JP3901527B2 - Dense processing composition for photographic color development and method for preparing color developer - Google Patents

Description

【００２９】
上記一般式（ＳＲ）において、Ｘ₁、Ｘ₂及びＹ₁、Ｙ₂は、ヒドロキシ基、炭素数１〜４のアルコキシ基（たとえばメトキシ基、エトキシ基、メトキシエトキシ基など）、アミノ基、炭素数１〜６のアルキルアミノ基（たとえばメチルアミノ基、エチルアミノ基、プロピルアミノ基、ジメチルアミノ基、シクロヘキシルアミノ基、β―ヒドロキシエチルアミノ基、ジーβ―ヒドロキシエチルアミノ基、β―スルホエチルアミノ基、Ｎ−（β―スルホシエチル）−Ｎ−エチルアミノ基など）、アリールオキシ基(たとえばフェノキシき、ｐ−スルホフェノキシ基など)、アリールアミノ基(たとえばアニリノ基、ｏ，ｍ，ｐ−スルホアニリノ基、ｏ，ｍ，ｐ−クロロアニリノ基、ｏ，ｍ，ｐ−トルイジノ基、ｏ，ｍ，ｐ−カルボキシアニリノ基、ｏ，ｍ，ｐ−アニシジノ基、ｏ，ｍ，ｐ−ヒドロキシアニリノ基など)を表す。
Ｍは、水素原子又は１価の陽イオンを表す。
以下に、一般式（ＳＲ）で表される化合物を示すが、本発明に用いられる蛍光増白剤はこれらの例示化合物に限定されない。
【００３０】
【表１】

【００３１】
【表２】

【００３２】
【表３】

【００３３】
【化２】

【００３４】
【化３】

【００３５】
処理組成物中の蛍光増白剤の含有量は該蛍光増白剤の濃度は現像液１リットル当たり１ミリモル〜５００ミリモル、好ましくは２ミリモル〜４００ミリモル、より好ましくは５ミリモル〜３００ミリモルとなる。
発色現像主薬パート中の蛍光増白剤含有量は前記したが、この現像処理組成物を用いて調製した現像液中の増白剤の濃度は、現像液１リットル当たり１ミリモル〜５００ミリモル、好ましくは２ミリモル〜４００ミリモル、より好ましくは５ミリモル〜３００ミリモルとなるように調製される。
【００３６】
発色現像主薬パートは、そのpH値は２〜６になるように、後述するｐＨ緩衝剤やアルカリ剤を適宜加えて組成物とする。
【００３７】
カラー現像組成物には、対象とする感光材料の種類によって少量の亜硫酸イオンを含んだり、あるいは実質的に含まない場合もあるが、本発明においては、亜硫酸イオンを少量含むことが好ましい。亜硫酸イオンは顕著な保恒作用を持つ反面、過剰の場合にはカラー現像の過程で写真的性能に好ましくない影響をあたえることもある。
また、ヒドロキシルアミンを少量含有してもよい。ヒドロキシルアミン（通常塩酸塩や硫酸塩の形で用いるが、以下塩の形を省略する）を含んでいると、亜硫酸イオンと同様に現像液の保恒剤として作用するが、同時にヒドロキシルアミン自身の銀現像活性のために写真特性に影響することもあるので、この添加量も少量に留める必要がある。
【００３８】
カラー現像組成物には、保恒剤として前記ヒドロキシルアミンや亜硫酸イオンのほかにも、有機保恒剤を添加してもよい。有機保恒剤とは、感光材料の処理液へ含ませることで、芳香族第一級アミンカラー現像主薬の劣化速度を減じる有機化合物全般を指している。即ち、カラー現像主薬の空気酸化などを防止する機能を有する有機化合物類であるが、中でも、前記のヒドロキシルアミン誘導体をはじめ、ヒドロキサム酸類、ヒドラジド類、フェノール類、α−ヒドロキシケトン類、α−アミノケトン類、糖類、モノアミン類、ジアミン類、ポリアミン類、四級アンモニウム塩類、ニトロキシラジカル類、アルコール類、オキシム類、ジアミド化合物類、縮環式アミン類などが特に有効な有機保恒剤である。これらは、特開昭63−4235号、同63-30845号、同63-21647号、同63-44655号、同63-53551号、同63-43140号、同63-56654号、同63-58346号、同63-43138号、同63−146041号、同63-44657号、同63-44656号、米国特許第3,615,503 号、同2,494,903 号、特開昭52−143020号、特公昭48-30496号などの各公報又は明細書に開示されている。
【００３９】
その他保恒剤として、特開昭57-44148号及び同57-53749号公報に記載の各種金属類、特開昭59−180588号公報に記載のサリチル酸類、特開昭54−3532号公報に記載のアルカノールアミン類、特開昭56-94349号公報に記載のポリエチレンイミン類、米国特許第3,746,544 号明細書等に記載の芳香族ポリヒドロキシ化合物等を必要に応じて含有しても良い。特に、例えばトリエタノールアミンやトリイソプロパノールアミンのようなアルカノールアミン類、ジスルホエチルヒドロキシルアミン、ジエチルヒドロキシルアミンのような置換又は無置換のジアルキルヒドロキシルアミン、あるいは芳香族ポリヒドロキシ化合物を添加してもよい。
【００４０】
前記の有機保恒剤のなかでも置換ヒドロキシルアミンの詳細については、特開平1-97953 号、同1-186939号、同1-186940号、同1-187557号公報などに記載されている。とりわけ、置換ヒドロキシルアミンとアミン類をともに添加することも、カラー現像液の安定性の向上、連続処理時の安定性向上の点で効果的なこともある。
前記のアミン類としては、特開昭63−239447号公報に記載されたような環状アミン類や特開昭63−128340号公報に記載されたようなアミン類やその他特開平1-186939号や同1-187557号公報に記載されたようなアミン類が挙げられる。処理剤中の補恒剤の含有量は、補恒剤の種類によって異なるが、一般に使用液中の濃度が現像液１リットル当たり１ミリモル〜２００ミリモル、好ましくは１０ミリモル〜１００ミリモルとなるように加えられる。
【００４１】
カラー現像組成物には、例えばカラーペーパー用の現像組成物は必要に応じて塩素イオンを添加してもよい。カラー現像液（とくにカラ−プリント材料用現像剤）は、通常塩素イオンを3.5 ×10^-2〜1.5 ×10^-1モル／リットル含有することが多いが、塩素イオンは、通常現像の副生成物として現像液に放出されるので補充用現像組成物には通常添加不要である。撮影用の感光材料用の現像組成物では塩素イオンを含まなくてもよい。
【００４２】
臭素イオンに関しては、カラー現像液中の臭素イオンは、撮影用材料の処理では１〜５ｘ１０^-3モル／リットル程度、また、プリント材料の処理では、 1.0×10^-3モル／リットル以下であることが好ましい。しかし、カラー現像補充液用組成物には、上記の塩素イオンと同様必要がないことが多いが、添加する場合には臭素イオン濃度が上記範囲になるように必要に応じて処理剤中に臭素イオンを加えることもある。
対象とする感光材料が、カラーネガフィルムやカラーリバーサルフィルムなどのヨウ臭化銀乳剤から得られるものである場合には、ヨウ素イオンに関しても同じ状況であるが、通常は感光材料からヨウ素イオンが放出されて現像液１リットル当たり０．５〜１０ｍｇ程度のヨウ素イオン濃度となるので、補充用処理組成物の中には含まない場合が普通である。
【００４３】
本発明においては、現像液のｐＨが９．０〜１２．５、補充液のpHが９．０〜１３．５になるように添加されることが好ましく、したがって現像剤及び補充剤には、そのｐＨ値を維持できるようにアルカリ剤、緩衝剤及び必要によっては酸剤を含ませることができる。
アルカリとしては各種水酸化物を添加することができる。例えば水酸化カリウム、水酸化ナトリウム、水酸化リチウム、燐酸水素３カリウムや燐酸水素３ナトリウム及びそれらの水和物あるいはトリエタノールアミン、ジエタノールアミン等をあげることができる。また、必要に応じて添加される酸剤としては無機・有機の水溶性の固体状の酸を用いることができる。例えば、琥珀酸、酒石酸、プロピオン酸、アスコルビン酸が挙げられる。
【００４４】
処理液を調製したときに、上記ｐＨを保持するためには、各種緩衝剤を用いるのが好ましい。緩衝剤としては、炭酸塩、リン酸塩、ホウ酸塩、四ホウ酸塩、ヒドロキシ安息香酸塩、グリシル塩、Ｎ，Ｎ−ジメチルグリシン塩、ロイシン塩、ノルロイシン塩、グアニン塩、３，４−ジヒドロキシフェニルアラニン塩、アラニン塩、アミノ酪酸塩、２−アミノ−２−メチル−１, ３−プロパンジオール塩、バリン塩、プロリン塩、トリスヒドロキシアミノメタン塩、リシン塩などを用いることができる。特に炭酸塩、リン酸塩、四ホウ酸塩、ヒドロキシ安息香酸塩は、pH 9.0以上の高pH領域での緩衝能に優れ、カラー現像液に添加しても写真性能面への悪影響（カブリなど）がなく、安価であるといった利点を有し、これらの緩衝剤を用いることが特に好ましい。
【００４５】
これらの緩衝剤の具体例としては、炭酸ナトリウム、炭酸カリウム、重炭酸ナトリウム、重炭酸カリウム、リン酸三ナトリウム、リン酸三カリウム、リン酸二ナトリウム、リン酸二カリウム、ホウ酸ナトリウム、ホウ酸カリウム、四ホウ酸ナトリウム（ホウ砂）、四ホウ酸カリウム、ｏ−ヒドロキシ安息香酸ナトリウム（サリチル酸ナトリウム）、ｏ−ヒドロキシ安息香酸カリウム、５−スルホ−２−ヒドロキシ安息香酸ナトリウム（５−スルホサリチル酸ナトリウム）、５−スルホ−２−ヒドロキシ安息香酸カリウム（５−スルホサリチル酸カリウム）などを挙げることができる。しかしながら本発明は、これらの化合物に限定されるものではない。
緩衝剤は、反応・消費される成分ではないので、その濃度は、処理剤から調製した現像液及び補充液ともに１リットルあたり０．０１〜２モル、好ましくは０．１〜０．５モルになるように組成物中の添加量が決められる。
【００４６】
カラー現像組成物には、その他のカラー現像液成分、例えばカルシウムやマグネシウムの沈澱防止剤であり、あるいはカラー現像液の安定性向上剤でもある各種キレート剤を添加することもできる。例えば、ニトリロ三酢酸、ジエチレントリアミン五酢酸、エチレンジアミン四酢酸、Ｎ，Ｎ，Ｎ−トリメチレンホスホン酸、エチレンジアミン−Ｎ，Ｎ，Ｎ′，Ｎ′−テトラメチレンスルホン酸、トランスシロヘキサンジアミン四酢酸、１，２−ジアミノプロパン四酢酸、グリコールエーテルジアミン四酢酸、エチレンジアミンオルトヒドロキシフェニル酢酸、エチレンジアミンジ琥珀酸（ＳＳ体）、Ｎ−（２−カルボキシラートエチル）−Ｌ−アスパラギン酸、β−アラニンジ酢酸、２−ホスホノブタン−１，２，４−トリカルボン酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸、Ｎ，Ｎ′−ビス（２−ヒドロキシベンジル）エチレンジアミン−Ｎ，Ｎ′−ジ酢酸、１，２−ジヒドロキシベンゼン−４，６−ジスルホン酸等が挙げられる。
これらのキレート剤は必要に応じて２種以上併用しても良い。
これらのキレート剤の量は、調製したカラー現像液中の金属イオンを封鎖するのに充分な量であれば良い。例えば１リットル当り 0.1ｇ〜10ｇ程度になるように添加する。
【００４７】
本発明に係るカラー現像組成物には、必要により任意の現像促進剤を添加することもできる。現像促進剤としては、特公昭37-16088号、同37−5987号、同38−7826号、同44-12380号、同45−9019号及び米国特許第3,813,247 号等の各公報又は明細書に表わされるチオエーテル系化合物、特開昭52-49829号及び同50-15554号公報に表わされるｐ−フェニレンジアミン系化合物、特開昭50−137726号、特公昭44-30074号、特開昭56−156826号及び同52-43429号公報等に表わされる４級アンモニウム塩類、米国特許第2,494,903 号、同3,128,182 号、同4,230,796 号、同3,253,919 号、特公昭41-11431号、米国特許第2,482,546 号、同2,596,926 号及び同3,582,346 号等の各公報又は明細書に記載のアミン系化合物、特公昭37-16088号、同42-25201号、米国特許第3,128,183 号、特公昭41-11431号、同42-23883号及び米国特許第3,532,501 号等の各公報又は明細書に表わされるポリアルキレンオキサイド、その他１−フェニル−３−ピラゾリドン類又はイミダゾール類を必要に応じて添加することができる。それらの濃度は、処理剤から調製した現像液及び補充液ともに１リットルあたり０．００１〜０．２モル、好ましくは０．０１〜０．０５モルになるように組成物中の添加量が決められる。
【００４８】
本発明にかかわるカラー現像組成物には、必要に応じて、前記ハロゲンイオンのほかに、任意のカブリ防止剤を添加できる。有機カブリ防止剤としては、例えばベンゾトリアゾール、６−ニトロベンズイミダゾール、５−ニトロイソインダゾール、５−メチルベンゾトリアゾール、５−ニトロベンゾトリアゾール、５−クロロ−ベンゾトリアゾール、２−チアゾリル−ベンズイミダゾール、２−チアゾリルメチル−ベンズイミダゾール、インダゾール、ヒドロキシアザインドリジン、アデニンの如き含窒素ヘテロ環化合物を代表例としてあげることができる。又、カラー現像剤には必要に応じてアルキルスルホン酸、アリールスルホン酸、脂肪族カルボン酸、芳香族カルボン酸等の各種界面活性剤を添加しても良い。それらの濃度は、処理組成物から調製した現像液及び補充液ともに１リットルあたり０．０００１〜０．２モル、好ましくは０．００１〜０．０５モルになるように組成物中の添加量が決められる。
【００４９】
処理組成物の溶媒としては、通常水が用いられるが、現像主薬含有処理組成物など水への溶解度が制約となる場合には、水性溶媒が用いられ、好ましくは、水を主体としてジエチレングリコール、トリエチレングリコール、エチレングリコールなど現像主薬などの溶解性を増大させる水混和性有機溶剤を１〜２０質量％含ませた混合溶媒が選択される。
さらに、現像主薬含有パートには、無機保恒剤として亜硫酸塩又は重亜硫酸塩を現像主薬の０．１〜１モル％含有させることもある。
【００５０】
本発明の自動処理液調製装置に用いられる液体調合処理組成物は、容器に充填された形態で処理剤を構成する処理組成物パートの個々の形態のまま、又は構成パートを一体に組んだ処理剤として主に大型の現像所に、あるいは調製ロットのサイズに合わせたキット構成の処理剤として主にミニラボ市場向け（店頭現像所向け）に供給される。前者の場合は、自動処理液調製装置で現像液を調製するのに好ましく用いられる。
【００５１】
処理組成物用容器の材料は、ポリエチレンが好ましく、とくに強度とガスバリア性の点でＨＤＰＥが適しており、中でも比重が０．９４以上のＨＤＰＥが好ましい。とりわけ、好ましい容器の例は、密度が０．９４１〜０．９６９の高密度ポリエチレン（以後ＨＤＰＥと呼ぶ） を単一の構成樹脂として作られた容器である。より好ましい密度は０．９５１〜０．９６９であり、さらに好ましくは０．９５５〜０．９６５である。
【００５２】
また、材料中には可塑剤やステアリン酸，その他の充填剤や添加剤を含んでいてもよいが、より好ましくは単一組成のＨＤＰＥであることがガスバリア性と強度上優れている。容器の厚みは、作業中の持ち運びなどがないので、薄くして軽量化を量る必要はないが、収納されている処理組成物を取り出しながら継続的に使用する合いだの酸化劣化を軽減するためにも、また強度維持の点からもある程度の厚みを必要としており、容器の厚みは柱状部の平均厚みで５リットルボトルでは、０．５ｍｍ以上、２０リットルボトルでは０．８ｍｍ以上、３０リットルボトルでは１ｍｍ以上あれば十分であり、厚みの上限には制約はないが、重量や材料原単位の上で不要に厚くすることは無意味である。
【００５３】
容器は、一般的なボトル成形に採用されている中空成形(射出中空成形を含む)や回転成形によって、好ましくは中空成形によって製造される。
処理組成物容器の酸素透過性は、漂白処理組成物専用容器以外は０．００５ｍｌ／ｍ² ・ｓ・ＭＰａ（２０℃、 ６５％ＲＨ）以下、好ましくは、０．００２ｍｌ／ｍ² ・ｓ・ＭＰａ（２０℃、 ６５％ＲＨ）以下であり、酸素透過性が低いほどこのましい。その下限は容器の取り扱い性、経済性などの制約が許す範囲で決められる。尚、酸素透過係数は「Ｏ₂パーミエイション オブ プラスチック コンティナー、モダーンパッキング（Ｏ₂ permeation of plastic container, Modern Packing; N.J. Calyan, 1968）の１２月号第１４３〜１４５頁に記載の方法により測定することができる。
【００５４】
容器の水分（湿分）透過係数は、０．００５ｍｌ／ｍ² ・ｓ・ＭＰａ（２０℃、６５％ＲＨ）以下、好ましくは、０．００２ｍｌ／ｍ² ・ｓ・ＭＰａ（２０℃、 ６５％ＲＨ）以下であり、水分透過性が低いほどこのましい。その下限は容器の取り扱い性、経済性などの制約が許す範囲で決められる。
【００５５】
本発明の現像剤は、カラーネガ処理用、カラーペーパー処理用、カラーリバーサル処理用のいずれの現像剤にも適用できる。感光材料の処理に際しては、漂白(又は漂白定着)、定着、安定浴などの各処理工程用の処理剤とともに用いられる。
【００５６】
次ぎに現像所における処理液の調製について述べる。一般的に、大型現像所（大ラボ）は、１日当たりのフィルム処理量が１０００から１００００本の規模（カラーペーパーの処理量もフィルム処理量に見合う）であることが多い。このような規模の現像所では、１回当たりの調製量は、仕上がり量が１００〜５００リットル程度の規模であることが多いが、本発明の現像剤は、このような大ロットの現像液調製にも効果があるが、一方１回の調製の仕上がり量が３〜５リットルであって自動調製装置で省力的に行う現像液調製にも混合の際のにごりの発生がなく、好ましく適用できる。この場合は、床面積を必要としないので、省スペースの見地からも有利である。
【００５７】
本発明のカラー現像剤を用いて処理液を自動調製装置によって調製する一態様を、図面によって説明する。図１は、自動調製装置の構造と各部機能を示す概略系統図である。図１において、図１ａは装置断面図であり、図１ｂは、平面図である。処理液調製装置は、攪拌手段３を備えた混合槽１と混合槽の直上部に配されて、内容液が混合槽１に投入可能な開閉弁４を備えた計量槽２と、処理組成物を計量槽２に流入させる流入口５Ａ，５Ｂ，５Ｃと、計量槽２に流入して貯留された処理組成物の液面を検知するレベルセンサー６Ａ，６Ｂ，６Ｃを有している。混合槽１は攪拌機構３と、不要となった廃液などを排出する排出口９と、調製済み処理液を補充槽などの貯槽へ送液するための送液口８を有している。各流入口５Ａ，５Ｂ，５Ｃには、送液管７Ａ，７Ｂ，７Ｃ（図示しない）が，送液ポンプＰを経て処理組成物を収納した容器に接続している。送液管７Ａには送液ポンプＰを経て容器１０が接続しており、容器１０の口部１１から容器内に導入された送液管の端部には組成物吸い込み用のノズルがその先端を処理組成物液内に差し込まれて組成物を吸い込み可能に配されている。
図１において，流入口、レベルセンサー、送液管などは、Ａ，Ｂ，Ｃと添字が付された各３部材のみを代表させて示してあるが，実際には自動調製に使用される処理剤組成物の容器の種類を満たす数が設けられる。また、処理剤組成物容器などについては、添字Ａを付した送液管７Ａに接するもののみを代表として示してあるが，図示していない各送液管にも同じように処理組成物容器が接続されている。
【００５８】
次ぎにこの自動調製装置の作用について説明する。添字Ａを付した処理組成物添加系統について説明するが、他の添加系統についても同様に行なわれる。処理組成物容器１０内の組成物は、ノズルから送液管に吸い上げられ、口部１１、送液ポンプＰ、流入口５Ａを経て計量槽２に送液される。計量槽２の液面が液面レベルセンサー６Ａのセンシングポジションに達するとレベルセンサー６Ａが作動して開閉弁４が開き、計量槽２内の組成物は全量が混合槽１に投入される。同様にして、処理液の調製に関わる各構成処理組成物、調製に必用な所定量の希釈水及び再生の場合には使用済み処理液貯留槽からのオーバーフロー液もそれぞれ各送液管Ｂ，Ｃなどを経て同様に計量槽２で所要量が計量されて開閉弁４を経て混合槽１に添加され、そこで混合と攪拌が行なわれて処理液が完成する。完成した調製処理液は、送液口８から各処理液貯留槽に送られる。処理液を構成する各処理組成物、希釈水、オーバ−フロー液などはレベルセンサー６Aによって正確に軽量できるので、送液ポンプＰの送液精度は高い必要はなく、耐薬品性に優れたベローズポンプが好ましい。
【００５９】
上記の処理液自動調製装置を採用した大型現像所内の処理液の調製から、使用、使用済み処理液の再生などのフローの典型的な態様を図２によって概略説明する。
図２は、大型現像所における処理液調製工程のフロー概念図である。図１において、Ｓ１_A，Ｓ１_B，Ｓ１_C，-----Ｓ１_Xは、処理液Ｓ１調製用の構成処理組成物であり、それぞれ容器に充填された状態で処理組成物保管場所Ｓに用意されている。同様に処理液Ｓ２調製用の処理組成物Ｓ２_A-----などから処理液Ｓｎ調製用の構成処理組成物-----Ｓｎ_Xに至るまで現像所内で調製が行なわれる各処理液Ｓ１-----ＳＮ調製の貯性に用いる容器入り処理組成物Ｓ１_A-----Ｓｎ_Xが処理組成物保管場所Ｓに配置されている。
【００６０】
処理液調製部Ｍは、それぞれ処理液Ｓ１，Ｓ２，Ｓ３----Ｓｎ調製用の混合槽Ｍ１，Ｍ２，Ｍ３----Ｍｎが配列されており、処理液Ｓ１調製用の混合槽Ｍ１には処理組成物保管場所Ｓから構成処理組成物Ｓ１_A，Ｓ１_B，Ｓ１_C，-----Ｓ１_Xが前述のように送液ポンプと送液管を経て接続されており、ここで処理液Ｓ１の調製が行なわれる。同様に処理液Ｓ２----Ｓｎ調製用の混合槽Ｍ２，Ｍ３----Ｍｎも処理組成物保管場所Ｓから構成処理組成物Ｓ２_A，Ｓ２_B，Ｓ２_C-----Ｓｎ_Xがそれぞれの送液ポンプと送液管を経て接続されており、処理液Ｓ２----Ｓｎの調製が行なわれる。
【００６１】
処理液貯留場所Ｒは、現像所内で処理されるカラーネガ処理、カラーペーパー処理などの処理系統に用いられる補充液などの各処理液Ｓ１，Ｓ２，Ｓ３----Ｓｎがそれぞれの貯留槽Ｒ１，Ｒ２，Ｒ３----Ｒｎに保管される。
現像室内の処理サイトＧには、カラーネガ処理、カラーペーパー処理などの各現像機G-I、G-II、G-III----G-Xが処理系統別に設置されていて、各処理に用いられる補充液などの各処理液Ｓ１，Ｓ２，Ｓ３----Ｓｎがそれぞれの貯留槽Ｒ１，Ｒ２，Ｒ３----Ｒｎからそれぞれの現像機に補給される(図では、現像機Ｇ−Ｉが貯留槽槽Ｒ１，Ｒ２，Ｒ３から補充液が補給される)。
各現像機の各処理槽から排出されるオーバーフロー液(図では、現像機Ｇ−Iの図示しない３個の処理槽から３種のオーバーフロー)が集められてオーバーフロー貯留槽ＯＦ１，ＯＦ２，ＯＦ３に保管され、処理液調製の際に混合槽Ｍ１，Ｍ２，Ｍ３----Ｍｎに返送されて再使用される。また、余剰のオーバーフロー液や再生使用しない場合のオーバーフロー液は排水処理が行なわれて現像所外に排出され
る。
【００６２】
つぎに本発明のカラー現像処理組成物を現像工程に使用する際に現像以降の工程に用いられる処理組成物について説明する。
はじめにカラー現像工程に続く脱銀工程の漂白液用及び漂白定着液用の漂白剤について説明する。
漂白液又は漂白定着液において用いられる漂白剤としては、公知の漂白剤も用いることができるが、特に鉄(III) の有機錯塩（例えばアミノポリカルボン酸類の錯塩）もしくはクエン酸、酒石酸、リンゴ酸などの有機酸、過硫酸塩、過酸化水素などが好ましい。
【００６３】
これらのうち、鉄(III) の有機錯塩は迅速処理と環境汚染防止の観点から特に好ましい。鉄(III) の有機錯塩を形成するために有用なアミノポリカルボン酸、またはそれらの塩を挙げると、生分解性のあるエチレンジアミンジ琥珀酸（ＳＳ体）、Ｎ−（２−カルボキシラートエチル）−Ｌ−アスパラギン酸、ベ−ターアラニンジ酢酸、メチルイミノジ酢酸をはじめ、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸、１，３−ジアミノプロパン四酢酸、プロピレンジアミン四酢酸、ニトリロ三酢酸、シクロヘキサンジアミン四酢酸、イミノ二酢酸、グリコールエーテルジアミン四酢酸、などを挙げることができる。これらの化合物はナトリウム、カリウム、チリウム又はアンモニウム塩のいずれでもよい。これらの化合物の中で、エチレンジアミンジ琥珀酸（ＳＳ体）、Ｎ−（２−カルボキシラートエチル）−Ｌ−アスパラギン酸、βーアラニンジ酢酸、エチレンジアミン四酢酸、１，３−ジアミノプロパン四酢酸、メチルイミノ二酢酸はその鉄(III) 錯塩が写真性の良好なことから好ましい。これらの第２鉄イオン錯塩は錯塩の形で使用してもよいし、第２鉄塩、例えば硫酸第２鉄、塩化第２鉄、硝酸第２鉄、硫酸第２鉄アンモニウム、燐酸第２鉄などとアミノポリカルボン酸などのキレート剤とを用いて溶液中で第２鉄イオン錯塩を形成させてもよい。また、キレート剤を第２鉄イオン錯塩を形成する以上に過剰に用いてもよい。鉄錯体のなかでもアミノポリカルボン酸鉄錯体が好ましい。
【００６４】
漂白処理組成物の添加量は、調製した処理液の濃度が０．０１〜１．０モル／リットル、好ましくは０．０３〜０．８０モル／リットル、更に好ましくは０．０５〜０．７０モル／リットル、更に好ましくは０．０７〜０．５０モル／リットルとなるように定められる。
【００６５】
漂白処理組成物、漂白定着処理組成物あるいは定着処理組成物には、種々の公知の有機酸（例えばグリコール酸、琥珀酸、マレイン酸、マロン酸、クエン酸、スルホ琥珀酸など）、有機塩基（例えばイミダゾール、ジメチルイミダゾールなど）あるいは、２−ピコリン酸を始めとする特開平９−２１１８１９号公報に記載の一般式（Ａ−ａ）で表される化合物やコージ酸を始めとする同公報に記載の一般式（Ｂ−ｂ）で表される化合物を含有することが好ましい。これら化合物の添加量は、調製した処理液の濃度が１リットル当たり０．００５〜３．０モルが好ましく、さらに好ましくは０．０５〜１．５モルとなるように定められる。
【００６６】
カラー用の定着処理組成物（カラー用漂白定着処理組成物の定着組成物も含む）についてまとめて説明する。こられ漂白定着処理組成物又は定着処理組成物に使用される化合物は、公知の定着組成物、即ちチオ硫酸ナトリウム、チオ硫酸アンモニウムなどのチオ硫酸塩、チオシアン酸ナトリウム、チオシアン酸アンモニウムなどのチオシアン酸塩、エチレンビスチオグリコール酸、３，６−ジチア−１，８−オクタンジオールなどのチオエーテル化合物およびチオ尿素類などの水溶性のハロゲン化銀溶解剤であり、これらを１種あるいは２種以上混合して使用することができる。また、特開昭55−155354号公報に記載された定着剤と多量の沃化カリウムの如きハロゲン化物などの組み合わせからなる特殊な漂白定着液等も用いることができる。本発明においては、チオ硫酸塩特にチオ硫酸アンモニウム塩の使用が好ましい。処理組成物から調製した定着液及び漂白定着液中の定着組成物の濃度は、調合液１リットルあたり０．３〜３モルが好ましく、更に好ましくは０．５〜２．０モルの範囲である。
【００６７】
漂白定着組成物及び定着処理組成物の溶解時pH領域は、３〜８が好ましく、更には４〜８が特に好ましい。ｐＨがこれより低いと脱銀性は向上するが、液の劣化及びシアン色素のロイコ化が促進される。逆にｐＨがこれより高いと脱銀が遅れ、かつステインが発生し易くなる。
本発明の顆粒剤から作られる漂白液のｐＨ領域は８以下であり、２〜７が好ましく、２〜６が特に好ましい。ｐＨがこれより低いと液の劣化及びシアン色素のロイコ化が促進され、逆にｐＨがこれより高いと脱銀が遅れ、ステインが発生し易くなる。
ｐＨを調整するためには、必要に応じて前記した固体状の酸、及び前記した固体アルカリである水酸化カリウム、水酸化ナトリウム、水酸化リチウム、炭酸リチウム、炭酸ナトリウム、炭酸カリウム及び酸性又はアルカリ性緩衝剤等を添加することができる。
【００６８】
また、漂白定着処理組成物には、その他各種の蛍光増白剤や消泡剤或いは界面活性剤、ポリビニルピロリドン等を含有させることができる。なお、蛍光増白剤は、前記したカラー現像処理組成物に調製した現像液中の濃度が0.02〜1.0 モル／リットルになるように含ませることもできる。
漂白定着組成物や定着処理組成物は、保恒剤として亜硫酸塩（例えば、亜硫酸ナトリウム、亜硫酸カリウム、亜硫酸アンモニウム、など）、重亜硫酸塩（例えば、重亜硫酸アンモニウム、重亜硫酸ナトリウム、重亜硫酸カリウム、など）、メタ重亜硫酸塩（例えば、メタ重亜硫酸カリウム、メタ重亜硫酸ナトリウム、メタ重亜硫酸アンモニウム、など）等の亜硫酸イオン放出化合物や、ｐ−トルエンスルフィン酸、ｍ−カルボキシベンゼンスルフィン酸などのアリ−ルスルフィン酸などを含有するのが好ましい。これらの化合物は亜硫酸イオンやスルフィン酸イオンに換算して約0.02〜1.0 モル／リットル含有させることが好ましい。
保恒剤としては、上記のほか、アスコルビン酸やカルボニル重亜硫酸付加物、あるいはカルボニル化合物等を添加しても良い。
【００６９】
定着又は漂白定着を終了したのち水洗代替安定浴や画像安定化用安定浴が用いられることが多いが、これらの浴は、低濃度であって処理剤の効用は大きくはないが、必要があれば処理組成物を製造することができる。安定浴処理剤には、特開昭62−288838号公報に記載のカルシウム、マグネシウムを低減させる方法を極めて有効に用いることができる。また、特開昭57−8542号公報に記載のイソチアゾロン化合物やサイアベンダゾール類、同61−120145号公報に記載の塩素化イソシアヌール酸ナトリウム等の塩素系殺菌剤、特開昭61−267761号公報に記載のベンゾトリアゾール、銅イオン、その他堀口博著「防菌防黴の化学」（1986年）三共出版、衛生技術会編、「微生物の減菌、殺菌、防黴技術」（1982年）工業技術会、日本防菌防黴学会編「防菌防黴剤事典」（1986年）に記載の殺菌剤を用いることもできる。
【００７０】
また、残存するマゼンタカプラーを不活性化して色素の褪色やステインの生成を防止するホルムアルデヒド、アセトアルデヒド、ピルビンアルデヒドなどのアルセヒド類、米国特許第４７８６５８３号に記載のメチロール化合物やヘキサメチレンテトラミン、特開平２−１５３３４８号に記載のヘキサヒドロトリアジン類、米国特許第４９２１７７９号に記載のホルムアルデヒド重亜硫酸付加物、押収特許公開公報第５０４６０９号、同５１９１９０号などに記載のアゾリルメチルアミン類などを添加してもよい。更に、水切り剤として界面活性剤や、硬水軟化剤としてＥＤＴＡに代表されるキレート剤を用いることもできる。
【００７１】
本発明の現像処理組成物が用いられるカラー写真感光材料の処理工程は、カラー現像工程、脱銀工程、水洗又は安定浴工程及び乾燥工程からなり、各工程間にはリンス工程、中間水洗工程、中和工程などの補助的な工程を挿入することもできる。脱銀工程は漂白定着液による一工程処理又は漂白工程と定着工程から成る二工程処理によって行われる。また、水洗工程に代わる水洗代替安定浴のほかに画像安定化を目的とする画像安定浴を水洗又は安定浴工程と乾燥工程の間に設けることもできる。
本発明が適用できる処理は、迅速現像型、低補充型及び国際的に互換性のある標準型の処理のいずれでもよい。
【００７２】
現像処理される感光材料がカラーネガやカラーリバーサルフィルムなどのカラー撮影材料の場合、その処理温度は一般的には、３０〜４０°Ｃであるが、迅速処理では、３８〜６５°Ｃであり、好ましくは４０〜５５°Ｃである。その現像処理時間は、一般的な処理では１〜８分であるが、迅速処理では、１５〜１９５秒であり、好ましくは２０〜１５０秒で行う。補充量は、感光材料１ｍ²当たり標準現像では６００ミリリットルであるが、低補充の処理では、３０〜３９０ミリリットルであり、好ましくは５０〜３００ミリリットル、さらには８０〜２００ミリリットルで行うこともある。
現像処理される感光材料がカラー印画紙などのカラープリント用材料の場合、その処理温度は一般的には、３０〜４０°Ｃであるが、迅速処理では、３８〜６５°Ｃである。その現像処理時間は、一般的な処理では３０秒〜３分であるが、迅速処理では、５〜４５秒であり、好ましくは５〜２０秒で行う。補充量は、感光材料１ｍ²当たり標準現像では１６１ミリリットルであるが、低補充の処理では、１０〜１５０ミリリットルであり、好ましくは２０〜１００ミリリットル、さらには２５〜８０ミリリットルで行うこともある。
【００７３】
カラー現像処理では現像工程に続いて脱銀処理工程に入り、漂白液及び漂白定着液による処理がなされる。
漂白時間は、通常１０秒〜６分３０秒、好ましくは１０秒〜４分３０秒、とくに好ましくは、１５秒から２分である。
本発明に係る漂白定着処理又は定着処理は、処理時間５〜２４０秒、好ましくは１０〜６０秒である。処理温度は２５℃〜６０℃、好ましくは３０℃〜５０℃である。また、補充量は感光材料１ｍ²当たり１０ｍｌ〜２５０ｍｌ、好ましくは１０ｍｌ〜１００ｍｌ、特に好ましくは１５ｍｌ〜６０ｍｌである。
【００７４】
つぎに、本発明のカラー現像処理組成物が適用される感光材料について説明する。
本発明の処理組成物を用いる感光材料は、前記したように写真市場で汎用されている撮影用カラー写真感光材料、カラー印画紙であり、この感光材料は支持体上に少なくとも１層の感光性層が設けられている。典型的な例としては、支持体上に、実質的に感色性は同じであるが感光度の異なる複数のハロゲン化銀乳剤層から成る感光性層を少なくとも１つ有するハロゲン化銀写真感光材料である。
【００７５】
ハロゲン化銀カラー感光材料の層構成、膜厚、ハロゲン化銀乳剤については特開平３−１５０５６３号公報の第１１頁〜第１４頁に具体的に記載されている。また、カラー感光材料に使用できる写真用添加剤もＲＤに記載されており、下記の表に関連する記載箇所を示した。
【００７６】

【００７７】
また、各種カプラー及び溶媒については、特開平３−１５０５６３号公報及びここに引用された特許等に具体的に記載されている。
【００７８】
本発明の処理剤が適用されるカラー感光材料に適当な支持体は、例えば、前述のＲＤ.No.17643 の28頁、同No.18716の 647頁右欄から 648頁左欄、および同No.307105 の 879頁に記載されている。
【００７９】
本発明の処理剤が適用されるカラー感光材料は、乳剤層を有する側の反対側に、乾燥膜厚の総和が２μm 〜20μm の親水性コロイド層（バック層と称す）を設けることが好ましい。このバック層には、前述の光吸収剤、フィルター染料、紫外線吸収剤、スタチック防止剤、硬膜剤、バインダー、可塑剤、潤滑剤、塗布助剤、表面活性剤を含有させることが好ましい。このバック層の膨潤率は150 〜500 ％が好ましい。
【００８０】
本発明の処理剤が適用されるカラー感光材料は、磁気記録層を有していることが多い。
磁気記録層とは、磁性体粒子をバインダー中に分散した水性もしくは有機溶媒系塗布液を支持体上に塗設したものである。
【００８１】
撮影用のカラー感光材料には、セルローストリアセテート及びポリエステル支持体が用いられるが、その詳細については、公開技報、公技番号94-6023(発明協会;1994.3.15.)に記載されている。
ポリエステルはジオールと芳香族ジカルボン酸を必須成分として形成され、芳香族ジカルボン酸として２，６−、１，５−、１，４−、及び２，７−ナフタレンジカルボン酸、テレフタル酸、イソフタル酸、フタル酸、ジオールとしてジエチレングリコール、トリエチレングリコール、シクロヘキサンジメタノール、ビスフェノールＡ、ビスフェノールが挙げられる。この重合ポリマーとしては、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリシクロヘキサンジメタノールテレフタレート等のホモポリマーを挙げることができる。特に好ましいのは２，６−ナフタレンジカルボン酸を50モル％〜 100モル％含むポリエステルである。中でも特に好ましいのはポリエチレンー２，６−ナフタレートである。平均分子量の範囲は約 5,000ないし 200,000である。本発明のポリエステルのTgは50℃以上であり、さらに90℃以上が好ましい。
このポリエステルには紫外線吸収剤を練り込んでも良い。又ライトパイピング防止のため、三菱化成製のDiaresin、日本化薬製のKayaset 等ポリエステル用として市販されている染料または顔料を練り込むことにより目的を達成することが可能である。
【００８２】
本発明の処理剤を用いる感光材料は、支持体と感材構成層を接着させるために、下塗り層を施したのち、あるいは直接に表面処理することが好ましい。組成物処理、機械的処理、コロナ放電処理、火焔処理、紫外線処理、高周波処理、グロー放電処理、活性プラズマ処理、レーザー処理、混酸処理、オゾン酸化処理、などの表面活性化処理が挙げられる。表面処理の中でも好ましいのは、紫外線照射処理、火焔処理、コロナ処理、グロー処理である。
【００８３】
また感光材料を処理するには、特開平２−２０７２５０号公報の第２６頁右下欄１行目〜３４頁右上欄９行目、及び特開平４−９７３５５号公報の第５頁左上欄１７行目〜１８頁右下欄２０行目に記載の処理素材や処理方法が好ましく適用できる。
【００８４】
【実施例】
本発明のカラー現像処理組成物及びカラー現像液調製方法の具体的態様を以下の実施例によってさらに説明するが、本発明はこれに限定されるものではない。
〔実施例１〕
＜カラー現像補充液の調製＞
下記２種の処理液自動調製装置のそれぞれを用いて、下記カラー現像補充液用濃厚液体処理組成物（通常濃宿液ともいう）Ａ剤及びＢ剤を混合してカラー現像補充液を調製した。
Ａ）ノーリツ社製ミキシングタンク（ＭＸ−１２０：１２０Ｌサイズ）及び
Ｂ）ロックウエルハイテック（Rockwell HighTec）社製自動補充装置（Mixer HV-3：４．５Ｌサイズ）
ノーリツ社製ミキシングタンク及びロックウエルハイテック社製自動補充装置はいずれも市販されており、後者の装置は、図４に示した本発明の処理装置の一態様と原理的に同じ態様の装置であり、処理液の１回の調製量は３〜５リットルとするのに適した省スペース型の調製装置である。
【００８５】

【００８６】

【００８７】
・カラー現像補充液の調製
（補充液１リットル当たりの値で示す）
水 ７５０ｍｌ
カラー現像濃厚処理組成物Ａ剤 １００ｍｌ
カラー現像濃厚処理組成物Ｂ剤 １００ｍｌ
水を加えて １０００ｍｌ
【００８８】
＜補充液の液状評価＞
上記した処方で調製したカラー現像補充液の濁り、浮遊物や沈殿の有無を目視で観察し、下記の評価基準にしたがって評価してその結果を表４に示した。
評価基準
◎： 濁りが無く，浮遊物や沈殿物も無い
〇： わずかに濁りが認められる
×： 濁りが発生又は浮遊物や沈殿物が発生
××： 著しく浮遊物や沈殿物が発生
【００８９】
＜写真性能の評価＞
１）カラー現像液の調製
現像機の現像槽に投入するカラー現像液としては、上に記した補充液を下記のカラー現像スタータと混合して調製した。
・カラー現像液（１リットル当たりの値で示す）
水 ４００ｍｌ
カラー現像補充液 ４６０ｍｌ
カラー現像スターター １００ｍｌ
水を加えて １０００ｍｌ
・カラー現像スターター（カラー現像液１リットル当たりで示す）
水 ７０ｍｌ
塩化カリウム ７．４ｇ
臭化カリウム ０．０４ｇ
炭酸カリウム ７．７ｇ
炭酸水素ナトリウム ６．８ｇ
水を加えて全量 １００ｍｌ
【００９０】
２）カラーペーパーの処理
上記のカラー現像液を用い、下記の工程および処理液で、富士写真フィルム社製フジカラーペーパーEVE-BEAUTY PAPERに感光計（富士写真フィルム社製ＰＷＨ型、光源の色温度3200ケルビン）を使用して、センシトメトリー用階段露光を与えた。露光時間は、０．１秒で，露光量が２５０CMSになる照度で露光を行った。露光したカラーペーパーを下記の工程と処理液を用いて処理した。なお、処理機は富士写真フィルム社製ミニラボプリンタープロセサー フロンティア３５０を用いた。
【００９１】
処理工程 温度 時間
発色現像 ３８．５℃ ４５秒
漂白定着 ３８．０℃ ４５秒
リンス１ ３８．０℃ ２２秒
リンス２ ３８．０℃ ２２秒
リンス３ ３８．０℃ ２２秒
リンス４ ３８．０℃ ２２秒
乾燥 ８０℃ ３０秒
【００９２】
・カラー現像液：上記１）で調製
・漂白定着液：富士写真フイルム（株）製ミニラボ用処理剤ＣＰ−４８Ｓ Ｐ２スタートアップケミカル使用
・リンス： イオン交換水
【００９３】
３）写真特性の評価
上記処理済みのカラーペーパーの基準露光量からｌｏｇＥ（対数露光量）で＋１．３の露光量のマゼンタ発色濃度をマクベス濃度計を用いて測定し、結果を表４に示した。濃度値が高いほど感度が高く、濃度値が低いほど低感度である。
【００９４】
【表４】

【００９５】
・試験結果表４の結果から、蛍光増白剤を含有し、ｐＨ２〜４の現像主薬パートを用いて現像補充液を調製した場合、濁りや浮遊物の発生が無く、しかもこの補充液を用いた処理は感度が高い良好な写真性を示す結果が得られた。本発明の中でも、現像主薬パートのｐＨが２〜３の場合、処理液自動調製装置Ｂを用いるとさらに良好な結果が得られた。
【００９６】
実施例―２
下記のカラー現像用濃厚処理組成物を調製し、下記の処理工程にてランニングテストを実施した。感光材料試料には、富士写真フィルム社製フジカラーペーパーEVE-BEAUTY ＰＡＰＥＲを使用した。ランニングテストは、使用したカラー現像補充液の総量がカラー現像槽の液量の２倍になるまで行った。
使用した現像処理機は、富士写真フィルム社製ＦＰＲＰ４１２で、カラー現像補充液の調製は、実施例１と同様にロックウエルハイテック（Rockwell HighTec）社製自動補充装置（Mixer HV-3：４．５Ｌサイズ）を用いた。
【００９７】

【００９８】
・処理液処方
カラー現像液：富士写真フィルム社製ＣＰ−４５Ｘ Ｐ１Ｘ−ＬＲＰ１
カラー現像補充液：下記の濃厚処理組成物 Ａ及びＢを用いて調整した。

【００９９】

【０１００】
・カラー現像補充液の調製（補充液１リットル当たりの値で示す）
水 ７５０ｍｌ
カラー現像処理組成物Ａ剤 １００ｍｌ
カラー現像処理組成物Ｂ剤 １００ｍｌ
水を加えて １０００ｍｌ
ｐＨ １１．３５
【０１０１】
漂白定着液：富士写真フィルム社製ＣＰ−４５Ｘ Ｐ２Ｘ−ＬＲ Ｐ２
漂白定着補充液：富士写真フィルム社製ＣＰ−４５Ｘ Ｐ２Ｘ−ＬＲ
ランニング試験結果
ランニングテストの全期間を通して、補充液には、濁りや浮遊物の発生が無く、写真性能も感度が高い良好な結果が得られた。
【０１０２】
【発明の効果】
複数のパート、とりわけ２パートから構成されており、発色現像主薬を含むパートが蛍光増白剤をも含有するｐＨが２〜６のパートである本発明のハロゲン化銀写真用カラー現像処理組成物は、現像液を調製する際のにごり,沈殿析出、さらには感度の低下などの欠陥を伴なわず、しかも減容・軽量、調製容易という液体濃厚処理組成物の長所を具備している。とくにこのカラー現像用濃厚処理組成物による現像液調製方法は、攪拌不均一になり易い大ロットの処理液調製や自動調製装置による現像液の調製にもにごりや沈殿が生じないので、とりわけ大型の現像所に適した調製方法である。
【図面の簡単な説明】
【図１】本発明の処理組成物容器を効果的に適用できる処理液調製装置の概略図である。図１ａは、その装置断面図であり,図１ｂはその平面図である。
【図２】本発明の処理組成物容器を効果的に適用できる処理液調製装置を含む大型現像所の処理及び関連工程の概略図である。
【符号の説明】
１ 混合槽
２ 計量槽
３ 攪拌機構
４ 開閉弁
５Ａ，５Ｂ，５Ｃ 流入口
６Ａ，６Ｂ，６Ｃ レベルセンサー
７Ａ，７Ｂ，７Ｃ 送液管
８ 送液口
９ 排出口
１０ 容器
１１ 口部
Ｐ 送液ポンプ
Ｓ１，Ｓ２，Ｓ３，-----Ｓｎ 処理液
Ｓ１_A，Ｓ１_B，Ｓ１_C，-----Ｓ１_X 処理液Ｓ１調製用の構成処理組成物
Ｓ２_A 処理液Ｓ２調製用の構成処理組成物
ＳＮ_X 処理液Ｓｎ調製用の構成処理組成物
Ｍ１，Ｍ２，Ｍ３----Ｍｎ １〜ｎの各混合槽
Ｒ１，Ｒ２，Ｒ３----Ｒｎ １〜ｎの各混合槽
G-I、G-II、G-III---G-X Ｉ, II〜Ｘの各自動現像機
ＯＦ１，ＯＦ２，ＯＦ３ オーバーフロー貯留槽[0001]
BACKGROUND OF THE INVENTION
The present invention relates to color development processing of a silver halide photographic light-sensitive material (hereinafter sometimes simply referred to as light-sensitive material), and more particularly to the preparation of a color development processing composition and a development processing solution using the same. . In particular, the present invention relates to a color developing processing composition and a color developing solution adjustment method suitable for the large-scale preparation of photographic processing solutions in large-scale developing facilities.
[0002]
[Prior art]
The photographic processing solution used for photographic processing in a lab is an aqueous solution containing many chemicals including a developing agent. For example, a developing solution, a bleaching solution, or a fixing solution for each photosensitive material to be processed. It consists of several processing liquids with different functions. Since these processing solutions are prepared with chemicals including reducing and oxidizing chemicals, the burden of management and handling, the work equipment, and the operator's proficiency is required for preparation at each developer. It takes. Therefore, instead of preparing processing solutions by mixing and dissolving various types of developing chemicals in water at the development laboratory, the processing agent manufacturer prepares chemicals for each processing solution in advance and develops them in the form of a mixed processing agent. The form to supply to the place is generalized.
[0003]
The preparation treatment agent is a so-called solid treatment agent composed of only treatment chemicals (liquid composition chemicals may be accompanied by another liquid packaging form) and the composition treatment chemicals are stored in a container as an aqueous solution. Thus, there are liquid processing agent forms that are used simply by diluting in a developing laboratory, or in an extreme case without being diluted, each having advantages and disadvantages. (Note that in the art, the term “treatment agent” may refer to a treatment composition and the individual treatment chemicals that make up the treatment composition, but the present specification mainly describes the former. However, the term “treatment agent” is sometimes used for the latter, that is, individual treatment chemicals, in places where there is no possibility of misunderstanding).
[0004]
Among liquid processing agents (that is, liquid processing compositions), liquid processing agents that require water dilution are called concentrated liquid processing agents (also referred to as concentrated liquid processing agents), rather than processing agents in the form of working liquids. Since the volume is reduced, there are few disadvantages in transportation and handling, and the preparation of the treatment liquid is most generalized due to the simplicity of only water dilution.
[0005]
In particular, if the treatment composition is composed of multiple parts, further thickening and volume reduction can be achieved, so when preparing the treatment liquid, water dilution that involves mixing multiple concentrated liquids instead of simple water dilution However, the advantages of reducing the volume and reducing the weight of the treatment agent are much greater and are widely used.
[0006]
The form of each processing composition constituting the concentrated liquid processing agent is for a small scale laboratory such as an over-the-counter lab called a minilab, and is a form in a container of about 5 to 20 liters, and is generally referred to as a large lab. The developer unit is 100-1000 liters and the unit of the container is large, but in any case, the processing solution is usually prepared by putting the entire amount of the concentrated processing composition stored in the container into the preparation tank. It is carried out by mixing and diluting with water and / or overflow liquid from the processing tank of the developing machine.
[0007]
When preparing the treatment liquid, a concentrated treatment composition is mixed, and therefore, local non-uniformity of stirring tends to cause turbidity of the station and generation of precipitates. In particular, in the case of preparing a processing solution in a large laboratory where the preparation amount of the processing solution is large, a large amount of the concentrated processing composition is charged into the preparation tank, so that local unevenness of stirring is likely to occur. Turbidity and precipitation are likely to occur. In particular, when a large-scale treatment composition is rapidly added and mixed in order to shorten the treatment solution preparation time, the problem associated with this non-uniform stirring becomes prominent. It tends to be lost.
[0008]
[Problems to be solved by the invention]
The object of the present invention is to provide means for solving the problems associated with the preparation of processing solutions in the above-described developing laboratories, particularly large-scale developing laboratories, and satisfying all of volume reduction, light weight, easy preparation, and quality maintenance. Specifically, the first object of the present invention is to provide a concentrated processing composition for color development that is free from defects such as precipitation, precipitation, and sensitivity reduction when preparing a developer. It is to be.
The second object of the present invention is to provide a simple developer preparation method for preparing a developer by automatically preparing a concentrated processing composition for color development.
A further object of the present invention is to prepare a color developer without the above-mentioned defects even in the form of a developer that uses a concentrated processing composition carried out in a large-scale developing laboratory in a batch system (multiple intermittent use system). It is to present a method.
[0009]
[Means for Solving the Problems]
The inventor has analyzed in detail the chemical composition of the development processing composition and the liquid change when the composition is mixed, and the part containing the developing agent also contains a fluorescent brightening agent and is in a pH range within a specific range. In some cases, it was found that destabilization when mixed with other parts was remarkably suppressed, and further studies were made to arrive at the present invention.
That is, the present invention is as follows.
[0010]
    1. It is composed of a plurality of parts, and the part containing the color developing agent has a pH of 2 to 2 that also contains a fluorescent brightening agent.4ofHomogeneous liquid phaseA concentrated processing composition for color development for silver halide photography, wherein the composition is a part.
[0011]
The above-described present invention particularly exhibits the effects of the invention in the following aspects.
(1) The concentrated processing composition for color development for silver halide photography as described in 1 above, which comprises 2 parts.
(2) The concentrated processing composition for color development for silver halide photography according to the above (1), which is constituted in the form of a kit.
[0012]
2. The pH which is composed of a plurality of parts and the part containing the color developing agent also contains a fluorescent brightener is 2 to 24ofHomogeneous liquid phaseA method for preparing a silver halide photographic color developer, comprising mixing and diluting a predetermined amount of each constituent part of a concentrated color developing composition for color development into water to form a developer.
[0013]
In the second aspect of the present invention, the effects of the invention are particularly exerted in the following aspects.
(1) A plurality of parts constituting the treatment composition are accommodated in a plastic container, and the total amount or a predetermined amount of each part is taken out from the container and mixed with water to prepare the above 2. A method for preparing a silver halide photographic color developer as described.
(2) A plurality of parts constituting the treatment composition are stored in a plastic container, and a predetermined amount of each part is automatically measured from the container, and each measured predetermined amount is automatically mixed The silver halide photographic color as described in 2 above, wherein the processing solution is prepared by being mixed with water and automatically mixed with water, and the prepared processing solution is automatically sent to a storage tank. A method for preparing a developer.
[0014]
      The development processing composition of the present invention is characterized by a processing agent composed of a plurality of parts, wherein the part containing the color developing agent has a pH of 2 to 2 which also contains a fluorescent whitening agent.4By setting the color developing agent-containing part to this configuration, even if the color developing agent concentration is high, even when mixed with other parts, especially alkali agent parts, dust and precipitation Is effectively deterred. Further, the sensitivity of the developer is prevented from being lowered. The decrease in sensitivity is considered to be caused by a trace amount of oxide generated by oxidizing the developing agent in a non-uniform mixed state.
[0015]
These effects are widely recognized when using multi-part development processing agents, but when the developer preparation lot is large, conditions that are likely to cause inhomogeneous mixing such as rapid mixing, and color developing agents. The effect is significant when applied to a large-scale developing laboratory where such a processing solution is usually prepared, since it is noticeable when the part has a high concentration. In particular, in the case of developing solution preparation using an automatic preparation apparatus in which mixing and water dilution are performed automatically, the effect of the color developing agent part having the constitution of the present invention is remarkable.
[0016]
The color developer of the present invention includes both a developer (mother solution) charged into the developing tank at the start-up of the developing process and a developing replenisher supplied to the developing tank when the developing process is being performed. However, the effect is exhibited particularly when applied to a developing replenisher.
Even if the color developer has a so-called kit configuration in which the size of the development processing solution preparation lot is adjusted to one, it is effective to use the component configuration of the color developing agent-containing part of the present invention.
Further, in this specification, the term “concentrated” in the case of “concentrated treatment composition” means that it is not a composition that involves dilution with water when preparing a treatment liquid, that is, a composition in a working liquid state. I mean.
Hereinafter, specific embodiments of the present invention will be described in detail.
[0017]
DETAILED DESCRIPTION OF THE INVENTION
<Configuration of color developer>
Processing chemicals dissolved in a color developer generally have (1) a color developing agent as an essential component, (2) an alkali agent component that activates the color developing agent, and (3) a color developing agent that is oxidized by air. Antioxidants (preservatives) that prevent oxidative degradation such as (4) Hard water softeners (metal chelating agents) that block water-derived metal impurities that cause turbidity in the developer or promote oxidation (5) Dissolution aid for making the processing composition concentration higher and compact, (6) Surfactant for preventing the generation of bubbles on the surface of the photosensitive material to be processed and the development processing tank, (7 ) Antifoggant to prevent development fog and air fog, (8) Fluorescent whitening agent with effects such as improving whiteness of the finished photo (reflective print) and color image fastening, (9) Others Required depending on the application target of the developer It contains various treatment chemicals, such as a compound satisfying the Do function. Among these groups, (1) to (3) are development processing agents, and (4) to (9) may not be included depending on the target photosensitive material and processing form. Further, if the development processing agent is a start-up developer, (7) is also essential. Moreover, even if one is selected from each group, several compounds may be used.
[0018]
    The design of the part composition that divides these treatment chemicals into multiple groups and makes each part a part is stable even if the treatment chemicals belonging to one part coexist, is easy to dissolve in a common solvent system, and has a high solubility. As long as the chemicals are high, the parts can be divided into various forms depending on the market conditions such as the photosensitive material to be developed and the scale of the developing laboratory to be applied. In the present invention, the part containing the developing agent contains a fluorescent brightening agent, and has a pH of 24As long as it is, the composition of the other parts and the number of parts can be appropriately selected. In the present specification, “Part” is in accordance with a method commonly used in the industry, and conforms to International Standard 5989 (a term for a compounded processing agent for processing a silver halide photosensitive material).
[0019]
The color developing agent-containing part of the present invention comprises a color developing agent and a fluorescent brightening agent as essential components. However, if uniform solubility is ensured, the above-mentioned (2) to (7) and (9) Each processing chemical may be included. In particular, adding a known developing agent solubilizer such as sodium p-toluenesulfonate, potassium p-toluenesulfonate, sodium benzenesulfonate, potassium p-benzenesulfonate, ethylene glycol or triethylene glycol is a color developing agent. There is an effect of increasing the concentration of.
[0020]
The color developing agent of the color developing agent-containing part of the present invention has a concentration of 30 to 1000 mmol / liter, preferably 50 to 800 mmol / liter. The concentration of the optical brightener is 1 to 500 mmol / liter, preferably 2 to 400 mmol / liter.
Moreover, although pH of the color developing agent containing part of this invention is 2-6, Preferably it is 2-4, More preferably, it is 2-3.
[0021]
The color development processing agent of the present invention can be applied to any color photographic light-sensitive material for photographing and printing. Further, the number of processing composition parts constituting the color development processing agent is plural, preferably 2 to 6 parts, more preferably 2 to 4 parts, and most preferably 2 parts. JP-A-5-181245 discloses turbidity in the mixing of a two-part color developing composition, but this processing agent can be used to process replenishing components without preparing a developing replenisher. A processing composition for a direct replenishment system in which the composition is directly added to a developing tank, and the usage form of the processing composition is different from that of a normal color development processing, and no mixing of parts is performed. It is a problem different from the dust and precipitation related to the solution problem. Further, the above publication does not suggest the present invention because the developing agent-containing part does not contain a fluorescent brightening agent.
[0022]
The constituent chemicals of the color developer will be described below, but in the case of a processing liquid prepared by mixing a plurality of constituent processing compositions, it is not divided into each processing composition part except for the color developing agent part. The constituent chemicals for the color developer will be described together. The developer processing composition is mixed with water in a ratio determined at the time of use to develop a developer or a developer replenisher (hereinafter, if distinction between a developer and a developer replenisher does not have a special meaning, both The developing solution and the developing replenishing composition are also used.
[0023]
The color developing agent will be described. Preferable examples of the color developing agent used in the present invention are known aromatic primary amine color developing agents, particularly p-phenylenediamine derivatives. Representative examples are shown below, but are not limited thereto.
[0024]
1) N, N-diethyl-p-phenylenediamine
2) 4-Amino-3-methyl-N, N-diethylaniline
3) 4-Amino-N- (β-hydroxyethyl) -N-methylaniline
4) 4-Amino-N-ethyl-N- (β-hydroxyethyl) aniline
5) 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline
6) 4-Amino-3-methyl-N-ethyl-N- (3-hydroxypropyl) aniline
7) 4-Amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline
8) 4-Amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethylaniline)
9) 4-Amino-N, N-diethyl-3- (β-hydroxyethyl) aniline
10) 4-Amino-3-methyl-N-ethyl-N- (β-methoxyethyl) aniline
11) 4-Amino-3-methyl-N- (β-ethoxyethyl) -N-ethylaniline
12) 4-Amino-3-methyl-N- (3-carbamoylpropyl-Nn-propyl-aniline
13) 4-Amino-N- (4-carbamoylbutyl-Nn-propyl-3-methylaniline
15) N- (4-amino-3-methylphenyl) -3-hydroxypyrrolidine
16) N- (4-Amino-3-methylphenyl) -3- (hydroxymethyl) pyrrolidine
17) N- (4-Amino-3-methylphenyl) -3-pyrrolidinecarboxamide
[0025]
Of the above p-phenylenediamine derivatives, exemplary compounds 5), 6), 7), 8) and 12) are particularly preferred, and among them, compounds 5) and 8) are preferred. Moreover, these p-phenylenediamine derivatives are usually in the form of a salt such as sulfate, hydrochloride, sulfite, naphthalene disulfonate, p-toluenesulfonate in the state of a solid material.
Although the content of the aromatic primary amine developing agent in the processing composition is as described above, the concentration of the developing agent in the developer prepared using this composition is 2 to 200 mmol per liter of the developing solution. , Preferably 6 to 100 mmol, more preferably 10 to 40 mmol.
[0026]
In the present invention, a bis (triazinylamino) stilbene sulfonic acid compound is preferred as the optical brightener added to the color developing agent part. As the bis (triazinylamino) stilbene sulfonic acid compound, known or commercially available niaminostilbene-based brighteners can be used. As the known bis (triazinylamino) stilbene sulfonic acid compound, for example, compounds described in JP-A-6-329936, JP-A-7-140625, JP-A-10-14049 and the like are preferable. Examples of commercially available compounds are described in, for example, “Dyeing Note”, 9th edition (Color Dyeing), pages 165 to 168, and among the compounds described therein, Blankophor BSU liq. And Hakkol BRK and The following optical brighteners are preferred.
[0027]
A preferred compound of the bis (triazinylamino) stilbene sulfonic acid fluorescent whitening agent is represented by the following general formula (SR).
[0028]
[Chemical 1]

[0029]
In the above general formula (SR), X₁, X₂And Y₁, Y₂Is a hydroxy group, an alkoxy group having 1 to 4 carbon atoms (for example, methoxy group, ethoxy group, methoxyethoxy group, etc.), an amino group, an alkylamino group having 1 to 6 carbon atoms (for example, methylamino group, ethylamino group, propyl group). Amino group, dimethylamino group, cyclohexylamino group, β-hydroxyethylamino group, Gβ-hydroxyethylamino group, β-sulfoethylamino group, N- (β-sulfoethyl) -N-ethylamino group, etc.), aryl An oxy group (for example, phenoxy group, p-sulfophenoxy group, etc.), an arylamino group (for example, anilino group, o, m, p-sulfoanilino group, o, m, p-chloroanilino group, o, m, p-toluidino group, o, m, p-carboxyanilino group, o, m, p-anisidino group, o, m, p-hydroxyanily It represents a group, etc.).
M represents a hydrogen atom or a monovalent cation.
Although the compound represented by general formula (SR) is shown below, the fluorescent whitening agent used for this invention is not limited to these exemplary compounds.
[0030]
[Table 1]

[0031]
[Table 2]

[0032]
[Table 3]

[0033]
[Chemical formula 2]

[0034]
[Chemical Formula 3]

[0035]
The content of the optical brightener in the processing composition is such that the concentration of the optical brightener is 1 to 500 mmol, preferably 2 to 400 mmol, more preferably 5 to 300 mmol, per liter of developer. .
The content of the fluorescent brightening agent in the color developing agent part has been described above, but the concentration of the brightening agent in the developer prepared using this development processing composition is preferably 1 to 500 mmol per liter of the developer. Is prepared to be 2 to 400 mmol, more preferably 5 to 300 mmol.
[0036]
The color developing agent part is made into a composition by appropriately adding a pH buffering agent or an alkali agent to be described later so that the pH value becomes 2-6.
[0037]
The color developing composition may contain a small amount of sulfite ions or may be substantially free of sulfite ions depending on the type of the light-sensitive material, but in the present invention, it is preferable to contain a small amount of sulfite ions. While sulfite ions have a significant preserving action, excessive amounts may have an undesirable effect on photographic performance during color development.
Moreover, you may contain a small amount of hydroxylamine. If hydroxylamine (usually used in the form of hydrochloride or sulfate, but omits the salt form below), it acts as a preservative for the developer as well as sulfite ion, but at the same time it contains hydroxylamine itself. Since the silver developing activity may affect the photographic characteristics, it is necessary to keep this addition amount small.
[0038]
In addition to the hydroxylamine and sulfite ions, an organic preservative may be added to the color developing composition as a preservative. The organic preservative refers to all organic compounds that reduce the deterioration rate of the aromatic primary amine color developing agent by being contained in the processing solution of the photosensitive material. That is, it is an organic compound having a function of preventing air oxidation of color developing agents, among others, the above hydroxylamine derivatives, hydroxamic acids, hydrazides, phenols, α-hydroxy ketones, α-amino ketones. Saccharides, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, and condensed amines are particularly effective organic preservatives. These are disclosed in JP-A 63-4235, 63-30845, 63-21647, 63-44655, 63-53551, 63-43140, 63-56654, 63- 58346, 63-43138, 63-146041, 63-44657, 63-44656, U.S. Pat.Nos. 3,615,503, 2,494,903, JP-A-52-143020, JP-B-48-30496 It is disclosed in each gazette or specification such as No ..
[0039]
Other preservatives include various metals described in JP-A-57-44148 and 57-53749, salicylic acids described in JP-A-59-180588, and JP-A-54-3532. The alkanolamines described herein, polyethyleneimines described in JP-A-56-94349, aromatic polyhydroxy compounds described in US Pat. No. 3,746,544, and the like may be contained as necessary. In particular, alkanolamines such as triethanolamine and triisopropanolamine, substituted or unsubstituted dialkylhydroxylamines such as disulfoethylhydroxylamine, diethylhydroxylamine, or aromatic polyhydroxy compounds may be added. .
[0040]
Among the organic preservatives, details of substituted hydroxylamine are described in JP-A Nos. 1-97953, 1-186939, 1-186940, 1-187557 and the like. In particular, adding both a substituted hydroxylamine and amines may be effective in improving the stability of the color developer and improving the stability during continuous processing.
Examples of the amines include cyclic amines as described in JP-A-63-239447, amines as described in JP-A-63-128340, and other JP-A-1-86939. Examples thereof include amines described in JP-A-1-187557. The content of the preservative in the processing agent varies depending on the type of the preservative, but generally the concentration in the working solution is 1 to 200 mmol, preferably 10 to 100 mmol per liter of the developer. Added.
[0041]
In the color developing composition, for example, chlorine ion may be added to the developing composition for color paper, if necessary. Color developer (especially developer for color print materials) usually contains 3.5 x 10 chlorine ions.^-2~ 1.5 x10^-1Although it is often contained in mol / liter, chlorine ions are usually released to the developer as a by-product of development, and therefore usually need not be added to the replenishment developing composition. A developing composition for a light-sensitive material for photographing may not contain chlorine ions.
[0042]
Regarding bromine ions, bromine ions in the color developer are 1 to 5 × 10 in the processing of photographic materials.^-3About mol / liter, and in the processing of printing materials, 1.0 × 10^-3The mol / liter or less is preferable. However, the composition for color developer replenisher is often not necessary in the same manner as the above-mentioned chlorine ions, but when added, bromine ions are added to the processing agent as necessary so that the bromine ion concentration falls within the above range. Ions may be added.
When the photosensitive material to be obtained is obtained from a silver iodobromide emulsion such as a color negative film or a color reversal film, the situation is the same with respect to iodine ions, but usually iodine ions are released from the photosensitive material. Thus, the iodine ion concentration per liter of the developer is about 0.5 to 10 mg, and therefore it is usually not included in the replenishing processing composition.
[0043]
In the present invention, the developer is preferably added so that the pH of the developer is 9.0 to 12.5 and the pH of the replenisher is 9.0 to 13.5. An alkali agent, a buffering agent and, if necessary, an acid agent can be included so that the pH value can be maintained.
Various hydroxides can be added as the alkali. For example, potassium hydroxide, sodium hydroxide, lithium hydroxide, tripotassium hydrogen phosphate, trisodium hydrogen phosphate and their hydrates, triethanolamine, diethanolamine and the like can be mentioned. In addition, an inorganic / organic water-soluble solid acid can be used as the acid agent added as necessary. For example, succinic acid, tartaric acid, propionic acid, ascorbic acid can be mentioned.
[0044]
In order to maintain the pH when the treatment liquid is prepared, it is preferable to use various buffering agents. Examples of the buffer include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4- Dihydroxyphenylalanine salt, alanine salt, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. In particular, carbonate, phosphate, tetraborate, and hydroxybenzoate have excellent buffering ability in the high pH range of pH 9.0 or higher, and adverse effects on photographic performance even when added to color developers (fogging, etc.) It is particularly preferable to use these buffering agents.
[0045]
Specific examples of these buffering agents include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) ), Potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.
Since the buffer is not a component that is reacted and consumed, the concentration of the developer and the replenisher prepared from the processing agent is 0.01 to 2 mol per liter, preferably 0.1 to 0.5 mol. Thus, the amount of addition in the composition is determined.
[0046]
Various chelating agents which are precipitation inhibitors for other color developer components such as calcium and magnesium, or color developer stability improvers can also be added to the color developing composition. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ′, N′-tetramethylenesulfonic acid, transsiloxanediaminetetraacetic acid, 1 , 2-diaminopropanetetraacetic acid, glycol ether diamine tetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, 2 -Phosphonobutane-1,2,4-tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, 1,2- And dihydroxybenzene-4,6-disulfonic acid It is.
These chelating agents may be used in combination of two or more as required.
The amount of these chelating agents may be an amount sufficient to sequester metal ions in the prepared color developer. For example, it is added so as to be about 0.1 to 10 g per liter.
[0047]
If necessary, an arbitrary development accelerator can be added to the color developing composition according to the present invention. As development accelerators, see JP-B-37-16088, JP-A-37-5987, JP-A-38-7826, JP-A-44-12380, JP-A-45-9019 and U.S. Pat.No. 3,813,247. Thioether compounds represented, p-phenylenediamine compounds represented in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B 44-30074, JP-A-56- Quaternary ammonium salts represented in 156826 and 52-43429, etc., U.S. Pat.Nos. 2,494,903, 3,128,182, 4,230,796, 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Pat. 2,596,926 and 3,582,346, etc.Amine compounds described in each publication or specification, JP-B-37-16088, JP-A-42-25201, U.S. Pat.No. 3,128,183, JP-B-41-11431, JP-A-42-23883 And U.S. Pat.No. 3,532,501, etc. The 3-pyrazolidones or imidazoles may be added as needed. The added amount in the composition is determined so that the concentration of the developer and replenisher prepared from the processing agent is 0.001 to 0.2 mol, preferably 0.01 to 0.05 mol, per liter. It is done.
[0048]
An optional antifoggant can be added to the color developing composition according to the present invention, if necessary, in addition to the halogen ion. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2 -Representative examples include nitrogen-containing heterocyclic compounds such as thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine. In addition, various surfactants such as alkyl sulfonic acid, aryl sulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid may be added to the color developer as necessary. The added amount in the composition is such that the concentration of the developer and replenisher prepared from the processing composition is 0.0001 to 0.2 mol, preferably 0.001 to 0.05 mol, per liter. It is decided.
[0049]
As the solvent of the processing composition, water is usually used. However, when the solubility in water becomes a limitation, such as a developing agent-containing processing composition, an aqueous solvent is used, preferably diethylene glycol, triethylene mainly containing water. A mixed solvent containing 1 to 20% by mass of a water-miscible organic solvent that increases the solubility of developing agents such as ethylene glycol and ethylene glycol is selected.
Further, the developing agent-containing part may contain sulfite or bisulfite as an inorganic preservative in an amount of 0.1 to 1 mol% of the developing agent.
[0050]
The liquid preparation processing composition used in the automatic processing liquid preparation apparatus of the present invention is a process in which individual components of the processing composition part constituting the processing agent are filled in a container, or a process in which the constituent parts are assembled together. It is supplied mainly to large labs as an agent, or as a processing agent with a kit configuration tailored to the size of the preparation lot, mainly for the minilab market (for over-the-counter labs). In the former case, it is preferably used for preparing a developer with an automatic processing solution preparation apparatus.
[0051]
The material of the container for the treatment composition is preferably polyethylene, and HDPE is particularly suitable in terms of strength and gas barrier properties, and HDPE having a specific gravity of 0.94 or more is particularly preferable. In particular, an example of a preferable container is a container made of high density polyethylene (hereinafter referred to as HDPE) having a density of 0.941 to 0.969 as a single constituent resin. A more preferable density is 0.951 to 0.969, and still more preferably 0.955 to 0.965.
[0052]
The material may contain a plasticizer, stearic acid, other fillers and additives, but more preferably a single composition HDPE is excellent in gas barrier properties and strength. The thickness of the container does not have to be carried during work, so it is not necessary to reduce the weight and reduce the weight, but it reduces the oxidative deterioration that occurs while the stored treatment composition is being used continuously. Therefore, a certain amount of thickness is required from the standpoint of maintaining the strength, and the thickness of the container is an average thickness of the columnar portion of 0.5 mm or more for a 5-liter bottle, 0.8 mm or more for a 20-liter bottle, and 30 liters. For the bottle, 1 mm or more is sufficient, and there is no restriction on the upper limit of the thickness, but it is meaningless to make the thickness unnecessarily thick on the weight or material unit basis.
[0053]
The container is manufactured by hollow molding (including injection hollow molding) or rotational molding, which is adopted for general bottle molding, preferably by hollow molding.
The oxygen permeability of the treatment composition container is 0.005 ml / m except for the bleach treatment composition container.².S.MPa (20 ° C., 65% RH) or less, preferably 0.002 ml / m²・ S · MPa (20 ° C., 65% RH) or less, and the lower the oxygen permeability, the better. The lower limit is determined within the limits allowed by the handling and economics of the container. The oxygen permeability coefficient is “O₂Permeation of plastic container, modern packing (O₂ permeation of plastic container, Modern Packing; N.J. Calyan, 1968), December pp. 143-145.
[0054]
The moisture (moisture) permeability coefficient of the container is 0.005 ml / m².S.MPa (20 ° C., 65% RH) or less, preferably 0.002 ml / m²・ S · MPa (20 ° C., 65% RH) or less, and the lower the moisture permeability, the better. The lower limit is determined within the limits allowed by the handling and economics of the container.
[0055]
The developer of the present invention can be applied to any developer for color negative processing, color paper processing, and color reversal processing. In processing the light-sensitive material, it is used together with a processing agent for each processing step such as bleaching (or bleach-fixing), fixing, and stabilizing bath.
[0056]
Next, the preparation of the processing solution at the developing station will be described. In general, large-scale developing laboratories (large laboratories) often have a film processing amount of 1000 to 10,000 per day (the processing amount of color paper corresponds to the film processing amount). In a developing laboratory of such a scale, the amount of preparation per time is often a scale of about 100 to 500 liters, but the developer of the present invention is prepared in such a large lot of developer. On the other hand, the finished amount of one preparation is 3 to 5 liters, and it can be preferably applied to the preparation of a developer which is labor-saving by an automatic preparation apparatus without generation of dust during mixing. In this case, since a floor area is not required, it is advantageous from the viewpoint of space saving.
[0057]
One embodiment of preparing a processing solution by an automatic preparation apparatus using the color developer of the present invention will be described with reference to the drawings. FIG. 1 is a schematic system diagram showing the structure of the automatic preparation apparatus and the functions of each part. In FIG. 1, FIG. 1 a is an apparatus cross-sectional view, and FIG. 1 b is a plan view. The treatment liquid preparation apparatus is provided with a mixing tank 1 provided with a stirring means 3 and a measuring tank 2 provided with an on-off valve 4 that can be put into the mixing tank 1 by being placed immediately above the mixing tank, and a treatment composition. 5A, 5B, and 5C, and level sensors 6A, 6B, and 6C that detect the liquid level of the treatment composition that has flowed into and stored in the measuring tank 2. The mixing tank 1 has a stirring mechanism 3, a discharge port 9 for discharging waste liquid that is no longer necessary, and a liquid supply port 8 for supplying the prepared processing liquid to a storage tank such as a replenishing tank. Liquid inlet pipes 7A, 7B, and 7C (not shown) are connected to the respective containers 5A, 5B, and 5C via a liquid supply pump P to containers containing processing compositions. A container 10 is connected to the liquid feeding pipe 7A via a liquid feeding pump P, and a nozzle for sucking the composition is provided at the tip of the liquid feeding pipe introduced into the container from the mouth 11 of the container 10. Is inserted into the treatment composition liquid so that the composition can be sucked.
In FIG. 1, the inlet, the level sensor, the liquid supply pipe, etc. are shown by representing only the three members A, B, C and the subscripts. A number satisfying the type of container of the agent composition is provided. In addition, as for the treatment agent composition container and the like, only those in contact with the liquid feeding pipe 7A attached with the subscript A are shown as representatives. It is connected.
[0058]
Next, the operation of this automatic preparation apparatus will be described. Although the treatment composition addition system | strain which attached | subjected the subscript A is demonstrated, it carries out similarly about another addition system | strain. The composition in the treatment composition container 10 is sucked up from the nozzle to the liquid feeding pipe, and fed to the measuring tank 2 through the mouth portion 11, the liquid feeding pump P, and the inflow port 5A. When the liquid level in the measuring tank 2 reaches the sensing position of the liquid level sensor 6A, the level sensor 6A is activated to open the on-off valve 4, and the entire composition in the measuring tank 2 is charged into the mixing tank 1. Similarly, each constituent treatment composition related to the preparation of the treatment liquid, a predetermined amount of dilution water necessary for the preparation, and an overflow liquid from the used treatment liquid storage tank in the case of regeneration are also supplied to the liquid feeding pipes B and C, respectively. In the same manner, a required amount is weighed in the measuring tank 2 and added to the mixing tank 1 through the on-off valve 4, where mixing and stirring are performed to complete the processing liquid. The completed prepared treatment liquid is sent from the liquid feed port 8 to each treatment liquid storage tank. Each treatment composition, dilution water, overflow liquid, etc. that make up the treatment liquid can be accurately reduced in weight by the level sensor 6A. Therefore, the liquid feed pump P does not need to have high liquid feed accuracy, and has excellent chemical resistance. A pump is preferred.
[0059]
A typical embodiment of a flow from preparation of a processing solution in a large-scale developing laboratory employing the above-described processing solution automatic preparation apparatus to use and regeneration of a used processing solution will be schematically described with reference to FIG.
FIG. 2 is a conceptual flow diagram of a processing solution preparation process in a large-scale developing station. In FIG. 1, S1_A, S1_B, S1_C, ----- S1_XIs a constituent treatment composition for preparing the treatment liquid S1, and is prepared in the treatment composition storage place S in a state of being filled in containers. Similarly, the treatment composition S2 for preparing the treatment liquid S2_A----- Composition processing composition for preparation of processing solution Sn from ----- Sn_XEach processing solution S1 that is prepared in the developing station until the process up to step S1 ----- Contained processing composition S1 used for storage of SN preparation_A----- Sn_XIs disposed in the treatment composition storage location S.
[0060]
In the treatment liquid preparation unit M, the mixing tanks M1, M2, M3, and Mn for preparing the processing liquids S1, S2, S3, and S3 are arranged, and the mixing tank M1 for preparing the processing liquid S1 is arranged. The composition composition composition S1 from the composition composition storage location S_A, S1_B, S1_C, ----- S1_XIs connected to the liquid feed pump via the liquid feed pipe as described above, and the treatment liquid S1 is prepared here. Similarly, the mixing tanks M2, M3 ---- Mn for preparing the processing liquid S2 ---- Sn are also prepared from the processing composition storage place S to the constituent processing composition S2._A, S2_B, S2_C----- Sn_XAre connected to each liquid feed pump via a liquid feed pipe, and the treatment liquid S2 ---- Sn is prepared.
[0061]
In the processing liquid storage location R, the processing liquids S1, S2, S3 ---- Sn such as replenishing liquids used in processing systems such as color negative processing and color paper processing processed in the development laboratory are stored in the respective storage tanks R1, R2, R3 ---- Stored in Rn.
At processing site G in the developing chamber, color negative processing, color paper processing and other developing machines GI, G-II, G-III ---- GX are installed for each processing system, and the replenisher used for each processing Each processing solution S1, S2, S3 ---- Sn is replenished to each developing device from each storage tank R1, R2, R3 ---- Rn (in the drawing, the developing device GI is stored). The replenisher is replenished from the tanks R1, R2, R3).
Overflow liquid discharged from each processing tank of each developing machine (in the figure, three types of overflow from three processing tanks (not shown) of the developing machine GI) are collected and stored in the overflow storage tanks OF1, OF2, OF3. When the processing liquid is prepared, it is returned to the mixing tanks M1, M2, M3 --- Mn and reused. Also, excess overflow liquid and overflow liquid when not used for recycling are drained and discharged outside the laboratory.
The
[0062]
Next, when the color development processing composition of the present invention is used in the development step, the processing composition used in the steps after development will be described.
First, the bleaching agent for the bleaching solution and the bleach-fixing solution in the desilvering step following the color development step will be described.
As the bleaching agent used in the bleaching solution or the bleach-fixing solution, known bleaching agents can also be used. Particularly, iron (III) organic complex salts (for example, complex salts of aminopolycarboxylic acids) or citric acid, tartaric acid, malic acid. Organic acids such as persulfate, hydrogen peroxide and the like are preferable.
[0063]
Of these, organic complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids useful for forming an organic complex salt of iron (III), or salts thereof include biodegradable ethylenediamine disuccinic acid (SS form), N- (2-carboxylate ethyl) -L-aspartic acid, beta-alanine diacetic acid, methyliminodiacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1,3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, iminodiacetic acid And glycol ether diamine tetraacetic acid. These compounds may be any of sodium, potassium, thylium or ammonium salts. Among these compounds, ethylenediamine disuccinic acid (SS form), N- (2-carboxylateethyl) -L-aspartic acid, β-alanine diacetic acid, ethylenediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, methyliminodioxy Acetic acid is preferable because its iron (III) complex salt has good photographic properties. These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. And a chelating agent such as aminopolycarboxylic acid may be used to form a ferric ion complex salt in a solution. Moreover, you may use a chelating agent in excess rather than forming a ferric ion complex salt. Of the iron complexes, aminopolycarboxylic acid iron complexes are preferred.
[0064]
The amount of the bleaching treatment composition added is such that the concentration of the prepared treatment liquid is 0.01 to 1.0 mol / liter, preferably 0.03 to 0.80 mol / liter, more preferably 0.05 to 0.70. It is determined to be mol / liter, more preferably 0.07 to 0.50 mol / liter.
[0065]
Various known organic acids (for example, glycolic acid, succinic acid, maleic acid, malonic acid, citric acid, sulfosuccinic acid, etc.), organic bases (for example, bleaching processing composition, bleach-fixing processing composition or fixing processing composition) can be used. For example, imidazole, dimethylimidazole, etc.), or compounds represented by the general formula (Aa) described in JP-A-9-211819 including 2-picolinic acid and kojic acid. It is preferable to contain the compound represented by general formula (Bb). The amount of these compounds added is determined so that the concentration of the prepared treatment liquid is preferably 0.005 to 3.0 mol, more preferably 0.05 to 1.5 mol per liter.
[0066]
The color fixing processing composition (including the fixing composition of the color bleach-fixing processing composition) will be described together. These bleach-fixing processing compositions or compounds used in the fixing processing compositions are known fixing compositions, i.e., thiosulfates such as sodium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate and ammonium thiocyanate. , A water-soluble silver halide solubilizer such as thioether compounds such as ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol, and thioureas. Can be used. A special bleach-fixing solution comprising a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can also be used. In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The concentration of the fixing composition in the fixing solution and the bleach-fixing solution prepared from the processing composition is preferably 0.3 to 3 mol, more preferably 0.5 to 2.0 mol, per liter of the prepared solution. .
[0067]
The dissolution pH range of the bleach-fixing composition and the fixing processing composition is preferably from 3 to 8, more preferably from 4 to 8. When the pH is lower than this, the desilvering property is improved, but the deterioration of the solution and the leuco conversion of the cyan dye are promoted. On the contrary, if the pH is higher than this, desilvering is delayed and stain is likely to occur.
The pH range of the bleaching solution made from the granule of the present invention is 8 or less, preferably 2 to 7, and particularly preferably 2 to 6. If the pH is lower than this, the deterioration of the liquid and the leuco conversion of the cyan dye are promoted. Conversely, if the pH is higher than this, desilvering is delayed and stain is likely to occur.
In order to adjust the pH, the solid acid described above and the solid alkali potassium hydroxide, sodium hydroxide, lithium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate and acidic or alkaline as necessary are used. Buffering agents and the like can be added.
[0068]
In addition, the bleach-fixing treatment composition may contain various other fluorescent whitening agents, antifoaming agents, surfactants, polyvinyl pyrrolidone, and the like. The fluorescent brightening agent can also be included so that the concentration in the developer prepared in the color developing composition described above is 0.02 to 1.0 mol / liter.
Bleach fixing compositions and fixing processing compositions may contain sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.), bisulfites (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite, ), Sulfite ion-releasing compounds such as metabisulfite (for example, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.), and ants such as p-toluenesulfinic acid and m-carboxybenzenesulfinic acid. -It is preferable to contain rusulphinic acid and the like. These compounds are preferably contained in an amount of about 0.02 to 1.0 mol / liter in terms of sulfite ion or sulfinate ion.
As a preservative, ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, or the like may be added in addition to the above.
[0069]
After completion of fixing or bleach-fixing, a water-washing alternative stabilizing bath or a stabilizing bath for image stabilization is often used, but these baths are low in concentration and the utility of the processing agent is not great, but it is necessary. Treatment compositions can be produced. As the stabilizing bath treating agent, the method of reducing calcium and magnesium described in JP-A-62-288838 can be used very effectively. Further, chlorinated bactericides such as isothiazolone compounds and siabendazoles described in JP-A-57-8542, chlorinated sodium isocyanurate described in JP-A-61-120145, JP-A-61-267761 Benzotriazole, copper ion, and other publications described in the publication, Hiroshi Horiguchi, "Chemistry of Antibacterial and Antifungal" (1986) Sankyo Publishing, Hygiene Technology Association, "Microbial sterilization, sterilization and antifungal technology" (1982) It is also possible to use the bactericides described in the Industrial Technology Association, Japanese Society for Antibacterial and Antifungal Studies, “Encyclopedia of Antibacterial and Antifungal Agents” (1986).
[0070]
Further, aldehydes such as formaldehyde, acetaldehyde, and pyrubinaldehyde that inactivate the remaining magenta coupler to prevent dye fading and stain formation, methylol compounds and hexamethylenetetramine described in US Pat. No. 4,786,583, Hexahydrotriazines described in U.S. Pat. No. 153348, formaldehyde bisulfite adducts described in U.S. Pat. No. 4,921,779, azolylmethylamines described in Seized Patent Publication Nos. 504609, 519190, etc. Also good. Furthermore, a surfactant can be used as a draining agent, and a chelating agent represented by EDTA can be used as a water softening agent.
[0071]
The color photographic light-sensitive material processing step in which the development processing composition of the present invention is used consists of a color development step, a desilvering step, a water washing or stabilizing bath step and a drying step, and between each step a rinsing step, an intermediate water washing step, An auxiliary process such as a neutralization process may be inserted. The desilvering process is performed by a one-step process using a bleach-fixing solution or a two-process process including a bleaching process and a fixing process. In addition to a water washing alternative stabilizing bath instead of the water washing step, an image stabilizing bath for the purpose of image stabilization can be provided between the water washing or stabilizing bath step and the drying step.
The processing to which the present invention can be applied may be any of rapid development type, low replenishment type and internationally compatible standard type processing.
[0072]
When the photosensitive material to be developed is a color photographing material such as a color negative or a color reversal film, the processing temperature is generally 30 to 40 ° C., but in the rapid processing, it is 38 to 65 ° C. Preferably it is 40-55 degreeC. The development processing time is 1 to 8 minutes in general processing, but 15 to 195 seconds in rapid processing, and preferably 20 to 150 seconds. Replenishment amount is 1m photosensitive material²The standard development per shot is 600 ml, but in low replenishment processing, it is 30 to 390 ml, preferably 50 to 300 ml, more preferably 80 to 200 ml.
When the photosensitive material to be developed is a color printing material such as color photographic paper, the processing temperature is generally 30 to 40 ° C., but is 38 to 65 ° C. for rapid processing. The development processing time is 30 seconds to 3 minutes in general processing, but 5 to 45 seconds in rapid processing, and preferably 5 to 20 seconds. Replenishment amount is 1m photosensitive material²The standard development per hit is 161 ml, but the low replenishment processing is 10 to 150 ml, preferably 20 to 100 ml, more preferably 25 to 80 ml.
[0073]
In the color development process, the desilvering process is performed after the development process, and the bleaching solution and the bleach-fixing solution are used.
The bleaching time is usually 10 seconds to 6 minutes 30 seconds, preferably 10 seconds to 4 minutes 30 seconds, particularly preferably 15 seconds to 2 minutes.
The bleach-fixing process or the fixing process according to the present invention has a processing time of 5 to 240 seconds, preferably 10 to 60 seconds. The treatment temperature is 25 ° C to 60 ° C, preferably 30 ° C to 50 ° C. The replenishment amount is 1m of photosensitive material.²It is 10 ml to 250 ml, preferably 10 ml to 100 ml, particularly preferably 15 ml to 60 ml.
[0074]
Next, a photosensitive material to which the color developing composition of the present invention is applied will be described.
The photosensitive material using the processing composition of the present invention is a color photographic photosensitive material for photography and color photographic paper which are widely used in the photographic market as described above, and this photosensitive material has at least one layer of photosensitive material on a support. A layer is provided. A typical example is a silver halide photographic light-sensitive material having at least one photosensitive layer comprising a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivity on a support. It is.
[0075]
The layer structure, film thickness, and silver halide emulsion of the silver halide color light-sensitive material are specifically described on pages 11 to 14 of JP-A-3-150563. Further, photographic additives that can be used in color light-sensitive materials are also described in RD, and the description locations related to the following table are shown.
[0076]

[0077]
Various couplers and solvents are specifically described in JP-A-3-150563 and the patents cited therein.
[0078]
Examples of the support suitable for the color light-sensitive material to which the processing agent of the present invention is applied include the above-mentioned RD. No. 17643, page 28, No. 18716, page 647, right column to page 648, left column, and 307105, page 879.
[0079]
The color light-sensitive material to which the processing agent of the present invention is applied is preferably provided with a hydrophilic colloid layer (referred to as a back layer) having a total dry film thickness of 2 μm to 20 μm on the side opposite to the side having the emulsion layer. This back layer preferably contains the aforementioned light absorber, filter dye, ultraviolet absorber, antistatic agent, hardener, binder, plasticizer, lubricant, coating aid, and surfactant. The swelling rate of this back layer is preferably 150 to 500%.
[0080]
The color photosensitive material to which the processing agent of the present invention is applied often has a magnetic recording layer.
The magnetic recording layer is obtained by coating a support with an aqueous or organic solvent-based coating liquid in which magnetic particles are dispersed in a binder.
[0081]
Cellulose triacetate and a polyester support are used for the color photographic material for photographing. Details thereof are described in the published technical bulletin, public technical number 94-6023 (Invention Association; 1994.3.15).
Polyester is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid, as aromatic dicarboxylic acid, Examples of phthalic acid and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of this polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred is a polyester containing 50 mol% to 100 mol% of 2,6-naphthalenedicarboxylic acid. Of these, polyethylene-2,6-naphthalate is particularly preferred. The average molecular weight range is about 5,000 to 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, more preferably 90 ° C. or higher.
This polyester may be kneaded with an ultraviolet absorber. In order to prevent light piping, the purpose can be achieved by kneading commercially available dyes or pigments for polyester, such as Mitsubishi Chemical's Diaresin and Nippon Kayaku's Kayaset.
[0082]
The light-sensitive material using the processing agent of the present invention is preferably subjected to a surface treatment after applying an undercoat layer or directly to adhere the support and the light-sensitive material constituting layer. Surface activation treatments such as composition treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment and the like can be mentioned. Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment, and glow treatment are preferable.
[0083]
For processing photosensitive materials, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5, upper left column 17 The processing materials and processing methods described in the 20th line of the lower right column of the 18th page to the 18th page are preferably applicable.
[0084]
【Example】
Specific embodiments of the color development processing composition and the color developer preparation method of the present invention will be further described by the following examples, but the present invention is not limited thereto.
[Example 1]
<Preparation of color developer replenisher>
Using each of the following two types of processing solution automatic preparation apparatuses, a color developing replenisher solution was prepared by mixing the following concentrated liquid processing composition for color developing replenisher solution (usually also referred to as a concentrated sardine solution) agent A and agent B. .
A) Noritz mixing tank (MX-120: 120L size) and
B) Automatic replenisher (Mixer HV-3: 4.5L size) manufactured by Rockwell HighTec
Both the mixing tank manufactured by Noritz and the automatic replenishing device manufactured by Rockwell Hightech are commercially available, and the latter device is a device having the same principle as that of the processing device of the present invention shown in FIG. This is a space-saving preparation device suitable for adjusting the amount of the treatment liquid to be 3 to 5 liters at a time.
[0085]

[0086]

[0087]
・ Preparation of color developer replenisher
(Indicated by the value per liter of replenisher)
750 ml of water
Color development concentrated processing composition A agent 100 ml
Color development concentrated processing composition B agent 100ml
1000ml with water
[0088]
<Liquidity evaluation of replenisher>
The color developer replenisher prepared with the above formulation was visually observed for the presence of turbidity, suspended matter and precipitation, and evaluated according to the following evaluation criteria. The results are shown in Table 4.
Evaluation criteria
◎: No turbidity, no suspended matter or sediment
○: Slight turbidity is observed
×: Turbidity occurs or suspended matter or sediment occurs
XX: Remarkably suspended matter and sediment are generated
[0089]
<Evaluation of photographic performance>
1) Preparation of color developer
The color developer to be introduced into the developing tank of the developing machine was prepared by mixing the replenisher described above with the following color developer starter.
・ Color developer (value per liter)
400 ml of water
460 ml of color developer replenisher
Color development starter 100ml
1000ml with water
-Color development starter (shown per liter of color developer)
70ml water
7.4g of potassium chloride
Potassium bromide 0.04g
7.7 g of potassium carbonate
6.8g of sodium bicarbonate
100ml with water
[0090]
2) Color paper processing
Using the above color developer and the following process and processing solution using Fuji Photo Film Fuji Color Paper EVE-BEAUTY PAPER with a sensitometer (Fuji Photo Film PWH type, light source color temperature 3200 Kelvin) A stair exposure for sensitometry was given. The exposure time was 0.1 seconds, and the exposure was performed with the illuminance at which the exposure amount was 250 CMS. The exposed color paper was processed using the following steps and processing solution. The processing machine used was a minilab printer processor frontier 350 manufactured by Fuji Photo Film Co., Ltd.
[0091]
Processing temperature Temperature Time
Color development 38.5 ° C 45 seconds
Bleach fixing 38.0 ° C 45 seconds
Rinse 1 38.0 ° C 22 seconds
Rinse 2 38.0 ° C 22 seconds
Rinse 3 38.0 ° C 22 seconds
Rinse 4 38.0 ° C 22 seconds
Dry 80 ° C 30 seconds
[0092]
-Color developer: prepared in 1) above
・ Bleaching fixer: Fuji Photo Film Co., Ltd. minilab processing agent CP-48S P2 startup chemical used
・ Rinse: Ion exchange water
[0093]
3) Evaluation of photographic characteristics
Using the Macbeth densitometer, the magenta color density at an exposure amount of +1.3 in log E (logarithmic exposure amount) from the reference exposure amount of the processed color paper was measured, and the results are shown in Table 4. The higher the density value, the higher the sensitivity, and the lower the density value, the lower the sensitivity.
[0094]
[Table 4]

[0095]
  Test results From the results in Table 4, containing a fluorescent brightening agent, pH 24When the developing replenisher was prepared using the above developing agent part, no turbidity or floating matter was generated, and the processing using this replenisher resulted in high sensitivity and good photographic properties. Among the present invention, when the pH of the developing agent part is 2 to 3, even better results were obtained when the processing solution automatic preparation apparatus B was used.
[0096]
Example-2
The following concentrated processing composition for color development was prepared, and a running test was performed in the following processing steps. Fuji color film EVE-BEAUTY PAPER manufactured by Fuji Photo Film Co., Ltd. was used as the photosensitive material sample. The running test was conducted until the total amount of the color developer replenisher used was twice the amount of the color developer tank.
The developing processor used was FPRP412 manufactured by Fuji Photo Film Co., Ltd., and the color developer replenisher was prepared in the same manner as in Example 1 by using an automatic replenisher (Mixer HV-3: 4.5 L size) manufactured by Rockwell HighTec. ) Was used.
[0097]

[0098]
・ Processing liquid formulation
Color developer: CP-45X P1X-LRP1 manufactured by Fuji Photo Film Co., Ltd.
Color developing replenisher: prepared using the following thick processing compositions A and B.

[0099]

[0100]
・ Preparation of color developer replenisher (indicated per liter of replenisher)
750 ml of water
Color development processing composition A agent 100 ml
Color development processing composition B agent 100ml
1000ml with water
pH 11.35
[0101]
Bleach fixing solution: CP-45X P2X-LR P2 manufactured by Fuji Photo Film Co., Ltd.
Bleach-fixing replenisher: Fuji Photo Film CP-45X P2X-LR
Running test results
Throughout the running test, the replenisher solution was free from turbidity and suspended matter, and good results with high photographic performance were obtained.
[0102]
【The invention's effect】
A silver halide photographic color developing composition of the present invention comprising a plurality of parts, particularly two parts, wherein the part containing the color developing agent is a part having a pH of 2 to 6 which also contains a fluorescent brightening agent Has the advantages of a liquid-concentrated composition that is free from defects such as precipitation, precipitation, and sensitivity reduction in preparation of a developing solution, and is reduced in volume, light weight, and easy to prepare. In particular, the developer preparation method using the concentrated processing composition for color development is particularly large in size because it does not cause clogging or precipitation in the preparation of a large lot of processing solution that tends to be non-uniform in stirring or in the preparation of a developer using an automatic preparation device. This is a preparation method suitable for a developing laboratory.
[Brief description of the drawings]
FIG. 1 is a schematic view of a treatment liquid preparation apparatus to which a treatment composition container of the present invention can be effectively applied. FIG. 1a is a sectional view of the apparatus, and FIG. 1b is a plan view thereof.
FIG. 2 is a schematic view of processing and related processes in a large-scale developer including a processing solution preparation apparatus to which the processing composition container of the present invention can be effectively applied.
[Explanation of symbols]
1 Mixing tank
2 Weighing tank
3 Stirring mechanism
4 On-off valve
5A, 5B, 5C Inlet
6A, 6B, 6C Level sensor
7A, 7B, 7C Liquid feeding pipe
8 Liquid inlet
9 Discharge port
10 containers
11 mouth
P liquid pump
S1, S2, S3, ----- Sn Treatment liquid
S1_A, S1_B, S1_C, ----- S1_XComposition treatment composition for preparation of treatment liquid S1
S2_AComposition treatment composition for preparation of treatment liquid S2
SN_XComposition treatment composition for the preparation of treatment liquid Sn
M1, M2, M3 ---- Mn 1 to n mixing tanks
R1, R2, R3 ---- Rn 1 to n mixing tanks
G-I, G-II, G-III --- G-X I, II-X automatic processors
OF1, OF2, OF3 Overflow storage tank

Claims (2)

Concentrated for color development for silver halide photography, characterized in that it is composed of a plurality of parts, and the part containing the color developing agent is a uniform liquid phase part having a pH of 2 to 4 which also contains a fluorescent brightening agent Treatment composition. A predetermined amount of each component part of the concentrated processing composition for color development, which is a homogeneous liquid phase part having a pH of 2 to 4 and comprising a plurality of parts and the part containing the color developing agent also containing a fluorescent brightening agent A method for preparing a silver halide photographic color developer comprising mixing and diluting in water to obtain a developer.

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