JPH0327104B2

JPH0327104B2 -

Info

Publication number: JPH0327104B2
Application number: JP6437884A
Authority: JP
Inventors: Satoru Kuze
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1984-03-30
Filing date: 1984-03-30
Publication date: 1991-04-12
Also published as: JPS60205541A

Description

[Detailed description of the invention]

〔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、更に詳しくは保恒性の改良され
た安定な現像液によ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。〔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。実際の現像処理工程では、上記の発色現像およ
び脱銀を目的とする基本的な工程のほかに、画像
の写真的または物理的特性の向上に対する必要性
から、停止浴、硬膜浴、安定浴、パツキング除去
処理浴などの補助的な処理浴を設けている。一方、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
より効果的な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。近年、経済的理由ならびに公害的理由から現像
液は低補充化される傾向になり、これによつて現
像液の滞溜時間も長期化する傾向にあり、現像液
は空気酸化を受けることが多くなつている。さら
にまた、処理の迅速化に伴ない、写真感光材料を
30℃以上の高温下に処理するようになつてきてお
り、高温酸化による現像液の着色等の支障が更に
著しくなつて来ている。〔発明の目的〕本発明の目的はこれらの問題に関つて、第１の
目的は長期保存性のよいまた処理耐用性のよい現
像液を用いるハロゲン化銀カラー写真感光材料
（以後カラー感光材料と略称する）の処理方法を
提供することである。第２の目的は長期保存時の発色現像主薬の酸化
によるタールの発生域はスラツジの発生の改善さ
れた現像液を用いたカラー感光材料の処理方法の
提供にある。更に第３の目的は前記タール或はスラツジによ
る自動現像機処理槽の汚れ、フイルター目詰りに
よる処理支障のないカラー感光材料の処理方法を
提供することにある。〔発明の構成〕本発明のカラー感光材料処理方法は、カラー感
光材料を像様露光した後、下記(イ)，(ロ)並びに(ハ)の
存在下に発色現像処理することを特徴として構成
される。 (イ) 芳香族第１級アミン発色現像主薬系化合物 (ロ) マンガン塩及び／又はセリウム塩 (ハ) 下記一般式（）及び（）から選ばれる少
なくとも一種の金属イオン封鎖剤。（以下本発
明の化合物と称す）式中、R₁，R₂，R₃およびR₄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のアルキル基、−OR₅，−COOR₆，
[Industrial Application Field] The present invention relates to a method for processing a silver halide color photographic light-sensitive material, and more particularly to a method for processing a silver halide color photographic light-sensitive material using a stable developer with improved preservability. [Prior Art] In general, a silver halide color photographic light-sensitive material forms a dye image by a series of photographic processes whose basic steps are a color development step and a desilvering step after image exposure. 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 the actual processing process, in addition to the basic steps for color development and desilvering mentioned above, stopping baths, hardening baths, and stabilizing baths are required due to the need to improve the photographic or physical properties of images. , auxiliary treatment baths such as a packing removal treatment bath are provided. On the other hand, 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 adding hydroxylamine as a water-soluble salt can provide effective preservability since adding these sulfites alone to the developer does not necessarily provide sufficient preservability. There is. Additionally, dihydroxyacetone, anilinoethanol, hydroxylurea, etc. are known as preservatives in place of sulfites and hydroxylamine. In recent years, there has been a trend toward low replenishment of developing solutions for economic and pollution reasons, and as a result, the residence time of the developing solution has also tended to become longer, and the developing solution is often subject to air oxidation. It's summery. Furthermore, as processing becomes faster, photosensitive materials
Processing is now being carried out at high temperatures of 30° C. or higher, and problems such as coloring of the developer due to high temperature oxidation are becoming more and more serious. [Object of the Invention] The purpose of the present invention is to solve these problems, and the first object is to develop silver halide color photographic materials (hereinafter referred to as color photographic materials) that use a developer that has good long-term storage stability and good processing durability. The purpose of the present invention is to provide a processing method for The second object is to provide a method for processing a color photosensitive material using a developer in which the generation of tar and sludge due to oxidation of a color developing agent during long-term storage is improved. A third object of the present invention is to provide a method for processing color photosensitive materials that does not cause problems in processing due to contamination of the processing tank of an automatic processor due to tar or sludge or clogging of filters. [Structure of the Invention] The color photosensitive material processing method of the present invention is characterized in that after the color photosensitive material is imagewise exposed, color development processing is performed in the presence of the following (a), (b), and (c). be done. (a) Aromatic primary amine color developing agent compound (b) Manganese salt and/or cerium salt (c) At least one sequestering agent selected from the following general formulas () and (). (Hereinafter referred to as the compound of the present invention) In the formula, R ₁ , R ₂ , R ₃ and R ₄ each represent a hydrogen atom, a halogen atom, a sulfonic acid group, or a carbon atom number of 1.
-7 alkyl group, -OR ₅ , -COOR ₆ ,

【式】又は、フエニル基を表わす。また、R₅，R₆，R₇およびR₈はそれぞれ水素原子又
は炭素原子数１〜18のアルキル基を表わす。ただ
し、R₂が−OHまたは水素原子を表わす場合、R₁
はハロゲン原子、スルホン酸基、炭素原子数１〜
７のアルキル基、−OR₅，−COOR₆，
[Formula] or represents a phenyl group. Further, R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, if R ₂ represents -OH or a hydrogen atom, R ₁
is a halogen atom, a sulfonic acid group, and a carbon atom number of 1 to
7 alkyl group, -OR ₅ , -COOR ₆ ,

〔Example〕

以下、実施例によつて本発明を更に詳細に説明
するが、本発明の実施態様がこれらに限定される
ものではない。〔実施例１〕（実験１）下記のカラーネガ用発色現像液を基本処方とし
て実験を行なつた。（発色現像液組成）炭酸カリウム 30ｇ炭酸水素ナトリウム 2.5ｇ亜硫酸カリウム５ｇ臭化ナトリウム 1.3ｇ沃化カリウム２mg ヒドロキシルアミン硫酸塩 2.5ｇ塩化ナトリウム 0.6ｇＮ−エチル−Ｎ−（β−ヒドロキシエチル）−３
メチル−ｐ−フエニレンジアミン硫酸塩（発色
現像主薬） 4.8ｇ水酸化カリウム 1.2ｇ水を加えて１とし、水酸化カリウム又は20％
硫酸を用いて、PH10.06に調整した。上記現像液を対照試料(A)とし、これに第１表に
示す金属塩及び金属イオン封鎖剤を添加し、１
の現像液を100cm²の開口面積を有する１ビーカ
ーに20日間室温にて保存した。保存後の現像液中
の発色現像主薬の分解量を定量し、また分光光度
計で450nmの吸収を測定し現像液のタール度を測
つた。（実験２）サクラカラーネガテイブフイルム（小西六写
真工業(株)製）をKS−７型感光計（小西六写真工
業(株)製）を用いて白色階段露光を与えた後、実験
１で４日間放置した後の現像液試料(A)〜（Ｑ）を
それぞれ用いて、次の工程に従つて発色現像処理
を行なつた。処理工程温度(℃) 時間(分) 発色現像 38 ３分15秒漂白 38 ６分30秒水洗 33 ３分定着 38 ６分30秒水洗 33 ４分安定 33 ２分乾燥 43〜52 使用した漂白液、定着液、安定液は全てサクラ
カラーネガテイブフイルム処理剤・タイプ−４
（CNK−４）（小西六写真工業(株)製）を使用した。上記発色現像処理を終つたものについて、
PDA−60型光電濃度計（小西六写真工業(株)製）
を用いて、ブルー濃度の最高濃度を測定した。以上の結果をまとめて第２表に示す。 EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited thereto. [Example 1] (Experiment 1) An experiment was conducted using the following color developing solution for color negatives as a basic formulation. (Color developer composition) Potassium carbonate 30g Sodium hydrogen carbonate 2.5g Potassium sulfite 5g Sodium bromide 1.3g Potassium iodide 2mg Hydroxylamine sulfate 2.5g Sodium chloride 0.6g N-ethyl-N-(β-hydroxyethyl)-3
Methyl-p-phenylenediamine sulfate (color developing agent) 4.8g Potassium hydroxide 1.2g Add water to make 1, potassium hydroxide or 20%
The pH was adjusted to 10.06 using sulfuric acid. The above developer was used as a control sample (A), and the metal salts and metal ion sequestering agents shown in Table 1 were added to it.
The developer solution was stored in one beaker with an opening area of 100 cm ² at room temperature for 20 days. The amount of decomposed color developing agent in the developer solution after storage was quantified, and the tar degree of the developer solution was measured by measuring absorption at 450 nm with a spectrophotometer. (Experiment 2) Sakura color negative film (manufactured by Konishiroku Photo Industry Co., Ltd.) was subjected to white stepwise exposure using a KS-7 sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.). After being left for one day, developer samples (A) to (Q) were used to perform color development according to the following steps. Processing process Temperature (°C) Time (min) Color development 38 3 minutes 15 seconds Bleaching 38 6 minutes 30 seconds Washing 33 3 minutes Fixing 38 6 minutes 30 seconds Washing 33 4 minutes Stabilizing 33 2 minutes Drying 43~ 52 The bleaching solution, fixing solution, and stabilizing solution used were all Sakura Color negative film processing agent type-4.
(CNK-4) (manufactured by Konishiroku Photo Industry Co., Ltd.) was used. For those that have undergone the above color development treatment,
PDA-60 photodensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.)
The maximum blue density was measured using The above results are summarized in Table 2.

【表】【table】

[Example 2]

実施例１で用いられた現像液(C)に添加されたセ
リウムイオンの量をそれぞれ０，0.1，0.3，0.5，
1.0，5.0，8.0，20.0，30.0，40.0mg／に変えて
実施例１と同じ実験を行なつた。その結果を第３
表に示す。 The amount of cerium ions added to the developer (C) used in Example 1 was 0, 0.1, 0.3, 0.5, and
The same experiment as in Example 1 was conducted except that the concentrations were changed to 1.0, 5.0, 8.0, 20.0, 30.0, and 40.0 mg/. The result is the third
Shown in the table.

〔Effect of the invention〕

本発明のカラー感光材料の処理方法を用いると
きは、次のような優れた効果がある。 (1) 本発明に係る化合物の添加により空気及び現
像液に溶存した酸素による現像液中の有効成分
の酸化や分解がなく、長期にわたつて現像液の
効力を持続させ常に一定の処理結果が得られ
る。 (2) 長期保存しても発色現像主薬の酸化物による
タールの発生やスラツジの発生がなく、自動現
像機の処理槽の汚れや、フイルターの目づまり
がなく、さらに被処理物であるカラー感光材料
を汚染することがない。 When the method of processing color photosensitive materials of the present invention is used, the following excellent effects can be obtained. (1) By adding the compound according to the present invention, the active ingredients in the developer will not be oxidized or decomposed by air or oxygen dissolved in the developer, and the effectiveness of the developer can be maintained over a long period of time to ensure constant processing results. can get. (2) Even after long-term storage, there is no generation of tar or sludge due to oxides of color developing agents, there is no dirt in the processing tank of automatic processors, there is no clogging of filters, and the color photosensitive material to be processed is not affected. will not contaminate.

Claims

[Scope of Claims] 1. A silver halide color photographic material, which is imagewise exposed and then subjected to color development treatment in the presence of (a), (b), and (c) below. A method of processing color photographic materials. (a) an aromatic primary amine color developing agent compound; (b) a manganese salt and/or a cerium salt; (c) at least one sequestering agent selected from the following general formulas () and (). (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -OR ₅ , -COOR ₆ ,
[Formula] or represents a phenyl group. Further, R ₅ , R ₆ , R ₇ and R ₈ each represent a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. However, if R ₂ represents -OH or a hydrogen atom, R ₁
is a halogen atom, a sulfonic acid group, and a carbon atom number of 1 to
7 alkyl group, -OR ₅ , -COOR ₆ ,
[Formula] or represents a phenyl group. )