks after use in Experiment-2, and the occurrence of precipitation during storage was visually observed. The results are shown in Table 2 below.
【表】【table】
【表】
第２表の沈澱発生の欄における○印は沈澱発生
がないことを表わし、×印は沈澱発生があること
を意味し、その数が多いほど沈澱発生が著るしい
ことを表わす。
前記第１表および第２表の結果から明らかなよ
うに、本発明に係わる１，２−ジヒドロキシベン
ゼン−３，５−ジスルホン酸とＮ，Ｎ−ビス（２
−ヒドロキシエチル）グリシンのような窒素原子
にカルボン酸基を１つ有するキレート剤との併用
では、キレート力が小さく、沈澱が発生する。そ
して上記の併用ではヒドロキシルアミンの分解率
も大きく実用に供し得ない。また窒素原子に３つ
以上のアルキルカルボン酸基を有するニトリロト
リ酢酸やエチレンジアミンテトラ酢酸の如きアミ
ノポリカルボン酸もしくはアルキリデンジホスホ
ン酸等のようなキレート剤のみでは、鉄イオンの
みの混入に際しても実質的には問題なく実用する
ことができるが、鉄イオンと銅イオンの共存下で
はヒドロキシルアミンの分解率が高くなり、写真
特性、特にガンマ値が大きくなつて画像特性が劣
化する。
本発明の現像液に有機ホスホン酸を添加するこ
とができる。有機ホスホン酸としてはヒドロキシ
アルキリデンジホスホン酸を添加することが望ま
しい方法である。この化合物は下記一般式で示さ
れる。
R1は炭素数１〜５のアルキル基
これに対して本発明に係わる上記ジスルホン酸
とイミノジ酢酸またはその誘導体を併用せしめた
本発明の試料No.５、６、７ならびに12、13、14
は、鉄イオンのみの混入に際しても、鉄イオンと
銅イオンとの混入に際してもヒドロキシルアミン
の分解率は低く、写真特性のガンマ値も異常に高
くなることもなく、長期間の保存に際しても現像
液の沈澱は発生しないので、優れた組成物である
ことが解る。そして特にヒドロキシエチルイミノ
ジ酢酸の使用が最も好ましいことも理解できた。
実施例 ２
実施例１において用いられた発色現像液の現像
主薬を４−アミノ−Ｎ，N′−ジエチルパラフエ
ニレンジアミン塩酸塩を当り4.5ｇの使用に変
えたものを調製し、実施例における実験−１と同
じ条件で下記第３表に示す如き試料No.1′〜No.
17′の現像液を作成した。
次いでこの現像液を実験−２と同じ条件で保存
し、この現像液を用いて発色現像を行なつた。処
理して得られた結果のうち、最低濃度のみを第３
表に実験−２により得られた結果として実施例１
の本発明の試料（試料No.１〜No.17）と比較して示
した。[Table] In the column of precipitation occurrence in Table 2, a circle indicates that no precipitation occurs, an x mark indicates that precipitation occurs, and the larger the number, the more significant the precipitation is. As is clear from the results in Tables 1 and 2 above, 1,2-dihydroxybenzene-3,5-disulfonic acid and N,N-bis(2
When used in combination with a chelating agent having one carboxylic acid group on the nitrogen atom, such as (hydroxyethyl)glycine, the chelating power is small and precipitation occurs. In addition, when the above-mentioned combinations are used, the decomposition rate of hydroxylamine is too high and it cannot be put to practical use. Furthermore, when using only chelating agents such as aminopolycarboxylic acids such as nitrilotriacetic acid and ethylenediaminetetraacetic acid, or alkylidene diphosphonic acids, which have three or more alkylcarboxylic acid groups on the nitrogen atom, even when only iron ions are mixed, can be put to practical use without any problems, but in the coexistence of iron ions and copper ions, the decomposition rate of hydroxylamine increases, photographic properties, especially gamma values increase, and image properties deteriorate. Organic phosphonic acids can be added to the developer of the present invention. A desirable method is to add hydroxyalkylidene diphosphonic acid as the organic phosphonic acid. This compound is represented by the following general formula. R 1 is an alkyl group having 1 to 5 carbon atoms. On the other hand, samples No. 5, 6, 7 and 12, 13, 14 of the present invention in which the above disulfonic acid and iminodiacetic acid or a derivative thereof according to the present invention are used in combination
The decomposition rate of hydroxylamine is low whether only iron ions are mixed or iron and copper ions are mixed, the gamma value of the photographic property does not become abnormally high, and even during long-term storage, the decomposition rate of hydroxylamine is low. It can be seen that this is an excellent composition since no precipitation occurs. It was also understood that the use of hydroxyethyliminodiacetic acid is particularly preferred. Example 2 A color developing solution used in Example 1 was prepared by changing the developing agent to 4.5 g of 4-amino-N,N'-diethylparaphenylenediamine hydrochloride. Samples No. 1' to No. 1 as shown in Table 3 below were prepared under the same conditions as Experiment-1.
A 17' developer was prepared. Next, this developer was stored under the same conditions as in Experiment 2, and color development was performed using this developer. Of the results obtained by processing, only the lowest concentration is
The table shows Example 1 as the results obtained from Experiment-2.
The results are shown in comparison with the samples of the present invention (Samples No. 1 to No. 17).
【表】【table】
【表】
第３表の結果からもわかる通り、鉄イオンと銅
イオンを混入させた現像液を長期にわたつて保存
した場合には本発明の発色現像主薬を使用したと
きのみステインの発生を防止出来るが、従来知ら
れていたジアルキルアミノパラフエニレンジアミ
ンを用いた場合には他の金属イオン封鎖剤を本発
明に従つて組合わせて使用してもマゼンタステイ
ンの発生を完全に抑制出来ない事がわかる。
実施例 ３
一般式〔〕〜〔〕で表される化合物及び添
加量を第４表記載のとおりとし、重金属イオンの
混入を鉄イオン3ppm、銅イオン3ppmとしたほか
は実施例１と同様の実験を行つた。その結果を第
５表に示す。[Table] As can be seen from the results in Table 3, when a developer mixed with iron and copper ions is stored for a long period of time, staining is prevented only when the color developing agent of the present invention is used. However, when the conventionally known dialkylamino paraphenylene diamine is used, the generation of magenta stain cannot be completely suppressed even if other sequestering agents are used in combination according to the present invention. I understand. Example 3 The same experiment as Example 1 was carried out except that the compounds represented by the general formulas [] to [] and the amounts added were as shown in Table 4, and the heavy metal ions were mixed in at 3 ppm of iron ions and 3 ppm of copper ions. I went to The results are shown in Table 5.
【表】【table】
【表】【table】
【表】【table】
【表】
（発明の効果）
本発明による前記(a)、(b)および(c)で表わされる
組成物を含有せしめた発色現像液は、ヒドロキシ
ルアミンの分解が少く、画像特性にも優れ、かつ
長期間保存しても沈澱を生ずることもない。[Table] (Effects of the Invention) The color developing solution containing the compositions represented by (a), (b) and (c) according to the present invention exhibits less decomposition of hydroxylamine and has excellent image properties. Moreover, no precipitation occurs even after long-term storage.
Claims (1)
る写真用発色現像剤組成物。 (a) 少なくとも１つの水溶性基をアミノ基上に有
する芳香族第１級アミン発色現像主薬。 (b) 下記一般式〔〕で表わされる化合物。 一般式〔〕 〔式中、R1は水素原子、フエニル基、炭素
原子数１〜６の非置換アルキル基、またはヒド
ロキシ基、アミノ基、ホスホノ基もしくはスル
ホ基で置換された炭素原子数１〜６のアルキル
基を表わす。〕 (c) 下記一般式〔〕又は〔〕で表される化合
物。 一搬式〔〕 一般式〔〕 〔式中、R2、R3、R4およびR5はそれぞれ水
素原子、ハロゲン原子、スルホン酸基、炭素原
子数１〜７の非置換アルキル基、カルバモイル
基、−OR6または−COOR7を表わし、R6および
R7はそれぞれ水素原子または炭素原子数１〜
６のアルキル基を表わす。〕[Scope of Claims] 1. A photographic color developer composition comprising the following (a), (b) and (c). (a) An aromatic primary amine color developing agent having at least one water-soluble group on an amino group. (b) A compound represented by the following general formula []. General formula [] [In the formula, R 1 is a hydrogen atom, a phenyl group, an unsubstituted alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms substituted with a hydroxy group, an amino group, a phosphono group, or a sulfo group. represents. ] (c) A compound represented by the following general formula [] or []. Single transport type [] General formula [] [In the formula, R 2 , R 3 , R 4 and R 5 each represent a hydrogen atom, a halogen atom, a sulfonic acid group, an unsubstituted alkyl group having 1 to 7 carbon atoms, a carbamoyl group, -OR 6 or -COOR 7 Representation, R 6 and
R 7 is each a hydrogen atom or 1 to 1 carbon atom
6 represents an alkyl group. ]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22751283A JPS60118837A (en) | 1983-11-30 | 1983-11-30 | Photographic color developing composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22751283A JPS60118837A (en) | 1983-11-30 | 1983-11-30 | Photographic color developing composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60118837A JPS60118837A (en) | 1985-06-26 |
| JPH0374815B2 true JPH0374815B2 (en) | 1991-11-28 |
Family
ID=16862059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22751283A Granted JPS60118837A (en) | 1983-11-30 | 1983-11-30 | Photographic color developing composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60118837A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3773250D1 (en) * | 1986-04-19 | 1991-10-31 | Konishiroku Photo Ind | METHOD FOR TREATING A COLOR PHOTOGRAPHIC LIGHT-SENSITIVE SILVER HALOGENIDE MATERIAL. |
| JPH06105345B2 (en) * | 1986-07-21 | 1994-12-21 | 富士写真フイルム株式会社 | Color photographic developer composition and method for processing silver halide color photographic light-sensitive material |
| JPH03182750A (en) * | 1989-12-12 | 1991-08-08 | Konica Corp | Processing liquid and processing method for silver halide color photographic sensitive material |
| DE4209347A1 (en) * | 1992-03-23 | 1993-09-30 | Agfa Gevaert Ag | developer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5632140A (en) * | 1979-08-24 | 1981-04-01 | Konishiroku Photo Ind Co Ltd | Processing method for silver halide color photographic material |
| JPS59180558A (en) * | 1983-03-31 | 1984-10-13 | Fuji Photo Film Co Ltd | Method for processing color photosensitive silver halide material |
-
1983
- 1983-11-30 JP JP22751283A patent/JPS60118837A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5632140A (en) * | 1979-08-24 | 1981-04-01 | Konishiroku Photo Ind Co Ltd | Processing method for silver halide color photographic material |
| JPS59180558A (en) * | 1983-03-31 | 1984-10-13 | Fuji Photo Film Co Ltd | Method for processing color photosensitive silver halide material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60118837A (en) | 1985-06-26 |
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