JP3690687B2 - Solid processing agent for silver halide photographic material and processing method using the processing agent - Google Patents

Description

【０１４６】
一般式［Ａ］において、Ｒ₁及びＲ₂は同時に水素原子ではないそれぞれアルキル基、アリール基、
【０１４７】
【化２】

【０１４８】
または水素原子を表すが、Ｒ₁及びＲ₂で表されるアルキル基は、同一でも異なってもよく、それぞれ炭素数１〜３のアルキル基が好ましい。更にこれらアルキル基はカルボン酸基、リン酸基、スルホン酸基、又は水酸基を有してもよい。
【０１４９】
Ｒ′はアルコキシ基、アルキル基又はアリール基を表す。Ｒ₁、Ｒ₂及びＲ′のアルキル基及びアリール基は置換基を有するものも含み、また、Ｒ₁及びＲ₂は結合して環を構成してもよく、例えばピペリジン、ピリジン、トリアジンやモルホリンの如き複素環を構成してもよい。
【０１５０】
【化３】

【０１５１】
式中、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃は水素原子、置換又は無置換の、アルキル基、アリール基、またはヘテロ環基を表し、Ｒ₁₄はヒドロキシ基、ヒドロキシアミノ基、置換又は無置換の、アルキル基、アリール基、ヘテロ環基、アルコキシ基、アリールオキシ基、カルバモイル基、アミノ基を表す。ヘテロ環基としては、５〜６員環であり、Ｃ、Ｈ、Ｏ、Ｎ、Ｓ及びハロゲン原子から構成され飽和でも不飽和でもよい。Ｒ₁₅は−CO−、−SO₂−または
【０１５２】
【化４】

【０１５３】
から選ばれる２価の基を表し、ｎは０又は１である。特にｎ＝０の時Ｒ₁₄はアルキル基、アリール基、ヘテロ環基から選ばれる基を表し、Ｒ₁₃とＲ₁₄は共同してヘテロ環基を形成してもよい。
【０１５４】
前記一般式［Ａ］で示されるヒドロキシルアミン系化合物の具体例は、米国特許3,287,125号、同33,293,034号及び同3,287,124号等に記載されているが、特に好ましい具体的例示化合物としては、特願平2-203169号明細書第36〜38頁記載の（Ａ−１）〜（Ａ−39）及び特開平3-33845号明細書第３〜６頁記載の（１）〜（53）及び特開平3-63646号明細書第５〜７頁記載の（１）〜（52）が挙げられる。
【０１５５】
次に前記一般式［Ｂ］で示される化合物の具体例は、特願平2-203169号明細書第40〜43頁記載の（Ｂ−１）〜（Ｂ−33）及び特開平3-33846号明細書第４〜６頁記載の（１）〜（56）が挙げられる。
【０１５６】
これら一般式［Ａ］又は一般式［Ｂ］で示される化合物は、通常遊離のアミン、塩酸塩、硫酸塩、p-トルエンスルホン酸塩、シュウ酸塩、リン酸塩、酢酸塩等の形で用いられる。
【０１５７】
本発明に用いられる発色現像剤及び黒白現像剤中には、保恒剤として亜硫酸塩を微量用いることができる。該亜硫酸塩としては、亜硫酸ナトリウム、亜硫酸カリウム、重亜硫酸ナトリウム、重亜硫酸カリウム等が挙げられる。
【０１５８】
本発明に用いられる発色現像剤及び黒白現像剤には、緩衝剤を用いることが必要で、緩衝剤としては、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（ホウ酸）、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)等を挙げることができる。
【０１５９】
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3,813,247号等に表されるチオエーテル系化合物、特開昭52-49829号及び同50-15554号に表される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号等に表される４級アンモニウム塩類、米国特許2,610,122号及び同4,119,462号記載のp-アミノフェノール類、米国特許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2,482,546号、同2,596,926号及び同3,582,346号等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3,128,183号、特公昭41-11431号、同42-23883号及び米国特許3,532,501号等に表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、ヒドロジン類、メソイオン型化合物、イオン型化合物、イミダゾール類、等を必要に応じて添加することができる。
【０１６０】
発色現像剤はベンジルアルコールを実質的に含有しないものが好ましい。実質的にとはカラー現像液１ｌに換算して2.0ml以下、更に好ましくは全く含有しないことである。実質的に含有しない方が連続処理時の写真特性の変動、特にステインの増加が小さく、より好ましい結果が得られる。
【０１６１】
カブリ防止等の目的で塩素イオン及び臭素イオンが処理槽のカラー現像液中に必要である。本発明においては現像速度、ステイン、最小濃度の変動の点で好ましくは塩素イオンとして1.0×10^-2〜1.5×10^-1モル／ｌ、より好ましくは４×10^-2〜１×10^-1モル／ｌ含有する。従って固体処理剤は処理槽のカラー現像液が上記の濃度範囲になる様調整することが好ましい。
【０１６２】
本発明において、処理槽中のカラー現像液は現像速度、最大濃度、感度及び最小濃度の点で臭素イオンを好ましくは3.0×10^-3〜1.0×10^-3モル／ｌ含有する。より好ましくは5.0×10^-3〜５×10^-4モル／ｌである。特に好ましくは１×10^-4〜３×10^-4モル／ｌである。これも塩素イオンと同様、固体処理剤中の臭素濃度を上記の範囲になる様調整することが好ましい。
【０１６３】
発色現像剤に直接添加される場合、塩素イオン供給物質として、塩化ナトリウム、塩化カリウム、塩化アンモニウム、塩化ニッケル、塩化マグネシウム、塩化マンガン、塩化カルシウム、塩化カドミウムが挙げられるが、そのうち好ましいものは塩化ナトリウム、塩化カリウムである。
【０１６４】
また、発色現像剤及び現像剤中に添加される蛍光増白剤の対塩の形態で供給されてもよい。臭素イオンの供給物質として、臭化ナトリウム、臭化カリウム、臭化アンモニウム、臭化リチウム、臭化カルシウム、臭化マグネシウム、臭化マンガン、臭化ニッケル、臭化カドミウム、臭化セリウム、臭化タリウムが挙げられるが、そのうち好ましいものは臭化カリウム、臭化ナトリウムである。
【０１６５】
本発明に用いられる発色現像剤及び現像剤には、必要に応じて、塩素イオン、臭素イオンに加えて任意のカブリ防止剤を添加できる。カブリ防止剤としては、沃化カリウムの如きアルカリ金属ハロゲン化物及び有機カブリ防止剤が使用できる。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挙げることができる。
【０１６６】
本発明に用いられる発色現像剤及び現像剤にはトリアジニルスチルベン系蛍光増白剤を含有させることが本発明の目的の効果の点から好ましい。かかる蛍光増白剤としては下記一般式［Ｅ］で示される化合物が好ましい。
【０１６７】
【化５】

【０１６８】
上式において、Ｘ₂，Ｘ₃，Ｙ₁及びＹ₂は各々水酸基、塩素又は臭素等のハロゲン原子、アルキル基、アリール基、
【０１６９】
【化６】

【０１７０】
または−OR₂₅を表す。ここでＲ₂₁及びＲ₂₂は各々水素原子、アルキル基（置換体を含む）、又はアリール基（置換体を含む）を、Ｒ₂₃及びＲ₂₄はアルキレン基（置換体を含む）を、Ｒ₂₅は水素原子、アルキル基（置換体を含む）又はアリール基（置換体を含む）を表し、Ｍはカチオンを表す。
【０１７１】
なお一般式［Ｅ］の各基あるいはそれらの置換基の詳細については、特願平2-240400号の63頁下から第８行〜第64頁下から第３行の記載と同義である。
【０１７２】
以下に一般式［Ｅ］で示される化合物の具体例を挙げる。
【０１７３】
【化７】

【０１７４】
【化８】

【０１７５】
【化９】

【０１７６】
【化１０】

【０１７７】
【化１１】

【０１７８】
【化１２】

【０１７９】
上記の化合物は公知の方法で合成することができる。上記例示化合物の中で特に好ましく用いられるのはＥ−４、Ｅ−24、Ｅ−34、Ｅ−35、Ｅ−36、Ｅ−37、Ｅ−41である。これらの化合物の添加量は発色現像液１ｌ当り0.2ｇ〜10ｇの範囲になる様に固体処理剤を調整することが好ましく、更に好ましくは0.4ｇ〜５ｇの範囲である。
【０１８０】
さらに、本発明に用いられる発色現像剤及び黒白現像剤組成物には、必要に応じて、メチルセロソルブ、メタノール、アセトン、ジメチルホルムアミド、β−シクロデキストリン、その他特公昭47-33378号、同44-9509号各公報記載の化合物を現像主薬の溶解度を上げるための有機溶剤として使用することができる。
【０１８１】
さらに、現像主薬とともに補助現像剤を使用することもできる。これらの補助現像剤としては、例えばメトール、フェニドン、N,N-ジエチル-p-アミノフェノール塩酸塩、N,N,N′,N′-テトラメチル-p-フェニレンジアミン塩酸塩等が知られている。
【０１８２】
さらにまた、その他ステイン防止剤、スラッジ防止剤、重層効果促進剤等各種添加剤を用いることができる。
【０１８３】
また発色現像剤及び黒白現像剤組成物には、特願平2-240400号公報第63頁下から第８行〜第64頁下から第３行に記載の下記一般式［Ｋ］で示されるキレート剤及びその例示化合物Ｋ−１〜Ｋ−22が添加されることが本発明の目的を効果的に達成する観点から好ましい。
【０１８４】
【化１３】

【０１８５】
これらキレート剤の中でも、とりわけ、Ｋ−２，Ｋ−９，Ｋ−12，Ｋ−13，Ｋ−17，Ｋ−19，が好ましく用いられ、とりわけ特に、Ｋ−２及びＫ−９が本発明の効果を良好に奏する。
【０１８６】
これらキレート剤の添加量は発色現像液及び黒白現像液１ｌ当たり0.1〜20ｇの範囲になる様に固体処理剤に添加することが好ましく、より好ましくは0.2〜８ｇの範囲である。
【０１８７】
さらにまた上記発色現像剤及び黒白現像剤にはアニオン、カチオン、両性、ノニオンの各界面活性剤を含有させることができる。
【０１８８】
また、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よい。
【０１８９】
本発明に係る漂白剤又は漂白定着剤に好ましく用いられる漂白主剤は下記一般式[Ｃ]で表わされる有機酸の第２鉄錯塩である。
【０１９０】
【化１４】

【０１９１】
［式中、Ａ₁〜Ａ₄はそれぞれ同一でも異ってもよく、−CH₂OH、−COOM又は−PO₃M₁M₂を表す。Ｍ、Ｍ₁、Ｍ₂はそれぞれ水素原子、アルカリ金属又はアンモニウムを表す。Ｘは炭素数３〜６の置換、未置換のアルキレン基を表す。］
以下に一般式［Ｃ］で示される化合物について詳述する。
【０１９２】
なお式中、Ａ₁〜Ａ₄は特願平1-260628号12頁上から15行〜15頁上から３行記載のＡ₁〜Ａ₄と同義であるので詳細な説明を省略する。
【０１９３】
一般式［Ｃ］で表わされる有機酸の第２鉄錯塩は漂白能力が高い為に固形化する際の使用量が少なくても済み、軽量化、小型化の固形化が計れるばかりでなく固形化処理剤の保存性が良くなるという効果があり、本発明に好ましく用いられる。
【０１９４】
以下に、前記一般式［Ｃ］で示される化合物の好ましい具体例を示す。
【０１９５】
【化１５】

【０１９６】
【化１６】

【０１９７】
これら（Ｃ−１）〜（Ｃ−12）の化合物の第２鉄錯塩としては、これらの第２鉄錯塩のナトリウム塩、カリウム塩又はアンモニウム塩を任意に用いることができる。本発明の目的の効果及び溶解度の点からは、これらの第２鉄錯塩のアンモニウム塩が好ましく用いられる。
【０１９８】
前記化合物例の中で、本発明において特に好ましく用いられるものは、（Ｃ−１）、（Ｃ−３）、（Ｃ−４）、（Ｃ−５）、（Ｃ−９）であり、とりわけ特に好ましいものは（Ｃ−１）である。
【０１９９】
本発明において漂白剤又は漂白定着剤には、漂白主剤として上記一般式［Ｃ］で示される化合物の鉄錯塩以外に下記化合物の第２鉄錯塩等を用いることができる。
【０２００】
〔Ａ′−１〕エチレンジアミン四酢酸
〔Ａ′−２〕トランス-1,2-シクロヘキサンジアミン四酢酸
〔Ａ′−３〕ジヒドロキシエチルグリシン酸
〔Ａ′−４〕エチレンジアミンテトラキスメチレンホスホン酸
〔Ａ′−５〕ニトリロトリスメチレンホスホン酸
〔Ａ′−６〕ジエチレントリアミンペンタキスメチレンホスホン酸
〔Ａ′−７〕ジエチレントリアミン五酢酸
〔Ａ′−８〕エチレンジアミンジオルトヒドロキシフェニル酢酸
〔Ａ′−９〕ヒドロキシエチルエチレンジアミン三酢酸
〔Ａ′−10〕エチレンジアミンジプロピオン酸
〔Ａ′−11〕エチレンジアミンジ酢酸
〔Ａ′−12〕ヒドロキシエチルイミノジ酢酸
〔Ａ′−13〕ニトリロトリ酢酸
〔Ａ′−14〕ニトリロ三プロピオン酸
〔Ａ′−15〕トリエチレンテトラミン六酢酸
〔Ａ′−16〕エチレンジアミン四プロピオン酸
〔Ａ′−17〕β-アラニンジ酢酸
前記有機酸第２鉄錯塩の添加量は漂白液又は漂白定着液１ｌ当り0.01モル〜2.0モルの範囲で含有することが好ましく、より好ましくは0.05〜1.5モル／ｌの範囲である。従って、固体処理剤は処理槽中の漂白液又は漂白定着液の有機酸第２鉄錯塩の濃度が上記範囲になる様に調整することが好ましい。
【０２０１】
漂白剤、漂白定着剤及び定着剤には、特開昭64-295258号明細書に記載のイミダゾール及びその誘導体又は同明細書記載の一般式［Ｉ］〜［IX］で示される化合物及びこれらの例示化合物の少なくとも一種を含有することにより迅速性に対して効果を奏しうる。
【０２０２】
上記の促進剤の他、特開昭62-123459号明細書の第51頁から第115頁に記載の例示化合物及び特開昭63-17445号明細書の第22頁から第25頁に記載の例示化合物、特開昭53-95630号、同53-28426号公報記載の化合物等も同様に用いることができる。
【０２０３】
漂白剤又は漂白定着剤には、上記以外に臭化アンモニウム、臭化カリウム、臭化ナトリウムの如きハロゲン化物、各種の蛍光増白剤、消泡剤あるいは界面活性剤を含有せしめることもできる。
【０２０４】
本発明における定着剤又は漂白定着剤に用いられる定着主剤としては、チオシアン酸塩、チオ硫酸塩が好ましく用いられる。チオシアン酸塩の含有量は少なくとも定着液又は漂白定着液１ｌ当り0.1モル／ｌ以上が好ましく、カラーネガフィルムを処理する場合、より好ましくは0.5モル／ｌ以上であり、特に好ましくは1.0モル／ｌ以上である。またチオ硫酸塩の含有量は少なくとも0.2モル／ｌ以上が好ましく、カラーネガフィルムを処理する場合、より好ましくは0.5モル／ｌ以上である。また本発明においては、チオシアン酸塩とチオ硫酸塩を併用することにより更に効果的に本発明の目的を達成できる。
【０２０５】
本発明に用いられる定着剤又は漂白定着剤には、これら定着主剤の他に各種の塩から成るpＨ緩衝剤を単独或いは２種以上含むことができる。さらにアルカリハライドまたはアンモニウムハライド、例えば臭化カリウム、臭化ナトリウム、塩化ナトリウム、臭化アンモニウム等の再ハロゲン化剤を多量に含有させることが望ましい。またアルキルアミン類、ポリエチレンオキサイド類等の通常定着剤又は漂白定着剤に添加することが知られている化合物を適宜添加することができる。
【０２０６】
定着剤または漂白定着剤には、特開昭64-295258号明細書第56頁に記載の下記一般式［ＦＡ］で示される化合物及びこの例示化合物を添加するのが好ましく、本発明の効果をより良好に奏するばかりか、少量の感光材料を長期間にわたって処理する際に定着能を有する処理液中に発生するスラッジも極めて少ないという別なる効果が得られる。
【０２０７】
【化１７】

【０２０８】
同明細書記載の一般式［ＦＡ］で示される化合物は米国特許3,335,161号明細書及び米国特許3,260,718号明細書に記載されている如き一般的な方法で合成できる。これら、前記一般式［ＦＡ］で示される化合物はそれぞれ単独で用いてもよく、また２種以上組合せて用いてもよい。
【０２０９】
また、これら一般式［ＦＡ］で示される化合物の添加量は定着液又は漂白定着液１ｌ当り0.1ｇ〜200ｇの範囲で好結果が得られる。
【０２１０】
本発明において安定液には第２鉄イオンに対するキレート安定度定数が８以上であるキレート剤を含有することが好ましい。ここにキレート安定度定数とは、L.G.Sillen・A.E.Martell著、”Stability Constants of Metal-ion Complexes”，The Chemical Society，London（1964）。S.Chaberek・A.E.Martell著、”Organic Sequestering Agents”，Wiley（1959）等により一般に知られた定数を意味する。
【０２１１】
第２鉄イオンに対するキレート安定度定数が８以上であるキレート剤としては特願平2-234776号、同1-324507号等に記載のものが挙げられる。
【０２１２】
上記キレート剤の使用量は安定液１ｌ当り0.01〜50ｇが好ましく、より好ましくは0.05〜20ｇの範囲で良好な結果が得られる。
【０２１３】
また安定液に添加する好ましい化合物としては、アンモニウム化合物が挙げられる。これらは各種の無機化合物のアンモニウム塩によって供給される。アンモニウム化合物の添加量は安定液１ｌ当り0.001モル〜1.0モルの範囲が好ましく、より好ましくは0.002〜2.0モルの範囲である。
【０２１４】
さらに安定剤には亜硫酸塩を含有させることが好ましい。
【０２１５】
さらにまた安定液には前記キレート剤と併用して金属塩を含有することが好ましい。かかる金属塩としては、Ba，Ca，Ce，Co，In，La，Mn，Ni，Bi，Pb，Sn，Zn，Ti，Zr，Mg，Al又はSrの金属塩があり、ハロゲン化物、水酸化物、硫酸塩、炭酸塩、リン酸塩、酢酸塩等の無機塩又は水溶性キレート剤として供給できる。使用量としては安定液１ｌ当り１×10^-4〜１×10^-1モルの範囲が好ましく、より好ましくは４×10^-4〜２×10^-2モルの範囲である。
【０２１６】
本発明を適用できる自動現像機（以下、単に自現機ともいう）の一例を図面に基づいて説明する。図１は、自現機Ａと写真焼付機Ｂとを一体的に構成したプリンタープロセッサーの概略図である。
【０２１７】
図１において写真焼付機Ｂの左下部には、未露光のハロゲン化銀写真感光材料である印画紙をロール状に収納したマガジンＭがセットされる。マガジンから引き出された印画紙は、送りローラＲ及びカッター部Ｃを介して所定のサイズに切断され、シート状印画紙となる。このシート状印画紙は、ベルト搬送手段Ｂ₁によって搬送され、露光部Ｅにおいて原画Ｏの画像を露光される。露光されたシート状印画紙はさらに複数対の送りローラＲにより搬送され、自現機Ａ内に導入される。自現機Ａでは、シート状印画紙は、処理槽である夫々発色現像槽１Ａ、漂白定着槽１Ｂ、安定槽１Ｃ，１Ｄ，１Ｅ内（実質的に３槽構成の）をローラ搬送手段（参照記号ナシ）により順次搬送され、それぞれ、発色現像処理、漂白定着処理、安定化処理がなされる。前記各処理がなされたシート状印画紙は、乾燥部35において乾燥されて機外に排出される。
【０２１８】
なお、図中の一点鎖線は、ハロゲン化銀写真感光材料の搬送経路を示す。また、実施例においては、感光材料はカットされた状態で自現機Ａ内に導かれるものであるが、帯状で自現機内に導かれるものであってもよい。その場合、自現機Ａと写真焼付機Ｂとの間に、感光材料を一時的に滞留させるアキュムレータを設けると処理効率が上がる。また、本願発明に係る自現機は、写真焼付機Ｂと一体的に構成しても、自現機単体だけでもよいことは言うまでもない。また、本発明に係る自現機によって処理されるハロゲン化銀写真感光材料は、露光済の印画紙に限られるものでははなく、露光済のネガフィルム等でもよいことは言うもでもない。また、本発明の説明として、発色現像槽、漂白定着槽、安定槽を有する実質的に３槽構成の自現機について行うが、これに限られるものではなく、発色現像槽、漂白槽、定着槽、安定槽を有する実質的に４槽構成の自現機であっても本発明は適用できるものである。
【０２１９】
図２は、図１の自現機ＡのＩ−Ｉ断面における処理槽である発色現像槽１Ａの概略図である。なお、漂白定着槽１Ｂ、安定槽１Ｃ，１Ｄ，１Ｅにおいては、発色現像槽１Ａと同じ構成となるので、以下、処理槽１として説明する場合は、発色現像槽１Ａ、漂白定着槽１Ｂ、安定槽１Ｃ，１Ｄ，１Ｅいずれも指すここととする。なお、図には、構成をわかりやすくするために、感光材料を搬送する搬送手段等は省略してある。また、本例においては、固体処理剤として錠剤13を用いた場合について説明する。
【０２２０】
処理槽１は、感光材料を処理する処理部２と、該処理部を形成する仕切壁の外側に一体的に設けた錠剤13を供給する固体処理剤投入部11とを有する。これら処理部２と固体処理剤投入部11とは連通窓が形成された仕切壁12により仕切られており、処理液は流通できるようになっている。そして投入部11には処理剤を受容する区分14を設けたので、固体のまま処理部２に移動することがない。
【０２２１】
筒状のフィルター３は、固体処理剤投入部11の下方に交換可能に設けられ、処理液中の不溶物、例えば紙くず等を除去する機能を果たす。このフィルター３の中は、固体処理剤投入部11の下方壁を貫通して設けられた循環パイプ４を介して循環ポンプ５（循環手段）の吸引側に連通している。
【０２２２】
循環系は、液の循環通路を形成する循環パイプ４、循環ポンプ５、および、処理槽１等で構成されていることになる。前記循環ポンプ５の吐出側に連通した循環パイプ４の他端は処理部２の下方壁を貫通し、該処理部２に連通している。このような構成により、循環ポンプ５が作動すると処理液は固体処理剤投入部11から吸い込まれ、処理部２に吐出されて処理液は処理部２内の処理液と混じり合い、再び固体処理剤投入部11へと入る循環を繰り返すことになる。この循環流の流量は、１分間当たりタンク容量に対して0.1（回転＝循環量／タンク容量）以上の流量であることが好ましく、より好ましくは、0.5〜2.0回転である。また、処理液の循環方向は、図２に示した方向に限られる必要はなく、逆方向であってもよい。
【０２２３】
排（廃）液管６は、処理部２内の処理液をオーバーフローさせるためのものであり、液面レベルを一定に保つとともに、他の処理槽から感光材料に付着して持ち込まれる成分や、感光材料から浸み出す成分が貯留し、増加することを防ぐのに役立つ。
【０２２４】
棒状のヒータ７は、固体処理剤投入部11の上方壁を貫通して固体処理剤投入部11内の処理液中に浸漬するよう配設されている。このヒータ７は、処理槽１内の処理液を加温するものであり、換言すると処理槽１内の処理液を処理に適した温度範囲（例えば20〜55℃）に保持する温度調整手段である。
【０２２５】
処理量情報検出手段８は、自現機の入口に設けられ、処理される感光材料の処理量を検出するために用いられる。この処理量情報検出手段８は、左右方向に複数の検出部材を配してなり、感光材料の幅を検出するとともに、検出されている時間をカウントするための要素として機能する。感光材料の搬送速度は機械的に予め設定されているので、幅情報と時間情報とから感光材料の処理面積が算出できる。なお、この処理量情報検出手段は、赤外線センサー、マイクロスイッチ、超音波センサー等の感光材料の幅および搬送時間を検出できるものであればよい。また、間接的に感光材料の処理面積が検出できるもの、例えば図１のようなプリンタープロセッサーの場合、焼付を行った感光材料の量、あるいは、予め決まっている面積を有する感光材料の処理数を検出するものでもよい。さらに、検出するタイミングは、本例では処理される前であるが、処理した後、あるいは処理液中に浸漬されている間でも良い（このような場合は、処理量情報検知手段８を設ける位置を処理後に検出できる位置や処理中に検出できる位置に適宜変更することによりできる）。さらに、検出される情報として、上述の説明では、感光材料の処理面積について述べたが、これに限られるものではなく、処理される、処理された、あるいは、処理中の感光材料の処理量に比例した値であればよく、処理槽に収容された処理液の濃度あるいは濃度変化等であってもよい。また、処理量情報検出手段８は、各処理槽１Ａ，１Ｂ，１Ｃ，１Ｄ，１Ｅ毎に設ける必要はなく、１台の自現機に対して１つ設けることが好ましい。
【０２２６】
収納手段であるカートリッジ15に収納された固体処理剤を処理槽に投入する処理剤供給手段17は、濾過部（区分）14の上方に配設され、固体処理剤である錠剤13を封入してあるカートリッジ15と錠剤13を一個又は複数個押し出す構成の押出部材10とを有している。この処理剤供給手段17は、後述する処理剤供給制御手段９によって制御され、処理剤供給制御手段９から発せられる供給信号と連動して、待機中であった錠剤13を押出部材10で押し出し、錠剤13を固体処理剤投入部11内の濾過部（区分）14に供給する。なお、本願発明では、固体処理剤13を固体処理剤投入（受容）部11内の濾過部（区分）14に供給したが、供給される場所は処理槽１内であればどこに供給されてもよく、即ち、本願発明では処理液を用いて固体処理剤を溶解できればよく、感光材料の処理量情報に応じた成分が確実に投入され、処理槽１内の処理液の処理特性を一定に保つことが必要なのであるが、より好ましくは、処理液の循環経路内に固体処理剤が供給されることがよい。また、この処理剤供給手段17は、自現機の処理槽内や外気の湿気、処理液の飛散したものが、処理槽に供給される前の固体処理剤と接触しないようにされていることが好ましい。
【０２２７】
濾過部（区分）14は、固体処理剤投入部11内の処理液に浸漬され、処理剤供給手段17によって供給された錠剤13による不溶成分、例えば錠剤13中に混入していた溶解しない成分、錠剤13が崩壊してできる錠剤13の塊などのみならず固体処理剤由来のものが感光材料に付着すると出来上がった画像に傷をつけてしまったり、付着した箇所の処理不足等の原因となるものを、除去するものである。この濾過部（区分）14は樹脂で加工されている。なお、濾過部（区分）14は固体処理剤投入部11内に設けることは必須ではなく、処理剤供給手段17によって供給される錠剤13が図１に示す感光材料の搬送経路、あるいは、処理部２内の処理液に投入されるようにすればよいものである。
【０２２８】
処理剤供給制御手段９は、処理剤供給手段17を制御するものであり、処理量情報検出手段８によって検出された感光材料の処理量情報（本実施例では処理面積）が所定の一定値に達すると処理剤供給手段17に処理剤供給信号を発するものである。なお、処理剤供給制御手段９は、処理量情報に応じて必要な処理剤量を固形処理剤投入部11に供給するよう処理剤供給手段17を制御すればよい。
【０２２９】
次に、図２に基づいて、本願発明の動作を説明する。露光済の感光材料は、自現機Ａの入口において処理量情報検出手段８により処理量情報が検出される。処理剤供給制御手段９は、処理量情報検出手段８により検出された処理量情報に応じて、処理される感光材料の面積の累積が所定の面積に達すると、処理剤供給手段17に供給信号を発する。供給信号を受けた処理剤供給手段17は、押出部材10で錠剤13を押し出し、錠剤13を固体処理剤投入部11内の濾過部（区分）14に供給する。供給された錠剤13は、固体処理剤投入部11内の処理液によって溶解するが、循環手段によって固体処理剤投入部11→循環ポンプ５→処理部２→連通窓→固体処理剤投入部11と循環している処理液により溶解が促進される。一方、検出された感光材料は、発色現像槽１Ａ、漂白定着槽１Ｂ、安定槽１Ｃ，１Ｄ，１Ｅ内をローラ搬送手段により順次搬送される（図１の自現機Ａ参照）。なお、夫々処理槽である発色現像槽１Ａ、漂白定着槽１Ｂ、安定槽１Ｃ，１Ｄ，１Ｅそれぞれに、処理剤供給手段17を備え、それぞれ同時に供給してもよい。また、それぞれの供給手段により供給されるタイミングは各々別々であってもよく、さらに、処理剤供給制御手段９により処理剤供給手段が制御されるための所定の面積は、各処理槽１Ａ，１Ｂ，１Ｃ，１Ｄ，１Ｅ同じであってもよいが、それぞれ異なっていてもよいことはいうまでもない。
【０２３０】
本例に限らず以下に説明する例において、漂白定着槽１Ｂ、安定槽１Ｃ，１Ｄ，１Ｅにおいては、発色現像槽１Ａと同じ構成となるので、以下で処理槽１として説明する場合は、発色現像槽１Ａ、漂白定着槽１Ｂ、安定槽１Ｃ，１Ｄ，１Ｅいずれも指すこととし、図中の図番で、前述した図２と同じ機能をもつものは同じ番号とするので、ここではその説明を省略し、さらに、構成をわかりやすくするために、感光材料を搬送する搬送手段等は省略してある。なお本例において濾過手段を好しい例として記載したが、本発明においては濾過手段がなくても本発明の効果を十分奏することができる。
【０２３１】
以上説明したように、本発明によると従来必要であった補充タンクが不要となりそのためのスペースを確保する必要がないため自現機がコンパクトになり、また、固体処理剤を処理槽に供給するので調液作業が不要となり、調液時の液飛散や人体・衣服・周辺機器への付着・汚染がなく、取扱いが簡単であり、さらに、処理液への補充精度が高まり補充される処理成分の劣化がなく安定した処理特性を持つ、という優れた効果を奏する。
【０２３２】
次に、本発明の他の例として、図３は、図１の自現機ＡのＩ−Ｉ断面における発色現像槽１Ａの概略図で、補充水供給手段を追加した処理剤投入部と処理剤供給手段との断面図である。図４は、図１の自現機Ａを上面から示した概略平面図である（但し、説明上補水手段についてその経路を記載してある）。図５は、本例に係る制御に関するブロック図である。図６は制御手段に予めプログラムされた蒸発補水設定手段23を加えたブロック図である。なお、図３および図４中には、補充水を貯留する補水タンク43を図示している。また、本例においては、固形処理剤13として錠剤を用いた場合について説明する。
【０２３３】
まず、図３および図４において、図２と異なる部分について説明する。
【０２３４】
補充水供給手段42は、補充水を貯える補水タンク43から処理剤投入部11に補充水（補水）を補給する手段であって、ポンプ、温調機等からなる温水補給装置32、電磁弁33、補水管36を有する。この補充水供給手段42は、写真材料によって持ち出された水分とタンク表面から蒸発した水分を補いながら、反応によって溶出する累積抑制成分を薄めるためのものである。また、各処理槽１Ａ，１Ｂ，１Ｃ，１Ｄ，１Ｅ毎に補水タンクや補水ポンプを設けてもよいが、補給される補充水はいずれの槽においても同じ補充水を用いて、１つの補水タンクにすると自現機がコンパクトになり、さらに好ましくは、補水タンクと補水ポンプを自現機に１つだけ設け、補水する経路（パイプ41等）に電磁弁を設けて各処理槽に必要なときに必要量が補給されるようにする、あるいは、補水用のパイプの径の太さを調整して補給量を加減する、ことにより、補水タンク43と補水ポンプを自現機に１つだけ設けることができ、さらにコンパクトになる。なお、夫々処理槽である安定槽１Ｃ，１Ｄに関しては、それぞれ安定槽１Ｄ，１Ｅからオーバーフローした安定液を供給することにより、補充水供給手段を省くことも可能となる。また、補水タンクの補充水は、温調されていることが好ましい。
【０２３５】
補給される水は、井戸水、水道水等の一般的な水ばかりでなく、イソチアゾリン系、塩素放出化合物等の防黴剤や若干の亜硫酸塩キレート剤等を含有するものアンモニアや無機塩等を含有するもの等、写真性能に影響がないものであれば公知の化合物、方法を用いることができる。
【０２３６】
この補充水制御手段は、設置場所の環境温度・湿度（相対湿度）により予じめプログラムされた蒸発補水設定手段23（図５，６）により補充水供給手段42を制御するおよび／または処理量情報検出手段８により検出された処理量情報等に応じて補充水供給手段42を制御する制御手段である。なお、この補充水供給制御手段は、処理量情報検出手段８により検出された処理量情報に応じることに限られず、処理剤供給手段17により処理剤が供給されたという情報に応じて制御してもよい。
【０２３７】
なお、図３と図２とで上記以外で異なる部分に関しては、（その機能等は図２の場合と同じであり）それについて説明する。
【０２３８】
ヒータ７は、処理部２の底部に配置されており、処理部２内の処理液を加温するものであり、換言すると処理部２および固体処理剤投入部11内の処理液を処理に適した温度範囲（例えば20〜55℃）に保持する温度制御機能を行うものである。
【０２３９】
循環手段として、循環パイプ４および循環ポンプ５が図２と同様に設けられているが、図２と異なることは、処理液が循環する方向が逆である、即ち、処理液は処理部２→循環ポンプ５→固体処理剤投入部11→連通窓→処理部２と循環する。
【０２４０】
処理剤供給手段17は、カートリッジ15内に封入された固体処理剤である錠剤13を押し爪18によって固体処理剤投入部11内の濾過部（区分）14に供給するものである。図２と異なる部分は、カム19を軸１回転停止機構により作動し、押し爪18を作動させ、待機中であった錠剤13は処理槽１に供給され、次の錠剤13は、錠剤押しバネ21によって上方から下方へとバネ付勢されているので、速やかに待機状態となる。この際、処理剤供給手段17は、横置きまたは下方からの押し上げ方式でもよく、要は処理槽１に固体処理剤を投入できる手段であればよい。
【０２４１】
次に、図１、図３、図４および図５に基づいて、本願発明の動作を説明する。露光済の感光材料は、自現機Ａの入口において処理量情報検出手段８により処理量情報が検出される。処理剤供給制御手段９は、処理量情報検出手段８により検出された処理量情報に応じて、処理される感光材料の面積の累積が所定の面積に達すると、処理剤供給手段17に供給信号を発する。供給信号を受けた処理剤供給手段17は、押出部材10で錠剤13を押し出し、錠剤13を固体処理剤投入部11内の濾過部14に供給する。供給された錠剤13は、固体処理剤投入部11内の処理液によって溶解するが、循環手段によって処理部２→循環ポンプ５→固体処理剤投入部１１→連通窓→処理部２と循環している処理液により溶解が促進される。一方、補充水供給制御手段は、処理量情報検出手段８により検出された処理量情報に応じて、処理される感光材料の面積の累積が所定の面積に達すると、補充水供給手段42（温水補給装置32および電磁弁33）に補水信号を発する。補水信号を受けた補充水供給手段42は、温水補給装置32および電磁弁33を制御して、補水タンク43に貯えられた補充水を各処理槽、あるいは、必要になった処理槽に所定量又は必要量の補水を行う。この場合の所定の面積は、処理剤供給制御手段９におけるそれと同じ量であるが、これに限られず、それぞれ異なる所定の面積であってもよい。一方、検出された感光材料は、夫々処理槽である発色現像槽１Ａ、漂白定着槽１Ｂ、安定槽１Ｃ，１Ｄ，１Ｅ内をローラ搬送手段により順次搬送される。
【０２４２】
次に本発明の固体処理剤の供給装置について説明する。図７（Ａ）は粉状処理剤供給装置の断面図を示し、図７（Ｂ）はパッケージの斜視図である。供給装置50は粉状処理剤を収納するホッパーまたはパッケージ51と粉状処理剤を計量する計量孔53と定量投入するための回転式ドラム52よりなる。この回転式ドラム52は計量孔53と排出部56の位置をズラすことで防湿機能をもたせている。パッケージ51の封を切り供給装置の上部に装填した。粉末ケミカルは計量孔53に一定量計量され感光材料の処理量検出手段の指令でドラム52が回転し排出部56と連通状態となったとき停止し排出部56を通過し、定量の粉状ケミカルが自動現像機恒温部（フィルター槽）に供給される。供給終了後、ドラム52が回転し計量孔53と供給部57が連通したときドラム52は停止し粉状ケミカルの計量が開始される。
【０２４３】
図８は粉状処理剤の他の供給装置の斜視図である。
【０２４４】
供給装置60は粉状ケミカル収納部63が複数に分離されており従来の濃縮キットと同様にパート毎に分け収納するように工夫されている。又収納部における粉状ケミカルの保存性向上のために除湿装置65がある。
【０２４５】
感光材料の処理情報により回転体67は、テーブル66に受けた粉状処理剤を排出部68へ成分毎に定量移送し供給する。
【０２４６】
図９は他の粉状処理剤の供給装置の断面図である。
【０２４７】
供給装置70は粉状処理剤をホッパー71に入れ感光材料の処理量に応じピストン75が水平方向（右へ）に移動し計量孔72に定量の粉状剤が入りピストン75が水平反対方向（左へ）に移動し排出部74により定量粉状剤を恒温槽（フィルター槽）へ供給する。
【０２４８】
図10は粉状処理剤の更に他の供給装置を示す断面図である。
【０２４９】
供給装置80は粉状処理剤85入りパッケージ81を装着（装填）しローラ83により自動的に開封する機能を有しスクリュー82の回転数を制御することで粉状ケミカルを排出部84により供給する装置である。
【０２５０】
自動的にパッケージを開封する機能を有しているため開封及び装着時に微粉末が舞うことなく良好である。
【０２５１】
図11はPTP(Pressure Through Package）包装された固体処理剤の投入装置に関し、（Ａ）は処理剤供給装置の断面図、（Ｂ）は包装破断手段の斜視図、（Ｃ）は包装破断手段の斜視図、（Ｄ）はPTP包装された固体処理剤の積載状態を示す断面図。
【０２５２】
処理剤収納容器にはPTP包装された固体処理剤が収納されており、個々に収納容器に収納しても良いし、あらかじめ固体処理剤が収納されたカートリッジタイプであっても良い。PTP包装は公知の材質を用いることができ、固体処理剤は錠剤の形で包装されていることが好ましい。
【０２５３】
PTP包装された固体処理剤は収納容器の下方から供給され、感光材料が一定量処理されると処理量検知手段の情報が処理剤供給制御手段に送られモータによりPTP包装された固形処理剤をくさび形の固定板に押し出しておしつぶすことによってPTP包装の下部（主にアルミ使用）をはがし、投入口より固体処理剤が処理槽に投入される。投入後の空になったPTP包装は更に押し出されることによって廃棄口より廃棄される。押しつぶす手段としてはくさびを用いる以外にローラーを用いる方法もあり、任意に迸択できる。
【０２５４】
図12は一括包装した錠剤（予め分割秤量）用パーツフィーダ方式供給装置の１例を示したものである。
【０２５５】
一括包装した錠剤ケミカルの包材Ａ又はＢを開封しホッパー101に入れた。その際微粉末など発生しないし、ケーキングもなく取り扱い性良好であった。残量検出手段109の信号で撹拌機106が回転し、錠剤105が錠剤整列部110に整列する。感光材料の処理量に応じて、処理剤供給制御手段103が働き、回転テーブル107が錠剤を搬送し排出部108より投入部へ供給する。回転テーブル107は一回転し、回転テーブル制御手段の指示で停止する（一回の指示で数回錠剤を供給も可能）。錠剤が回転テーブル107の穴に入る。
【０２５６】
包装材料費用が安価で取り扱い性が良く、精度よく投入でき、特に錠剤整列部110があることにより回転テーブルによる空供給がなく非常に効率が良いという利点がある。ポリ容器の減少で環境適性に好ましい。又微粉末がでないことより供給装置内部が汚れずメンテナンスフリーである。
【０２５７】
図13は一括包装した錠剤（予め分割秤量）用パーツフィーダ方式供給装置120の１例を示したものである。
【０２５８】
一括包装した錠剤ケミカルの包材（Ａ）または（Ｂ）を開封しホッパー133に入れた。その際微粉末など発生しないし、ケーキングもなく取り扱い性良好であった。残量検出手段125の信号で可動部材124が回転し、錠剤ケミカルが錠剤整列部129に整列する。一定量整列すると可動部材124は停止する。この際スィーパ123は錠剤が可動部124のポケット122に入り錠剤整列部129に整列するのに非常に効果がある。
【０２５９】
感光材料の処理量に応じて処理剤供給手段126が働き第１のシャッター131が回転し錠剤ケミカルが下に落ちる。次に第１のシャッター131が逆回転し錠剤１ケをシャッター131と132の間に挾む。シャッター132が回転し錠剤ケミカルは排出部128を通過し投入部へ供給する。次にシャッター132が逆回転しシャッター131がしまる。
【０２６０】
包装材料が安価で取り扱い性が良く、精度良く投入でき特に錠剤整列部129があることにより空供給がなく良い。ポリ容器の減少で環境適性に好ましい。又微粉末がでないことより供給装置内部が汚れずメンテフリーである。
【０２６１】
図14は固体処理剤供給装置140の１例を示す斜視図であり、包装体に入った固体処理剤の包装体をはがすことによって固形処理剤を処理槽に投入するものである。
【０２６２】
固体処理剤を四方シールで包装した収納包材の先端部をローラ141を介して固定手段である巻き取り軸142にセットし、感光材料が処理されると処理量情報検出手段によって検知し、ある一定量に達した時に処理剤供給制御手段により信号が送られ処理剤供給手段でもある巻き取り軸142のモーターを動かすことで、固体処理剤の入った包装体をある一定の長さだけ移動させ、必要数の固体処理剤を投入する。包装体を移動させる方法は包装体に予め設けられたノッチを検出する方法、印刷柄の検出、包装体の処理剤検出等どんな方法でも良いが要は必要数の固体処理剤を精度よく検出し、ローラ141や巻き取り軸142によって移動させるものである。ローラ141は包装体を固定する、位置決めするなどの目的で設置しており、２つの巻き取り軸により剥離され、固体処理剤が投入される。
【０２６３】
この様な方式の場合、固体処理剤は顆粒、丸薬、錠剤、粉剤でも良いが好ましくは錠剤の方がシールに余り付着せず従って精度よく投入でき、汚れも発生しにくいという利点がある。巻き取り終了後は巻き取り軸から直接取ってもよく、又巻き戻して包装体がカートリッジごと廃棄することもできる。
【０２６４】
図15は本発明の好ましい実施態様の供給装置の１例を示し、（Ａ）は平面図、（Ｂ）は斜視図、（Ｃ）は各種包装体の平面図である。
【０２６５】
処理剤151は四方シールされた包装体152に図15（Ｃ）の様な形で包装されている。
【０２６６】
図15（Ｃ）の包装形態は本発明の１例である。包装に用いられる素材は一般に使用されている高分子樹脂製の包装、アルミ、又は複合材料を用いて良いが、要は防湿性が良く、酸素透過性が低い素材であれば良い。
【０２６７】
四方シールされた処理剤151は筒153を介してはがされ、処理剤151は投入口154を介して投入部155に投入される。ここでは筒153及び巻き取り軸156が処理剤供給手段として作用する。包装体152は巻き取り軸156で巻き取られる構造になっており、巻き取りの制御は感光材料処理量検知手段より信号を受けた処理剤供給手段により制御される様になっている。巻き取る際はつまみを開放状態にし、包装体151の先端部を筒を介して処理剤収納包材の固定手段である巻き取り軸156にセットし、つまみ157をひねることでクランパ158により固定され、巻き取られる。
【０２６８】
図16は固形処理剤161をスティック包装した場合の供給装置160の１例を示したものであり、（Ａ）は側断面図、（Ｂ）は正面断面図である。
【０２６９】
スティック包装した固体処理剤161を収納手段である収容容器162に入れる。
【０２７０】
収容容器162に入ったスティック包装固体処理剤161はブリッジ防止ローラ163及びターレットへの供給を兼ねたローラによりターレット164に送られる。ターレット164に送られたスティック包装固体処理剤161はクランパ165により両端を固定され、その後回転運動によりカッター部に送られ、スティック包装の中心部をカッター166により切りこみを入れ（又は切断）、更に回転により二ツ折り板167に送られて、スティック包装固体処理剤161を折り曲げ、回転カッター166によって切り込みを入れた部分からスティック包装内に充填された固体処理剤161をシュート168に投入する。投入後更に回転によりスクラップ落下バー169まで送られ、クランプ開閉用カム170によりクランパ165が解除され。スクラップ包装のスクラップ171が回収シュート172に廃棄される。
【０２７１】
図17は本発明の１実施態様を示す断面図及び斜視図である。
【０２７２】
処理部181と処理槽の一部を構成する恒温槽182内の投入部185は連通しており、処理槽下部から循環ポンプ183により強制的に液循環させ、フィルター部に吐出され、投入部185を通って処理部181に入るようになっている。
【０２７３】
感光材料が処理されると処理量検出手段192により処理量が検出され、ある一定の処理量に達すると処理量供給制御を介してモータＭ２を駆動させあらかじめ秤量された錠剤が恒温槽182内の投入部185に供給される様になっている。
【０２７４】
錠剤は収容容器187に直接投入され、投入後、整列量制御手段186の信号によりモータＭ１により整列手段188が駆動し、錠剤を整列させ、整列部189に供給される。整列部189に供給された錠剤は処理量供給制御手段190からの信号を受けてモータＭ２が駆動すると供給手段の回転運動により錠剤が投入部の上部まで運ばれ、投入部185に投入される。その際処理剤供給手段191は恒温槽182と実質的に遮断されていることが錠剤の防湿性の上から好ましい実施態様である。
【０２７５】
又収容容器187に投入する際の錠剤は図17（Ａ），（Ｂ）に示す様な容器に入ったものを破いて投入容器187に入れる。図17（Ａ），（Ｂ）に示す容器は紙、高分子性樹脂アルミ等公知の素材を使用することができるが好ましくは防湿性が良く、しかも酸素透過性が低い素材を用いることである。
【０２７６】
図18はブリスター個包装された固形処理剤の供給装置200の１例を示した断面図である。
【０２７７】
固体処理剤の入った個包装202を収納部203に装填する。
【０２７８】
感光材料の処理量に応じて円盤201が180°回転し、その後針205が個包装202を貫通し個包装202内の排出部204を通過し投入部へ供給する。空の個包装202は廃棄口より廃棄される。
【０２７９】
固体処理剤は粉体でも顆粒でも良いが粉体は容器に付着するため顆粒の方が好ましい。
【０２８０】
取り扱い性が良く、供給装置200の微粉末汚れがなくメンテナンスフリーである。
【０２８１】
図19は、本発明の１例を示す断面図である。
【０２８２】
感光材料の処理量に応じて錠剤ケミカル収納部211より直接処理槽内部にある投入部215に供給する。投入部215は未溶解の処理剤が直接感光材料に付着しないよう固体処理剤用フィルター216がある。このフィルター216の材質は特に限定されない。メッシュについても特に限定しないが液の流通及びフィルター効果より10〜100μmが好ましい。
【０２８３】
処理槽の一部を構成する恒温槽212に固体処理剤を供給した時と効果はほぼ同等である。唯一処理槽内に投入部215が別にあることでコンパクト性が劣る。
【０２８４】
次は４方シール、３方シールの包装の具体例を図20，図21に示す。ただし本発明はこれらに限定されない。図20（Ａ）で示すシール包装では、１つの包装単位の中で、数種の錠剤が入っている。図20（Ｂ）には種類サイズの異なる錠剤が個装されている。図20（Ｃ）は顆粒又は粉末を包装したものである。図20（Ｄ）は同一の大きさのものが１つづつ入っている。図20（Ｅ）では、同一の大きさの、同一ケミカルが、小錠剤として複数個入っている。
【０２８５】
図21（Ａ），（Ｂ），（Ｃ）は四方シールの例を示す平面図である。図21（Ｄ）は三方シールの例を示す。図22（Ａ），（Ｂ）はスティック包装の具体例を示す、ただしこれらに限定されない。
【０２８６】
図23は錠剤、顆粒又は粉末をシール包装してヒートシールしたのち、つづら折りにして容器内に収容した状態を示す断面図である。
【０２８７】
図24はPTP包装の具体例を示す。ただしこれらに限定されるものではない。図24（Ａ）は丸薬状の固体処理剤をPTP包装したものであり、図24（Ｂ）は処理剤の錠剤が複数個入って包装されている状態を示す。図24（Ｃ）は錠剤、顆粒又は粉末が入っているものを縦列配置した状態を示す。図24（Ｄ）はこれら包装体を横１列につながったものを示す。あるいは図24（Ｅ）に示すブリスター的なものでもよい。
【０２８８】
図25は一括包装の具体例を示す。ただしこれらに限定されない。図25（Ａ）は筒形容器内に固体処理剤を収容したもの、図25（Ｂ）は柔軟な二方シール又は三方シールされた袋内に固体処理剤を収容したもの、図25（Ｃ）は固体処理剤を収容した袋を一方シールしたものを示す。
【０２８９】
図26，図27はカートリッジの具体例を示す斜視図等である。
【０２９０】
これらのカートリッジは固体処理剤の入った包装材料のまま本発明自現機の供給装置に装着できる。材質は前記記載の化合物はどれも使用できる。固体処理剤が減少したとき、供給の障害にならない様に潰れないものが良い。
【０２９１】
図26（Ａ）は錠剤を円筒型カートリッジに収容したもの、図26（Ｂ）は顆粒または粉体をカートリッジに収容したものである。
【０２９２】
図26（Ｃ），（Ｄ）は開閉蓋を有する箱型カートリッジに固体処理剤を収容した形態を示す斜視図および断面図を示す。
【０２９３】
図27は錠剤または顆粒または粉体を仕切り壁を有する回転可能な容器内容に収容し、さらに外筒（本体）内に収容して、開口部から所定量を落下させるものである。図27（Ａ）は回転軸を水平支持した形式、図30（Ｂ）は回転軸を垂直支持した形式のものである。
【０２９４】
なお、本発明はこれら具体例に限定されるものではない。
【０２９５】
更に図28（ａ）（ｂ）、図29（ａ）（ｂ）及び図30、31、図32の実施例について説明する。
【０２９６】
図28（ａ）（ｂ）は「コの字」形半抜きパンチ方式を表わす。
【０２９７】
感光材料が処理されると処理量情報検知手段によって検知し、ある一定量に達したときに、処理剤供給制御手段により信号が送られ搬送ローラ100が回転し、固体処理剤107の入った図29（ａ）に示す包装体801を図28（ａ）の様な位置まで移動させ停止する。包装体801を移動させる方法は包装体801に予め設けられたノッチを検出する方法、印刷柄又はアイマークの検出、包装体801の固体処理剤107の検出等どんな方法でも良いが要は必要数の固体処理剤107を精度良く検出すれば良い。次に図28（ｂ）の様にパンチ雄型300が下方に動き包装体801を切断し固体処理剤107は図29（ａ）の投入口901を経て、自動現像機の処理槽に投入される。パンチ雄型300で切断された切り口は図29（ｂ）に示すようにパンチ形状601の様にコの字となる。
【０２９８】
この様な方式の場合、固体処理剤107は粉剤、顆粒、錠剤どれでも良いが好ましくはパンチ雄型に、薬品が付着しにくい錠剤が良い。又錠剤は包装体に余り付着せず従って汚れも発生しにくく、ユーザーが取扱う際にも安全である。使用済み包装体801は廃棄箱102に入りまとめて廃棄することができる。この廃棄箱102は、使用済みの包装体収納箱701を再使用することが好ましい。
【０２９９】
図30，31は包装体110の切り落とし方法を表わす。
【０３００】
感光材料が処理されると処理量情報検知手段によって検知し、ある一定量に達したときに、処理剤供給制御手段により信号が送られ搬送ローラ201が回転し、固体処理剤107の入った包装体110を固体処理剤107が処理槽フィルター部702の上部の位置にくるまで移動させ停止する。このとき包装体110の先端はしごきローラ401に入っている。
【０３０１】
包装体を移動させる方法は包装体110に予め設けられたノッチを検出する方法、印刷柄の検出、包装体の処理検出等どんな方法でも良いか要は必要数の固体処理剤107を精度良く検出すれば良い。次にセラミック製カッター2011が包装体110を切断する。切断が終了するとしごきローラ401及び搬送ローラ501が回転し固体処理剤107はしごきローラ401によりしごかれ排出口を通過し自動現像機の処理槽フィルター部702に投入される。カットされた廃棄包装体802は搬送ローラ501より排出され廃棄箱602に入る。この廃棄箱602は使用済みの包装体収納箱301を再使用するのが好ましい。
【０３０２】
この様な方式の場合、固体処理剤107は粉剤、顆粒、錠剤どれでも良いが、好ましくはセラミック製カッター201に薬品が付着しない錠剤が良い。又錠剤は包装体110に余り付着せず従って汚れも発生しにくいという利点がある。
【０３０３】
使用済み包装体110は廃棄箱602に入りまとめて廃棄することができる。
【０３０４】
図32（ａ），（ｂ）は連続包装体603の二分割カット方式を表わす。
【０３０５】
感光材料が処理されると処理量情報検出手段によって検知し、ある一定量に達したときに処理剤供給手段により信号が送られ搬送ローラ502が回転すると同時にセラミック製又はステンレス製の丸刃301が回転し、連続包装体603の下部を二分割カットし固体処理剤107を投入する。この二分割する際に連続包装体603はサクションガイド202にサクションにて両サイドに広げられ内部の固体処理剤107が落下し易くなっている。固体処理剤107がない空の包装体603は次の固体処理剤107の投入の時搬送ローラ401で移動し包装体収納箱101へ廃棄される。
【０３０６】
この二分割は上記方法の他連続包装体にノッチ等と付けておき、ローラーで巻き取りながら引き裂いても良い。
【０３０７】
この様な方式の場合、固体処理剤107は粉剤、顆粒、錠剤どれでも良いが好ましくはパンチ雄型に薬品が付着しない錠剤が良い。又錠剤は包装体のシールに余り付着せず従って、汚れも発生しにくいという利点がある。
【０３０８】
使用済みの連続包装体603は包装体収納箱101に入りまとめて廃棄することができる。
【０３０９】
【実施例】
（実施例１）
コニカＱＡペーパータイプＡ５（コニカ（株）社製）を像様露光した後、コニカビッグミニラボＢＭ−101（コニカ（株）社製）の補充剤添加部分を改造して図32に示す固体処理剤供給装置に改造し、さらに表１の処理工程となるように改造を加え連続処理を行った。
【０３１０】
【表１】

【０３１１】
安定は３から１への向流方式であり、安定−１のオーバーフロー液は全量漂白定着槽に流入された。また、感光材料１m²当りのキャリーオーバーは、全ての槽で50ml／m²であった。
【０３１２】
また、蒸発補正は温調時は、発色現像、漂白定着、安定に各々9.0ml／時、7.2ml／時、14.1ml／時ずつ１時間毎に行い、温調をしていない時には、各々3.8ml／時、3.1ml／時、6.1ml／時ずつを積算し、温調開始時にまとめて行った。
【０３１３】
スタート時のタンク液は、コニカカラーＱＡペーパー発色現像スタート剤82P-1B，（コニカ（株）社製コニカカラーＱＡペーパー漂白定着スタート剤82P-2B（同上），コニカカラーＱＡペーパー安定スタート剤82P-3B（同上）を用いて作成した。
【０３１４】
以下の操作（Ａ〜Ｇ）に従ってカラーペーパー用処理錠剤を作成した。
【０３１５】
１）カラーペーパー用発色現像補充用錠剤
操作（Ａ）
現像主薬のＣＤ−３[4-アミノ-3-メチル-N-エチル-N-〔β-(メタンスルホンアミド）エチル〕アニリン硫酸塩]1200gを市販のバンダムミル中で平均粒径10μmになるまで粉砕する。この微粉末を市販の撹拌造粒機中で室温にて約７分間、50mlの水を添加することにより造粒した後、造粒物を流動層乾燥機で40℃にて２時間乾燥して造粒物の水分をほぼ完全に除去する。このようにして、調整した造粒物にポリエチレングリコール6000（150ｇ）を25℃、40％RH以下に調湿された部屋で混合機を用いて10分間均一に混合する。次にN-ラウロイルアラニンナトリウム４ｇを添加し、３分間混合した後、得られた混合物を菊水製作所（株）製タフプレストコレクト1527ＨＵを改造した打錠機により１錠当たりの充填量を1.0ｇにして圧縮打錠を行い、400個のカラーペーパー用発色現像補充用直径15mmの錠剤Ａ剤を作成した。
【０３１６】
操作（Ｂ）
ジスルホエチルヒドロキシルアミン２ナトリウム塩120ｇを操作（Ａ）と同様、粉砕、造粒する。水の添加量は6.0mlとし、造粒後、50℃で30分間乾燥して造粒物の水分をほぼ完全に除去する。このようにして、調整した造粒物にN-ラウロイルアラニンナトリウム４を添加し、25℃、40％RH以下に調湿された部屋で混合機を用いて３分間混合する。次に得られた混合物を菊水製作所（株）製タフプレストコレクト1527ＨＵを改造した打錠機により１錠当たりの充填量を1.0gにして圧縮打錠を行い、100個のカラーペーパー用発色現像補充用直径15mmの錠剤Ｂ剤を作成した。
【０３１７】
操作（Ｃ）
チノパールＳＦＰ（チバガイギー社製）30.0ｇ、亜硫酸ナトリウム3.7ｇ、臭化カリウム0.3ｇ、ジエチレントリアミン５酢酸25ｇ、p-トルエンスルホン酸ナトリウム280ｇ、水酸化カリウム20ｇ、マンニトール10.6ｇを（Ａ）と同様粉砕した後、市販の混合機で均一に混合する。次に（Ａ）と同様にして、水の添加量を20mlにして造粒を行う。造粒後、造粒物を60℃で30分間乾燥して造粒物の水分をほぼ完全に除去する。このようにして、調整した造粒物にN-ラウロイルアラニンナトリウム４ｇを添加し、25℃、40％RH以下に調湿された部屋で混合機を用いて３分間混合する。次に得られた混合物を菊水製作所（株）製タフプレストコレクト1527ＨＵを改造した打錠機により１錠当たりの充填量を3.2ｇにして圧縮打錠を行い、100個のカラーペーパー用発色現像補充用直径20mmの錠剤Ｃ剤を作成した。
【０３１８】
操作（Ｄ）
炭酸カリウム350ｇを操作（Ａ）と同様、粉砕、造粒する。水の添加量は20mlとし、造粒後、700℃で30分間乾燥して造粒物の水分をほぼ完全に除去する。このようにして、調整した造粒物にポリエチレングリコール6000を15ｇを25℃、40％RH以下に調湿された部屋で混合機を用いて10分間均一に混合する。次にN-ラウロイルアラニンナトリウム４ｇを添加し、３分間混合した後、得られた混合物を菊水製作所（株）製タフプレストコレクト1527ＨＵを改造した打錠機により１錠当たりの充填量を3.0ｇにして圧縮打錠を行い、110個のカラーペーパー用発色現像補充用直径20mmの錠剤Ｄ剤を作成した。
【０３１９】
２）カラーペーパー用漂白定着補充用錠剤
操作（Ｅ）
ジエチレントリアミン５酢酸第２鉄アンモニウム１水塩1250ｇ、エチレンジアミン４酢酸25ｇ、マレイン酸250ｇ、パインフロー（松谷化学）46ｇを操作（Ｃ）と同様、粉砕、混合し造粒する。水の添加量は80mlとし、造粒後、60℃で２時間乾燥して造粒物の水分をほぼ完全に除去する。このようにして、調整した造粒物にN-ラウロイルサルコシンナトリウム15ｇを添加し、25℃、40％RH以下に調湿された部屋で混合機を用いて３分間混合する。次に得られた混合物を菊水製作所（株）製タフプレストコレクト1527ＨＵを改造した打錠機により１錠当たりの充填量を8.6ｇにして圧縮打錠を行い、170個のカラーペーパー用漂白定着補充用直径30mmの錠剤Ａ剤を作成した。
【０３２０】
操作（Ｆ）
チオ硫酸アンモニウム1640ｇ、亜硫酸ナトリウム750ｇ、臭化カリウム40ｇ、p-トルエンスルフィン酸50ｇを操作（Ｃ）と同様、粉砕、混合し造粒する。水の噴霧量は100mlとし、造粒後、60℃で120分間乾燥して造粒物の水分をほぼ完全に除去する。このようにして、調整した造粒物にN-ラウロイルサルコシンナトリウム20gを添加し、25℃、40％RH以下に調湿された部屋で混合機を用いて３分間混合する。次に得られた混合物を菊水製作所（株）製タフプレストコレクト1527ＨＵを改造した打錠機により１錠当たりの充填量を13.4ｇにして圧縮打錠を行い、180個のカラーペーパー用漂白定着補充用直径30mmの錠剤Ｂ剤を作成した。
【０３２１】
３）カラーペーパー用安定補充用錠剤
操作（Ｇ）
炭酸ナトリウム・１水塩10ｇ、1-ヒドロキシエタン-1,1-ジホスホン酸ジナトリウム200ｇ、チノパールＳＦＰ150ｇ、亜硫酸ナトリウム300ｇ、硫酸亜鉛７水塩20ｇ、エチレンジアミン４酢酸２ナトリウム150ｇ、硫酸アンモニウム200ｇ、o-フェニルフェノール10ｇ、パインフロー25ｇを操作（Ｃ）と同様、粉砕、混合し造粒する。水の添加量は60mlとし、造粒後、70℃で60分間乾燥して造粒物の水分をほぼ完全に除去する。このようにして、調整した造粒物にN-ラウロイルサルコシンナトリウム10ｇを添加し、25℃、40％RH以下に調湿された部屋で混合機を用いて３分間混合する。次に得られた混合物を菊水製作所（株）製タフプレストコレクト1527ＨＵを改造した打錠機により１錠当たりの充填量を3.1ｇにして圧縮打錠を行い、360個のカラーペーパー用安定補充用直径20mmの錠剤を作成した。また操作（Ａ）〜（Ｇ）における打錠圧力は各々650kg／cm²とした。
【０３２２】
次に、上記錠剤を発色現像補充用錠剤については、Ａ，Ｂ，Ｃ，Ｄ剤を各々１錠ずつ、計４錠を１分包とし、連続20分包分を四方シール方式で分包した。また漂白定着補充用錠剤については、Ａ剤を１錠、Ｂ剤を２錠分ずつ計３錠を１分包とし、連続20分包分を上記発色現像補充用錠剤と同様に分包した。
【０３２３】
さらに、安定補充用錠剤については、各１錠ずつを１分包とし、前記と同様に分包した。
【０３２４】
四方シール包材としては、無延伸ポリプロピレンフィルム／延伸ポリプロピレンフィルムの無延伸ポリプロピレンフィルム面でラミネートし、作成した。
【０３２５】
作成した無延伸ポリプロピレン／延伸ポリプロピレンフィルムをヒートシールし、上記錠剤を分包した。
【０３２６】
処理は１日当りカラーペーパーを５m²とし、オーバーフロー量がタンク液の２倍（2.0Ｒ）となるまで行い、2.0Ｒ時における各処理槽中の不溶解錠剤の蓄積数を測定した。さらに各々の錠剤の溶解性を観察した。
【０３２７】
錠剤の溶解性は処理槽中の錠剤供給部を改造し、透明アクリル板を処理槽部に設置することで目視により錠剤１分包投入直後から完全溶解するまでの時間を測定した。
【０３２８】
また、評価は下記に示す。
【０３２９】
○ ：問題なし
△ ：処理液中にわずかに沈澱物、オイルアウト物が発生
× ：処理液中に沈澱物が多量に発生
××：処理液中に沈澱物が多量に発生し感光材料に付着
また、固体処理剤が１回投入された直後と次の固体処理剤を投入する直前にウェッジ露光をほどこした試料を現像しブルーの反射濃度の最大濃度の差（ΔＤmax（Ｂ））を測定しランニング開始後から各々の固体処理剤が16回投入されるまでの平均値を算出した。
【０３３０】
上記の結果を表２に示す。
【０３３１】
【表２】

【０３３２】
表２から明らかなように本発明のＳ／Ｒ値は固体処理剤の溶解状況に対し密接な関係があり、Ｓ／Ｒ値が大きいと処理槽中に固体処理剤が蓄積し、不溶解現象をおこす。
【０３３３】
またＳ／Ｒ値が小さいと処理液中で局所的に濃厚部分が発生し、ここから沈澱が発生し成長するという現象がわかった。さらに、発色現像についてはＳ／Ｒが小さくなると処理バラツキが大きくなる問題があることがわかった。
【０３３４】
これらの現象は４≦Ｓ／Ｒ≦40の範囲であれば問題なく良好な結果を示すことがわかる。
【０３３５】
（実施例２）
実施例１において発色現像剤用錠剤の操作（Ａ）〜（Ｄ）における打錠圧力及び操作（Ｄ）における炭酸カリウム量を表３のように変化させ発色現像液について実施例（１）と同様の実験を行った。
【０３３６】
結果を表３に示す。
【０３３７】
【表３】

【０３３８】
表３から明らかなように錠剤中の素材及び打錠圧力をコントロールすることでも本発明の効果を明確に奏することができる。
【０３３９】
（実施例３）
実施例１において操作（Ａ）〜（Ｇ）の打錠工程を除き各々について、顆粒状処理剤を作製した。
【０３４０】
また、操作（Ａ）〜（Ｇ）の打錠工程及び造粒工程を除き、各々について粉状処理剤を作製した。
【０３４１】
得られた錠剤、顆粒剤、粉剤処理剤、各々の発色現像剤について実施例１と同様の実験を行った。
【０３４２】
結果を表４に示す。
【０３４３】
【表４】

【０３４４】
表４より明らかなように、本発明の効果である固体処理剤の溶解状況及び処理バラツキの改良は固体処理剤が顆粒であるとき好ましく、より好ましくは錠剤である時に本発明の効果をより顕著にすることがわかる。
【０３４５】
（実施例４）
コニカカラーネガティブフィルムスーパーＤＤ−100フィルムを像様露光した後、カラーネガフィルムプロセッサーＣＬ−ＫＰ−50ＱＡを四方シール包材が使用できる方式に改造し、連続処理を行った。
【０３４６】
【表５】

【０３４７】
定着は２から１への、安定は３から２，２から１への向流方式であり、漂白槽はエアーポンプでエアレーションを行った。
【０３４８】
また、蒸発補正は温調時は発色現像，漂白，定着−１，定着−２，安定−１，安定−２，安定−３槽に各々１時間に10ml，6.5ml，７ml，７ml，8.6ml，8.6ml，9.3mlの蒸発補水を行うプログラムにて蒸発補正を行った。また非稼働時は非稼働時間を積算し、発色現像，漂白，定着−１，定着−２，安定−１，安定−２，安定−３に蒸発補正水を各々１時間当たり7.5ml，５ml，６ml，６ml，５ml，５ml，５mlの量をまとめて稼働開始時に補水した。スタート時のタンク液はコニカカラーネガティブフィルム用処理剤（プロセスＣＮＫ−４−52）の補充液及びスターターを用いて作成した。
【０３４９】
以下の操作に従ってカラーネガフィルム用処理錠剤を作成した。
【０３５０】
１）カラーネガ用発色現像補充用錠剤
操作（１）
現像主薬のＣＤ−４〔4-アミノ-3-メチル-N-エチル-β-(ヒドロキシ）エチルアニリン硫酸塩〕150ｇを、市販バンダムミル中で平均粒径10μmになるまで粉砕する。この微粉末を市販の撹拌造粒機中で室温にて約７分間、10mlの水を添加することより造粒した後、造粒物を流動層乾燥機で40℃にて２時間乾燥して造粒物の水分をほぼ完全に除去する。このようにして、調整した造粒物にN-ラウロイルアラニンナトリウム0.3ｇと、ポリエチレングリコール6000を1.9ｇを添加し、25℃、40％RH以下に調湿された部屋で混合機を用いて10分間均一に混合する。次に混合物を菊水製作所（株）製タフプレストコレクト1527ＨＵを改造した打錠機により１錠当たりの充填量を1.1ｇにして圧縮打錠を行い、126個のカラーネガ用発色現像補充用錠剤Ａ剤を作成した。
【０３５１】
操作（２）
硫酸ヒドロキシルアミン69.4ｇとパインフロー（松谷化学製）４ｇを操作（１）と同様に粉砕した後、混合、造粒する。水の添加量は3.5mlとし、造粒後、60℃で30分間乾燥し、造粒物の水分をほぼ完全に除去する。このようにして、調整した造粒物にN-ラウロイルアラニンナトリウム0.3ｇを添加し、25℃、40％RH以下に調湿された部屋で混合機を用いて３分間混合する。さらに、操作（１）と同様な方法で打錠機を用い１錠当たりの充填量を0.56ｇにして圧縮打錠を行い、120個のカラーネガ用発色現像補充用錠剤Ｂ剤を作成した。
【０３５２】
操作（３）
1-ヒドロキシエタン-1,1-ジホスホン酸ジナトリウム15ｇ、亜硫酸カリウム72.8ｇ、炭酸カリウム375ｇ、炭酸水素ナトリウム３ｇ、臭化ナトリウム3.7ｇとマンニット22ｇを操作（１）と同様に粉砕、混合し、水の添加量を40mlにして造粒を行う。造粒後、造粒物を70℃で60分間乾燥して造粒物の水分をほぼ完全に除去する。このようにして、調整した造粒物にN-ラウロイルアラニンナトリウム２ｇを添加し、25℃、40％RH以下に調湿された部屋で混合機を用いて３分間混合する。さらに、操作（１）と同様な方法で打錠機を用い１錠当たりの充填量を3.9ｇにして圧縮打錠を行い、120個のカラーネガ用発色現像補充用錠剤Ｃ剤を作成した。
【０３５３】
２）カラーネガ用漂白補充用錠剤
操作（４）
1,3-プロパンジアミン４酢酸第２鉄アンモニウム１水塩175ｇ、1,3-プロパンジアミン４酢酸２ｇ、パインフロー（松谷化学製）17ｇを操作（１）と同様に粉砕、混合し、水の添加量を８mlにして造粒を行う。造粒後、造粒物を60℃で30分間乾燥して造粒物の水分をほぼ完全に除去する。
【０３５４】
操作（５）
コハク酸133ｇ、臭化アンモニウム200ｇとパインフロー10.2ｇを操作（１）と同様、粉砕、混合、造粒する。水の添加量は17mlとし、造粒後、70℃で60分間乾燥して造粒物の水分をほぼ完全に除去する。
【０３５５】
操作（６）
硫酸カリウム66.7ｇ、炭酸水素カリウム60ｇとマンニット８ｇを操作（１）と同様、粉砕、混合、造粒する。水の添加量は13mlとし、造粒後、60℃で60分間乾燥して造粒物の水分をほぼ完全に除去する。
【０３５６】
操作（７）
上記操作（４）−（６）で調整した造粒物を25℃、40％RH以下に調湿された部屋で混合機を用いて10分間均一に混合する。次にこの混合造粒物にN-ラウロイルサルコシンナトリウム６ｇを添加し、３分間混合する。次に混合物を菊水製作所（株）製タフプレストコレクト1527ＨＵを改造した打錠機により１錠当たりの充填量を6.5ｇにして圧縮打錠を行い、80個のカラーネガ用漂白補充用錠剤を作成した。
【０３５７】
３）カラーネガ用定着補充用錠剤
操作（８）
チオ硫酸アンモニウム2500ｇ、亜硫酸ナトリウム150ｇ、炭酸カリウム150ｇ、エチレンジアミン４酢酸２ナトリウム塩20ｇとパインフロー（松谷化学製）65ｇを操作（１）と同様、粉砕、混合、造粒する。水の添加量は50mlとし、造粒後、60℃で120分間乾燥して造粒物の水分をほぼ完全に除去する。
【０３５８】
操作（９）
上記操作（８）で調整した造粒物とN-ラウロイルサルコシンナトリウム13ｇを25℃、40％RH以下に調湿された部屋で混合機を用いて３分間混合する。次に混合物を菊水製作所（株）製タフプレストコレクト1527ＨＵを改造した打錠機により１錠当たりの充填量を9.3ｇにして圧縮打錠を行い、280個のカラーネガ用定着補充用錠剤を作成した。
【０３５９】
４）カラーネガ用安定補充用錠剤
操作（10）
m-ヒドロキシベンズアルデヒド150ｇ、ラウリル硫酸ナトリウム20ｇ、エチレンジアミン４酢酸ジナトリウム60ｇ、水酸化リチウム１水塩65ｇとパインフロー10ｇを操作（１）と同様、粉砕、混合、造粒する。水の添加量は10mlとし、造粒後、造粒物を50℃にて２時間乾燥して造粒物の水分をほぼ完全に除去する。
【０３６０】
操作（11）
上記操作（10）で調整した造粒物を25℃、40％RH以下に調湿された部屋で菊水製作所（株）製タフプレストコレクト1527ＨＵを改造した打錠機により１錠当たりの充填量を0.48ｇにして圧縮打錠を行い、280個のカラーネガ用安定補充用錠剤を作成した。
【０３６１】
次に上記錠剤を発色現像補充用錠剤についてはＡ，Ｂ，Ｃ剤を各々２錠，１錠，１錠，漂白補充用錠剤については２錠，定着補充用錠剤については３錠，安定補充用錠剤については１錠ずつを１分包とし、各々連続20分包分を四方シール方式で分包した。包材については実施例１で用いたものと同じものを用いた。
【０３６２】
処理は１日当り、発色現像タンク槽からのオーバーフローがタンク液の５％となるまでとし、オーバーフロー量がタンク液の２倍となるまで（2.0Ｒ）行い、実施例１と同様に2.0Ｒ時における各処理槽中の不溶解錠剤の蓄積数及び溶解状況について実験した。
【０３６３】
また、固体処理剤が１回投入された直後と次の固体処理剤を投入する直前にウエッジ露光をほどこしたコニカカラースーパーＤＤ−100フィルムを現像し、ブルー透過濃度の最大濃度の差（ΔＤmax（Ｂ））を測定し、ランニング開始後から各々の固体処理剤が10回投入されるまでの平均値を算出した。
【０３６４】
上記の結果を表６，７に示す。
【０３６５】
【表６】

【０３６６】
【表７】

【０３６７】
表６，７より明らかなように４≦Ｓ／Ｒ≦40のときに本発明の効果が明確にあらわれる。
【０３６８】
（実施例５）
以下の操作に従って発色現像用錠剤を作成した。
【０３６９】
操作（Ｈ）
ジスルホエチルヒドロキシルアミン２ナトリウム塩40ｇ、p-トルエンスルホン酸ナトリウム200ｇ、チノパールＳＦＰ（チバガイギー社製）30ｇ、ジエチレントリアミン五酢酸ナトリウム30ｇ、パインフロー（松谷化学社製）30ｇ、これら全てを市販の混合造粒機で水を少量づつ添加し造粒する、水の添加量は20mlとした。その後、乾燥機中で40℃12時間乾燥し、水分含有率を１％以下とした。最後にこれを16メッシュのふるいにかけた。
【０３７０】
操作（Ｉ）
発色現像主薬ＣＤ−３ 150ｇとポリエチレングリコール＃6000 100ｇ、Ｄ−マンニット 20ｇ、これを市販の混合造粒機で水を少量づつ添加し造粒する。
【０３７１】
水の添加量は20mlとした。その後、乾燥機中で40℃12時間乾燥し、水分含有率を１％以下とした。最後にこれを16メッシュのふるいにかけた。
【０３７２】
操作（Ｊ）
p-トルエンスルホン酸ナトリウム100ｇ、亜硫酸ナトリウム4.0ｇ、水酸化カリウム30ｇ、ポリエチレングリコール（平均分子量6000）100ｇ、炭酸カリウム330ｇ、Ｄ−マンニット 60ｇ、これらを市販の混合造粒機で水を少量づつ添加し造粒する。水の添加量は33mlとした。その後、乾燥機中で40℃12時間乾燥し、水分含有率を１％以下とした。最後にこれを16メッシュのふるいにかけた。
【０３７３】
操作（Ｋ）
上記操作（Ｈ）〜（Ｊ）で造粒した造粒物全てとN-ミリストイル-N-メチル-β-アラニンナトリウム10ｇを混合機中で10分間混合する。
【０３７４】
次に混合物を菊水製作所社製タフプレスコレクト1527ＨＵを改造した打錠機により錠剤を作成する。錠剤は充てん量は11.0ｇとして直径30mmの円筒型になるようにし、嵩密度が表８になるように圧縮圧力を変化させ発色現像液について実施例１と同様の実験を行った。錠剤は１回の投入作動に対し１錠投入するようにした。尚、嵩密度の調整においては圧縮圧力の他にパインフロー又は硫酸カリウムを混合物に適量加えた後に打錠することで変化させた。
【０３７５】
結果を表８に示す。
【０３７６】
【表８】

【０３７７】
表８より明らかなように、本発明の効果の１つである溶解性は錠剤の嵩密度が1.0〜2.5ｇ／cm³である時により顕著となることがわかる。
【０３７８】
（実施例６）
実施例５において、操作（Ｈ）中のチノパールＳＦＰを表９のように変化させた以外は操作（Ｈ）と同様にして得られた造粒物と、操作（Ｉ），（Ｊ）と同様にして得られた造粒物とをそれぞれ混合させ充てん量11ｇ、嵩密度1.4ｇ／cm³、直径30mmの錠剤を作成し、発色現像について実施例１と同様に実験を行った。
【０３７９】
結果を表９に示す。
【０３８０】
【表９】

【０３８１】
表９より明らかなように発色現像剤に前記一般式［Ｅ］で示されるトリアジニルスチルベン系蛍光増白剤を含有させることにより、溶解性及び処理安定性の点で本発明の効果をより顕著に奏することがわかる。
【０３８２】
【発明の効果】
第１に輸送上の危険や取扱い上の危険をともなう液体ケミカルをなくしユーザーへの煩雑な操作をなくした、第２にユーザー自身の手作業による濃縮キットの溶解作業をなくし完全自動化補充システムを完成する、第３に処理液に直接投入する固体処理剤において、処理安定性を損うことがなく、かつ処理槽中で沈澱発生なく溶解する、第４に液体補充液の貯蔵の必要性を一切なくした処理安定性が向上した固体処理剤の提供をすることができる。第５に液体用ポリボトルの使用をなくしたプラスチックの包材の使用を低減した低公害システムを達成することができる。
【図面の簡単な説明】
【図１】自動現像機Ａと写真焼付機Ｂとを一体的に構成したプリンタープロセッサーの概略構成図。
【図２】図１の自現機ＡのＩ−Ｉ断面における処理槽である発色現像槽１Ａの概略図である。
【図３】自動現像機の補充水供給手段を追加した処理剤投入部と処理剤供給手段との断面図。
【図４】上記自動現像機の平面図。
【図５】自動現像機の制御手段を含むブロック図。
【図６】制御手段に予めプログラムされた蒸発補水設定手段を加えたブロック図。
【図７】粉状処理剤供給装置の断面図とパッケージの斜視図。
【図８】粉状処理剤供給装置の斜視図。
【図９】他の粉状処理剤供給装置の断面図。
【図１０】粉状処理剤の更に他の供給装置を示す断面図。
【図１１】ＰＴＰ包装処理剤供給装置の断面図及び斜視図。
【図１２】パーツフィーダ方式供給装置の１例示す断面図。
【図１３】パーツフィーダ方式供給装置のさらに他の１例を示す断面図。
【図１４】固体処理剤供給装置のさらに他の１例を示す斜視図。
【図１５】供給装置の平面図と斜視図及び包装体の平面図。
【図１６】供給装置の側断面図及び正面断面図。
【図１７】供給装置の断面図及び包装体の斜視図。
【図１８】ブリスター個包装された固形処理剤の供給装置の断面図。
【図１９】本発明の（固形処理剤を直接処理槽に添加する）１例を示す断面図。
【図２０】シール包装の平面図。
【図２１】三方シール、四方シールのシール包装の具体例を示す平面図。
【図２２】スティック包装の具体例を示す平面図。
【図２３】シール包装体を容器内につづら折りにして収容した状態を示す断面図。
【図２４】ＰＴＰ包装の具体例を示す図。
【図２５】一括包装の具体例を示す図。
【図２６】カートリッジの具体例を示す図。
【図２７】カートリッジの他の具体例を示す斜視図。
【図２８】包装体をコの字に半抜きしてカットする装置。
【図２９】図28の包装体のコの字に半抜きする装置の斜視図。
【図３０】包装体を切り落す方式を示す装置。
【図３１】図30の切り落す方式を示す装置の斜視図。
【図３２】連続包装体の二分割カット方式を示す装置。
【符号の説明】
１ 処理槽
１Ａ〜１Ｅ 処理槽
Ｒ 送りローラ
２ 処理部
３ フィルター
４ 循環パイプ
５ 循環ポンプ
６ 排液管
７ ヒータ
８ 処理量情報検出（知）手段
９ 処理剤供給制御手段
10 押出部材
11 固体処理剤投入部
12 仕切壁
13 錠剤
14 濾過部（区分）
15 カートリッジ
17 処理剤供給手段
18 押し爪
19 カム
21 錠剤押しばね
23 予じめプログラムされた蒸発補水設定手段
32 温水補給装置
33 電磁弁
35 乾燥部
36 補水管
41 パイプ（補水用）
42 補充水供給手段
43 補水タンク[0001]
[Industrial application fields]
The present invention relates to a solid processing agent for a silver halide photographic light-sensitive material (hereinafter, sometimes simply referred to as a solid processing agent), and more specifically, an automatic processor for a silver halide photographic light-sensitive material (hereinafter simply referred to as a solid processing agent). The present invention relates to a solid processing agent that can be supplied stably and accurately and has good solubility when it is directly charged into a processing tank.
[0002]
[Prior art]
A silver halide color photographic light-sensitive material (hereinafter also referred to as a light-sensitive material or a photographic material) is processed by steps such as development, desilvering, washing and stabilization after exposure. The black and white silver halide photographic material is developed and fixed after exposure. Black-and-white developer, color developer, bleaching solution for desilvering processing, bleach-fixing solution, fixing solution for fixing processing, tap water or ion-exchanged water for washing, stabilizing solution for washing with anhydrous washing, and dye stabilization A stabilizing solution is used for each treatment.
[0003]
A liquid having a processing function for performing each of these processing steps is referred to as a processing liquid. The temperature of each processing solution is usually adjusted to 30 to 40 ° C., and the photosensitive material is immersed and processed in these processing solutions.
[0004]
Such a process is usually performed by sequentially transporting the inside of the processing tank containing the processing solution by an automatic developing machine (hereinafter also referred to as a self-processing machine).
[0005]
Here, when referring to a self-supporting machine, a developing machine having a developing unit, a fixing unit, a desilvering unit, a washing or stabilizing unit, and a drying unit, and means for automatically conveying the photosensitive material sequentially to each processing unit. Generally speaking.
[0006]
When processing with such an automatic machine, a method of replenishing a processing agent is generally widely adopted in order to keep the activity of the processing liquid in the processing tank constant.
[0007]
As this treatment agent replenishment method, a method of preparing a replenisher solution in which a treatment agent is dissolved is widely used.
[0008]
Specifically, the processing operation is performed while supplying a replenisher prepared in advance from the replenishing tank into the processing tank.
[0009]
In this case, the replenisher stored in the replenishment tank itself is generally prepared and prepared at a different location, but in a minilab, etc., a fixed amount is adjusted at once in a replenishment tank installed close to the inside of the developing machine. Usually, in the production thereof, manual dissolution or dissolution mixing by a mixer has been performed.
[0010]
That is, a processing agent for silver halide photographic light-sensitive materials (hereinafter sometimes referred to as a photographic processing agent) is commercially available in the form of powder or liquid. In the case of liquid form, it is also concentrated, so that it can be used by simply stirring and diluting by adding a certain amount of water.
[0011]
Since the replenishment tank may be installed beside the self-machine, it is necessary to secure a considerable space. In addition, in the mini-lab which has been increasing rapidly recently, a replenishment tank is built in the self-machine main body. However, at least 5 L to 10 L of liquids are necessary, and it is necessary to secure such a replenishment tank space.
[0012]
The replenishing processing agent is divided into several parts in order to obtain good and stable performance during photographic processing. The color developer for color is divided into 3 to 4 parts, and the replenisher for the color bleach-fixing solution is divided into an organic acid ferric salt part as an oxidizing agent and a thiosulfate part as a reducing agent. At the time of preparing the replenisher, the concentrated part of the organic acid ferric salt and the concentrated part containing thiosulfate are mixed and used by adding a certain amount of water.
[0013]
The thickened part is put in a container such as a plastic container, and these parts are put together in an outer bag (for example, a cardboard box) and marketed as one unit.
[0014]
The replenishment treatment agent in which the above-mentioned part agent is made into a kit is used after being dissolved, diluted and mixed and finished to a certain amount, but the present inventors have the following drawbacks. I found it.
[0015]
First, most of the conventional kits are concentrated aqueous solutions concentrated to improve workability, and most of them are extremely dangerous aqueous solutions with a pH of 2.0 or less or 12.0 or more. Many of them are also strong oxidizing agents or reducing agents, and they are extremely dangerous and corrosive for transportation by ship or aircraft. In addition, since it is an aqueous solution, its solubility is limited, and its weight and volume are larger than those of a solid. As mentioned above, because the concentrate is a hazardous material, it is necessary that the container does not break and does not spill even if dropped from a certain height. Is a problem.
[0016]
Secondly, each part is put in a container, and depending on the replenishing agent, there are several parts, and if one unit is used, the number of containers becomes considerably large, and a lot of space is required for storage and transportation. To do. For example, the color development replenisher for CPK-2-20QA, a color paper processing solution, contains 10 liters as one unit, a preservative-containing kit in Part A, a color developing agent-containing kit in Part B, and an alkaline agent in Part C. Separated, each A, B and C is in a 500 ml plastic container. Similarly, the bleaching solution is divided into 3 bottles with 8 l as one unit, and the stabilizing solution is divided into 2 bottles with 10 l as a unit. These replenishers are stored and transported in outer boxes of various sizes, but the outer box is a small stabilizing solution of about 17cm x 14cm x 16.5cm and a relatively large bleach-fixing agent of about 18.5. It becomes cm x 30.5 cm x 22.5 cm, and can only be stacked with the same type of replenisher for storage, transportation or in the store, and eventually requires a lot of space.
[0017]
A third drawback is the problem of disposal of empty containers. In recent years, environmental conservation and resource saving have been strongly demanded mainly in Europe and the United States, and disposal of plastic containers has become a problem especially in relation to photography. Although plastic containers for photography are cheap and convenient for storage and transportation and have excellent chemical resistance, poly containers are hardly biodegradable and accumulate, and when incinerated, a large amount of carbon dioxide is generated. In addition, it contributes to global warming, acid rain, etc., and as a user's problem, a large amount of plastic containers are piled up in a narrow work space, and it can not be crushed due to its strength. Problems such as narrow space are pointed out.
[0018]
Fourth, the chemical is very unstable.
[0019]
Normally, the life of the replenisher is 2 weeks, even with a floating lid. However, recently, the replenishment amount of each processing solution has been reduced, and 10 L of replenishing solution has been used for more than one month in minilabs that process orders for 30 color films on average per day.
[0020]
In such cases, it often happens that the replenisher in the replenisher tank is much more exposed to the air than the treatment liquid in the treatment tank, and it has deteriorated, so it does not make any sense to replenish. . Therefore, a device for reducing the replenishment tank to 5 L and a device for reducing the storage unit of the replenishment kit to 5 L have been devised. In this case, there is a further disadvantage that a packaging material is required.
[0021]
Another example is a color paper color developer replenisher. When preparing a color paper color developer replenisher, a certain amount of water is placed in a replenisher tank, and then a preservative-containing concentration kit A is placed. Stir, then add color developing agent-containing concentration kit B and stir, then add alkali agent-containing concentration kit C and stir, and finally add water to make a certain amount. At that time, several problems are likely to occur. For example, if stirring is inadequate or if you forget to add the first water, the color developing agent crystals are likely to precipitate, and the photographic performance becomes unstable because it accumulates in the bellows pump and is not replenished. Or the bellows pump is damaged. In addition, the concentration kit is not used immediately after manufacture, but may be used after one year from manufacture. In some cases, the color developing agent and the preservative are oxidized and the performance becomes unstable.
[0022]
Color developer replenishers made from concentrating kits and powders also have some problems in the replenishment tank. For example, if the replenisher is not used over a long period of time, crystals will adhere to the wall surface of the replenisher tank, the replenisher will be easily oxidized, and tar will be generated. Also, depending on the storage conditions, there is a problem that components that tend to crystallize in the replenisher, such as color developing agents, precipitate at low temperatures. For this reason, some manufacturers specify the replenisher storage conditions and manage it by the user. The actual situation is teaching.
[0023]
As described above, the method for preparing a replenisher using a commonly used concentration kit, or the method for preparing a replenisher using a powder, is the same as described above even when a color paper color developer is taken as an example. There are similar problems even with bleach-fixing solutions, bleaching solutions, and fixing solutions. For example, a bleach-fixing solution has a characteristic that storage stability is extremely poor. This is because the bleach-fixing process is carried out immediately after the color developer having a high pH, and usually this alkaline color developer is brought in by the paper to be processed, so it has a high acidity and a very low pH for the purpose of neutralization. It is customary. At low pH, it is said that the bleach-fixing solution composed of thiosulfate and an oxidizing agent has remarkably poor storage stability and cannot be replenished at a low replenishment rate. In addition, the same applies to the fixing solution and the stabilizing solution.
[0024]
Another problem is that recent replenishers are concentrated only to the limit of solubility as the replenishers are only concentrated while lowering and speeding up.
[0025]
This not only deteriorates the storage stability of the replenisher, but also has many practical problems such as crystal precipitation.
[0026]
On the other hand, a method of directly replenishing the concentration kit is known separately from the method of preparing the replenisher using the concentration kit or powder as described above.
[0027]
In this method, in order to improve the inefficiency of the dissolving operation, the concentration kit is directly replenished to the treatment tank using a supply means such as a bellows pump, and a certain amount of water replenishment is performed independently. Certainly, this method does not require preparation work as compared with the method of adjusting the replenisher from the above-described concentration kit or powder. Alternatively, since no replenisher is prepared, the problem of storage stability is eliminated.
[0028]
However, the present inventors have found that the above method also has many problems. That is, in order to supply the concentration kit, a tank for the concentration kit and a pump as a supply means are newly required, and this is a problem that the self-acting machine becomes larger. For example, consider CPK-2-20, which is a color paper processing solution. There are three parts for the color developer replenisher concentration kit, three parts for the bleach-fixing replenisher concentration kit, and concentration of the stable replenisher solution. There are two parts of the kit. To supply this kit, 8 tanks for the concentration kit and 8 pumps are required. In the case of the conventional replenishing method, it is sufficient if there are a tank and a pump for each replenishing solution, so three are sufficient for each. Even if only the concentration kit is supplied in this way, a larger number of tanks and pumps are required compared to the conventional method, and a pump for adjusting water is also required. In addition, the accuracy of the bellows pump is not so high, and it is difficult to discharge a plurality of liquids simultaneously with high accuracy, and there is a drawback that a component is crumpled.
[0029]
Furthermore, the concentration kit is difficult to maintain due to the concentration of crystals in the vicinity of the outlet of the replenishing nozzle because of the concentrated solution. In addition, the bellows pump does not have such a high supply accuracy, and in the case of replenishing concentrated liquid, there is a problem that the replenishment accuracy is further greatly shifted, resulting in a large variation in photographic performance. Another problem is that the conventional method of supplying the waste plastic container and the amount of the waste plastic container does not change because of the method of supplying the concentration kit.
[0030]
Several proposals have been made to eliminate the plastic container and improve the chemical stability of the replenisher by methods other than those described above.
[0031]
For example, Japanese Patent Application Laid-Open No. 58-11032 discloses a technique for wrapping developing components in microcapsules, and Japanese Patent Application Laid-Open No. 51-61837 discloses a photographic tablet containing a disintegrant. Further, JP-A Nos. 2-109042, 2-109043, 3-39735 and 3-39739 disclose a method using a granulated photographic processing agent having a certain average particle size. ing.
[0032]
A photographic tablet containing a disintegrant described in JP-A-51-61837 is merely a tablet that can be easily dissolved in water, and the solid processing agent is directly dissolved in the processing tank of the present invention. Thoughts cannot be recalled at all.
[0033]
Japanese Patent Application Laid-Open No. 2-109042 describes a granulated photographic processing agent having a certain average particle diameter.
[0034]
However, the above-mentioned publication does not propose that a self-acting machine eliminates the work of dissolving the replenishing solution to sufficiently simplify workability and obtain stable photographic performance, or eliminates the replenishing tank and proposes a compact self-acting machine.
[0035]
On the other hand, as a method of eliminating the need for a prior dissolution operation, a paste-like part in an amount corresponding to the mixing ratio of the part is extruded from each unit container in Japanese Patent Application Laid-Open No. 3-11344, and the extruded part Although a technique for accurately adjusting and supplying the composition by diluting the composition to a predetermined concentration is disclosed, the dissolution work is certainly reduced or almost eliminated by this method. Since it contains a solvent, it is not stable, it is difficult to extrude a certain amount over a long period of time, and if it is not used frequently, the nozzle is easily clogged, and it is difficult to keep the photographic performance constant. In addition, a container for the paste is required. In this case, a material that is flexible and difficult to break is required, and generally a composite material that is difficult to reuse is used, which is not environmentally favorable. In particular, it is known that pasty chemicals are often pasted with an organic solvent and are not so preservable.
[0036]
Japanese Utility Model Laid-Open No. 1-85732 discloses an automatic developing machine having means for adding a tablet-type antibacterial agent to a stabilizing solution. Therefore, there is no need to control the charging, which is not reminiscent of the processing agent replenishment control means, and it is not essential since the liquid itself is preserved.
[0037]
WO 91-07698 and WO 91-07699 disclose a method in which CD-3 or CD-4 is added as a solid, and other components are added as an activator, but this patent relates to regeneration. In particular, it is an invention related to low replenishment that is almost as close as no overflow. After adsorbing and removing bromide ions and chloride ions from the developer with an ion exchange resin, the alkali agent activator, which is a deficient component, or a solid or small amount of concentrated color development This is a method for adding ingredients without adding the active ingredient and increasing the volume.
[0038]
Japanese Patent Application Laid-Open No. 4-213454 describes that a powdery treatment agent is directly put into an auxiliary tank of an automatic machine. However, this does not describe the dissolution time of the powdery processing agent, and does not specifically describe the method of adding the processing agent to the photosensitive material to be processed. In the case of the conventional liquid replenisher method, in order to keep the processing solution in the processing tank constant, the components that are eluted and accumulated from the processed photosensitive material are diluted or consumed by the processed photosensitive material It was mainly playing a role to supplement. On the other hand, in the case of a method in which the solid processing agent is directly added to the processing liquid in the processing tank, it is for supplementing consumption components, and the role of diluting the accumulated components is to be performed by supplementary water. is there.
[0039]
However, the solid processing agent must be dissolved in the processing tank. In general, the faster the dissolution time, the faster it is usually considered to be better, but if the dissolution time when the solid processing agent is directly added to the processing solution is too fast, the consumption components in the processing tank are temporarily added excessively. Therefore, there is a problem in that the balance between consumption and supply due to processing of the photosensitive material is lost, resulting in variations in processability and poor stability. As a countermeasure, a method of reducing the amount of solid processing agent input and increasing the input frequency can be considered, but in this case, since the replenishment frequency increases, the load on the solid processing agent supply device also increases and the life of the device is shortened. The present inventors have found that another problem such as an increase in the number of packaging units arises in the case of a solid processing agent that is pre-dividedly weighed that is individually packaged in a tablet form or an input unit.
[0040]
If the dissolution time becomes too long, the supply of the solid processing agent becomes excessive compared to the dissolution time of the solid processing agent in the processing tank, and insoluble matter of the solid processing agent accumulates in the processing tank. The inventors have found that problems arise in which precipitates form.
[0041]
The present inventors discovered such a problem for the first time by repeating many experiments in the method of directly dissolving the solid processing agent in the processing tank.
[0042]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to first achieve the practical application of a solid processing agent that eliminates liquid chemicals that involve transportation and handling risks and eliminates complicated operations for users.
[0043]
Secondly, it is to provide a solid processing agent for completing a fully automated replenishment system by eliminating the work of dissolving the concentration kit by the user's own manual work.
[0044]
The third object is to provide a solid processing agent that does not impair processing stability and dissolves in a processing tank without causing precipitation in a solid processing agent that is directly charged into a processing solution.
[0045]
The fourth object is to provide a solid processing agent with improved processing stability that eliminates the necessity of storing a liquid replenisher.
[0046]
A fifth object is to achieve a low-pollution system that reduces the use of plastic packaging that eliminates the use of liquid plastic bottles.
[0047]
[Means for Solving the Problems]
The object is achieved by any one of the following configurations (1) to (10).
[0053]
( 1 ) Processing solution for automatic processing machine for silver halide photographic materials Solid processing agent Direct input Of processing silver halide photographic light-sensitive material In this case, the complete dissolution time S (min) of 1 weight unit of the solid processing agent and the amount R (m of silver halide photographic material processed per 1 weight unit of the solid processing agent ² )But
4 ≦ S / R ≦ 40 (min / m ² )
In the range Ruko And a method for processing a silver halide photographic material.
[0054]
( 2 The solid processing agent is a granulated or tableted tablet formed by a granulation step, and the solid processing agent is used as described above ( 1 The method for processing a silver halide photographic light-sensitive material described in the item).
[0055]
( 3 ) The solid processing agent is used in which the solid processing agent is pre-weighed. 1 Or 2 The method for processing a silver halide photographic light-sensitive material described in the item).
[0056]
( 4 ) The solid processing agent has a bulk density of 1.0 to 2.5 g / cm. ² A solid processing agent which is a tablet of 1 ), ( 2 Or 3 The method for processing a silver halide photographic light-sensitive material described in the item).
[0057]
( 5 (1) The solid processing agent contains a fluorescent sensitizer, 1 ), ( 2 ), ( 3 Or 4 The method for processing a silver halide photographic light-sensitive material described in the item).
[0058]
That is, the present inventors have stated that the above object is to provide a processing solution for a silver halide photographic material. Solid processing agent Direct input Of processing silver halide photographic light-sensitive material In this case, the complete dissolution time S (min) of 1 weight unit of the solid processing agent and the amount R (m of silver halide photographic material processed per 1 weight unit of the solid processing agent ² )But
4 ≦ S / R ≦ Four 0 (min / m ² )
Silver halide photographic light-sensitive material characterized by being in the range Processing method It has been found to be achieved by.
[0059]
The solid processing agent is directly charged into the processing liquid in the processing tank, but the processing liquid in the processing tank is always adjusted to the processing temperature and is maintained at a substantially constant temperature. That is, the dissolution speed is almost constant throughout the year.
[0060]
It was discovered that this has the great advantage that the insoluble phenomenon seen when dissolved in cold water does not appear. The insoluble phenomenon named by the present inventors is a solidification phenomenon that occurs when a solid treatment agent is poured into cold water all at once and slowly or hardly stirred. Then, it was found that even if vigorously stirred, it does not dissolve for a long time. On the other hand, such insoluble phenomenon could be greatly reduced by dissolving in hot water at the processing temperature of the automatic processor.
[0061]
However, as a result of further diligent investigations on the dissolution of the solid processing agent, the present inventors have determined that when the solid processing agent is directly charged into the processing tank, the total weight of the solid processing agent per one charge and the solids per one charge. It has been found that the amount of photosensitive material processed with a processing agent has an important relationship with processing stability and dissolution stability.
[0062]
Unlike the liquid type replenisher, when the solid processing agent is directly charged into the processing tank, the first stage requires a process for the solid processing agent to dissolve, and the second stage includes a process for making it uniform in the processing tank. is necessary.
[0063]
When the dissolution time is excessively fast, the dissolved part is extremely concentrated locally, and precipitation occurs before the process becomes uniform in the treatment tank.
[0064]
Further, it has been found that even when uniform, the processing stability is deteriorated because the balance between the consumption component by processing the photosensitive material in the processing tank and the supply component by the processing agent is lost.
[0065]
On the other hand, if the dissolution time is excessively slow, the supply of the solid processing agent becomes excessive from the dissolution time of the solid processing agent in the processing tank, and the insoluble matter of the solid processing agent accumulates in the processing tank. Dissolving phenomenon occurs even in temperature-controlled processing tanks. Eventually, insoluble substances accumulate in the processing tank, affecting the photosensitive material transport, and insoluble substances adhering to photosensitive materials. Was found to occur.
[0066]
In other words, the complete dissolution time S (min) of 1 weight unit of the solid processing agent charged directly into the processing tank is problematic even if it is too fast, and it is problematic if it is too slow. Yes, the amount of light-sensitive material processed per weight of the solid processing agent R (m ² ) And S found that there are more important laws.
[0067]
That is, 2 ≦ S / R ≦ 70 (min / m ² )
Particularly preferably 4 ≦ S / R ≦ 40 (min / m ² )
It was surprising that it was discovered for the first time that the above-mentioned problems could be solved with a solid processing agent satisfying the above, and that the unique merits of the solid processing agent could be put into practical use.
[0068]
Hereinafter, the present invention will be described in more detail.
[0069]
The solid processing agent referred to in the present invention is a powder processing agent as described above, a solid processing agent such as tablets, pills, granules, etc., and is subjected to moisture-proof processing as necessary. Pastes and slurries are semi-liquid and inferior in storage stability, and excluding those which are subject to regulations with the risk of transportation, and are not included in the solid processing agent of the present invention.
[0070]
The powder as referred to in the present invention means an aggregate of fine crystals. The granule as referred to in the present invention is a powder obtained by adding a granulation step, and means a granular material having a particle size of 50 to 5000 μm. The tablet referred to in the present invention refers to a powder or granule that has been compression molded into a certain shape.
[0071]
Among the solid processing agents, tablets are preferably used because of their high replenishment accuracy and easy handling.
[0072]
In order to solidify a photographic processing agent, a thick liquid or fine powder or granular photographic processing agent and a water-soluble binder are kneaded and molded, or a water-soluble binder is sprayed on the surface of a temporarily formed photographic processing agent. Any method can be adopted such as forming a coating layer by the method (Japanese Patent Laid-Open Nos. 4-29136, 4-85535, 4-85536, 4-85533, 4-85534, 4-172341).
[0073]
A preferable tablet production method is a method of granulating a powdery solid processing agent followed by a tableting process. There is an advantage that solubility and storage stability are improved and photographic performance is stabilized as a result, compared with a solid processing agent formed by a tableting process by simply mixing solid processing agent components.
[0074]
As the granulation method for tablet formation, known methods such as rolling granulation, extrusion granulation, compression granulation, pulverization granulation, stirring granulation, fluidized bed granulation, spray drying granulation and the like can be used. For tablet formation, the average particle size of the obtained granulated product is the dissolution time of the solid processing agent when the granulated product is mixed and pressed and compressed, so that component non-uniformity, so-called segregation is unlikely to occur. Is preferably 100 to 800 μm, more preferably 200 to 750 μm. Further, the particle size distribution is preferably such that 60% or more of the granulated particles are within a deviation of ± 100 to 150 μm. Next, when compressing and compressing the obtained granulated material, a well-known compressor, for example, a hydraulic press machine, a single shot type tableting machine, a rotary type tableting machine, and a briquetting machine can be used. The solid processing agent obtained by pressure compression can take any shape, but because the dissolution time is stable, or from the viewpoint of productivity and handling, or when used on the user side From the viewpoint of dust, a cylindrical type, so-called tablet is preferable.
[0075]
More preferably, at the time of granulation, the above effects become more remarkable by separately granulating each component, for example, alkali agent, reducing agent, bleaching agent, preservative and the like.
[0076]
For example, JP-A-51-61837, JP-A-54-155038, JP-A-52-88025, and British Patent No. 1213808 can be used to manufacture a tablet treatment agent. Furthermore, the granule treatment agent can be produced by a general method described in, for example, JP-A Nos. 2-109042, 2-109043, 3-39735 and 3-39739. Furthermore, the powder treating agent can be produced by a general method as described in, for example, JP-A Nos. 54-133332, British Patents 725892, 729862, and German Patent 3738661.
[0077]
The bulk density of the solid processing agent is 1.0 g / cm in the case of a tablet from the viewpoint of its solubility and the object effect of the present invention. ^Three ~ 2.5g / cm ^Three Is preferably 1.0 g / cm ^Three If it is larger, it is 2.5 g / cm in terms of strength of the solid material obtained. ^Three When smaller, it is more preferable at the solubility point of the solid substance obtained. When the solid processing agent is a granule or powder, the bulk density is 0.40 to 0.95 g / cm. ^Three Are preferred.
[0078]
The 1 weight unit of the solid processing agent referred to in the present invention means the total weight of the solid processing agent per one time to be replenished to each processing tank according to the processing information amount.
[0079]
For example, in the case where a plurality of types of solid processing agents are charged into an arbitrary processing tank as a part agent, the total weight of each part agent is one weight unit.
[0080]
The complete dissolution time S of 1 weight unit of the solid processing agent referred to in the present invention is completely dissolved from the time when the solid processing agent of 1 weight unit fed directly into the processing solution in the self-processing apparatus is charged in the processing tank. The complete dissolution means the state until the solid substance of the solid processing agent cannot be visually discriminated and is not the state until the dissolved substance becomes uniform in the treatment tank. Emphasize.
[0081]
Further, the temperature in the treatment tank may be adjusted at an arbitrary temperature, or a simple stirring function such as liquid circulation may be provided.
[0082]
The photosensitive material amount R processed per one weight of the solid processing agent in the present invention means the total area of the photosensitive material processed during the interval in which the solid processing agent per one weight is put into the processing tank.
[0083]
In the present invention, it is divided and weighed in advance, which means that it has already been divided and weighed into a predetermined amount before storing the processing agent in the present invention or before setting the packaging material storing the processing agent in the fixing means. For example, it refers to a mode in which tablets and pills of a predetermined size are formed, and a mode in which granules and powder are subdivided and packaged by a predetermined amount. It does not include a mode in which powder or granules are put in a storage means and the amount of one charge is measured at the time of supply. In a conventional replenisher supply and replenishment system, replenishment is performed by a bellows pump, but the accuracy of this pump is not constant and is not suitable for precise replenishment control. On the other hand, in the case of the present invention, the solid processing agent is, for example, weighed and divided into a certain amount at a processing agent production plant, and the replenishment control is ON / OFF control of whether or not to add the solid processing agent. There is no variation due to or dissolution time. Therefore, the accuracy of the treatment agent supply is remarkably high, and stable treatment performance can be obtained by this.
[0084]
When the solid processing agent is in powder form, the complete dissolution time S of the solid processing agent per weight unit used in the present invention depends on a material whose rate is limited as a solubility among the mixed materials. It is necessary to adjust by selection.
[0085]
When the solid processing agent is granular, it is necessary to adjust the material used in the granulation process and the average particle size of the granulated material in addition to the mixed material.
[0086]
Generally, since the dissolution time can be increased by increasing the surface area, the dissolution time can be increased for those having a small average particle size.
[0087]
When the solid processing agent is in the form of a tablet, it is necessary to adjust the tableting pressure and the surface area of the tablet in addition to the mixed material and granulation method. Generally, the tableting pressure and the dissolution time are in a linear relationship, and the dissolution time can be increased by increasing the tableting pressure.
[0088]
The solid processing agent used in the present invention is used for photographic processing agents such as color developers, black and white developers, bleaches, fixing agents, bleach-fixing agents, stabilizers, etc., but the effects of the present invention, in particular, the photographic performance is stabilized. A color developer is highly effective.
[0089]
Further, black and white developers, color developers, bleaches, bleach-fixers, and stabilizers can be excluded from the regulation of liquid dangerous goods.
[0090]
According to the embodiment of the present invention, it is most preferable that all the processing agents are solid processing agents, but it is preferable to solidify at least the color developer. That is, the color developer component contains a large number of components that cause chemical reactions with each other and also contains harmful components, so that the effects of the present invention are most prominent. More preferably, in addition to the color developer, the bleach-fixing agent, or the bleaching agent and the fixing agent are solid processing agents. These have conventionally been regarded as a problem in transportation by liquid packaging kits.
[0091]
It is within the scope of the present invention that the solid processing agent used in the present invention solidifies only one part of a component of a certain processing agent, but preferably all the components of the processing agent are solidified. It is desirable that each component is molded as a separate solid processing agent and is individually packaged. It is also desirable that the different components are packaged in the order in which they are periodically fed repeatedly.
[0092]
It is preferable to add all the processing agents to be replenished to each processing tank as solid processing agents according to the processing amount information. When replenishing water is required, the replenishing water is replenished based on the processing amount information or other replenishing water control information. In this case, the liquid to be replenished to the treatment tank can be only replenishment water. In other words, when there are two or more types of processing tanks that need to be replenished, only one tank can be used to store the replenishing liquid by sharing the replenishing water, and the automatic developing machine can be made compact. In particular, it is preferable to place one replenishing water tank outside in order to make the automatic machine compact.
[0093]
When the color developer is solidified, the solid used in the present invention is to convert all of the alkali agent, color developer and reducing agent into solid processing agents, and in the case of tablets, at least 4 agents are most preferable. This is a preferred embodiment of the treatment agent. In addition, when the solid treatment agent is divided into two or more agents, it is preferable that the plurality of tablets and granules are packaged in the same package.
[0094]
As moisture-proof packaging for tablets and pills, the following materials can be used.
[0095]
Synthetic resin materials include polyethylene (either high pressure method or low pressure method), polypropylene (either stretched or stretched), polyvinyl chloride, polyvinyl acetate, nylon (stretched, unstretched), polyvinylidene chloride, polystyrene Polycarbonate, vinylon, eval, polyethylene terephthalate (PET), other polyesters, hydrochloric acid rubber, acrylonitrile butadiene copolymer, epoxy-phosphate resin (polymers described in JP-A 63-63037, JP-A 57- No. 32952). Or a pulp may be sufficient.
[0096]
Usually, these films are laminated and adhered, but they may be applied layers.
[0097]
Furthermore, it is more preferable to use various gas barrier films, such as using an aluminum foil or an aluminum vapor-deposited synthetic resin between the above synthetic resin films.
[0098]
The total oxygen permeability of these laminated films is 50 ml / m. ² 24hr / atm or less (at 20 ℃ 65% RH), more preferably 30ml / m ² It is preferably 24 hr / atm or less.
[0099]
The total thickness of these laminated films is preferably 1 to 2000 μm, more preferably 10 to 1000 μm, and still more preferably 50 to 1000 μm.
[0100]
The above synthetic resin film may be a single (polymer) resin film or two or more laminated (polymer) resin films.
[0101]
As a single layer polymer resin film that meets the conditions of the present invention, for example,
(1) Polyethylene terephthalate (PET) with a thickness of 0.1 mm or more,
(2) an acrylonitrile butadiene copolymer having a thickness of 0.3 mm or more,
(3) Hydrochloric acid rubber having a thickness of 0.1 mm or more can be mentioned. Among them, polyethylene terephthalate is excellent in terms of alkali resistance and acid resistance, and can be suitably used in the present invention.
[0102]
Next, as a laminated polymer resin film suitable for the conditions of the present invention, for example,
(4) PET / polyvinyl alcohol / ethylene copolymer (eval) / polyethylene (PE),
(5) Expanded polypropylene (OPP) / Eval / PE,
(6) Unstretched polypropylene (CPP) / Eval / PE,
(7) Nylon (N) / Aluminum foil (Al) / PE,
(8) PET / Al / PE,
(9) Cellophane / PE / Al / PE,
(10) Al / paper / PE
(11) PET / PE / Al / PE,
(12) N / PE / Al / PE,
(13) Paper / PE / Al / PE,
(14) PET / Al / PET / polypropylene (PP),
(15) PET / Al / PET / high density polyethylene (HDPE),
(16) PET / Al / PE / low density polyethylene (LDPE),
(17) Eval / PP,
(18) PET / Al / PP,
(19) Paper / Al / PE,
(20) PE / PVDC-coated nylon / PE / ethyl vinyl acetate / polyethylene condensate (EVA),
(21) PE / PVDC coat N / PE,
(22) EVA / PE / aluminum-deposited nylon / PE / EVA
(23) Aluminum-deposited nylon / N / PE / EVA
(24) OPP / PVDC coat N / PE,
(25) PE / PVDC coat N / PE,
(26) OPP / Eval / LDPE,
(27) OPP / Eval / CPP,
(28) PET / Eval / LDPE,
(29) ON (stretched nylon) / Evar / LDPE,
(30) CN (unstretched nylon) / Eval / LDPE, etc. Among them, the above (20) to (30) are preferably used.
[0103]
As a more specific configuration of the packaging material, if the side in contact with the treatment agent is the inner surface, in order from the inner surface,
PE / main board / PE / Al / epoxy-phosphate resin layer / polyester resin layer / PE
PE / K-nylon / PE or adhesive / Al / PE / paperboard / PE,
PE / Vinylon / PE or Adhesive / Al / PE / Paperboard / PE
PE / vinylidene chloride / PE or adhesive / Al / PE / paperboard / PE
PE / polyester / PE or adhesive / Al / PE / paperboard / PE
Examples include polypropylene / K-nylon / polypropylene / Al / polypropylene / paperboard / polypropylene.
[0104]
As a method of moisture-proof packaging of tablets and granules,
4-way seal
3-way seal
Stick (pillow packaging, gusset packaging)
PTP
cartridge
There is.
[0105]
The four-side seal, three-side seal, and stick (pillow, gusset) packaging are different in form and the above materials are used. However, when used in a peel-open method, a sealant agent is laminated to give peel-open suitability.
[0106]
As the peel-open method, there are usually a cohesive failure method, an interface peeling method, and an interlayer peeling method.
[0107]
The cohesive failure method uses a hot melt adhesive (heat seal lacquer or the like) as a sealant, and peels off due to internal cohesive failure of the sealant layer when opened.
[0108]
The surface active peeling method is a method of peeling at the interface between films, and the sealing film (sealant) and the adherend are not completely fused and can be peeled off with an appropriate strength. The sealant is a film in which an adhesive resin is mixed, and polyethylene, polypropylene, a copolymer thereof, a polyester system, or the like can be selected depending on the material of the adherend.
[0109]
Further, the delamination method uses a multilayer coextruded film such as a laminate film to peel the sealant between the layers of the laminate film.
[0110]
In the peel open method using the film of the present invention, an interlayer peeling method or an interface peeling method is preferable.
[0111]
In addition, since such a sealant is thin, it is usually used by laminating other films such as polyethylene, polypropylene, polystyrene, polycarbonate, polyester (polyethylene terephthalate), polyvinyl chloride, nylon, eval, aluminum, etc. Preference is given to polyethylene, polypropylene, polyester, eval, etc. in consideration of environmental friendliness and matching with contents. In consideration of printability, the outermost surface is preferably unstretched polypropylene polyester or paper.
[0112]
Examples of the sealant film include Tosero, CMPS film, Dainippon Ink Diflan PP-100, PS-300 or Toppan Printing LTS film, Sanei Chemical's Sun Seal FR, Sun Seal MS, etc., already laminated with polyester Examples of such types include Declan C-1600T and C-1602T.
[0113]
PTP is a packaging form in which a solid processing agent is placed in a sheet of PVC, CPP or the like formed as a kind of blister packaging and heat-sealed with an aluminum sealing material.
[0114]
Environmentally, PVC is not used as a forming material, and recently, A-PET and highly moisture-proof PP (for example, TAS-1130, TAS-2230, TAS-3230: Taisei Kako Co., Ltd.) are preferably used.
[0115]
When the treatment agent is packaged or bound or coated with a water-soluble film or binder, the water-soluble film or binder may be polyvinyl alcohol, methyl cellulose, polyethylene oxide, starch, polyvinyl pyrrolidone, hydroxypropyl cellulose. Films made of base materials such as poly-, pullulan, dextran and gum arabic, polyvinyl acetate, hydroxyethyl cellulose, carboxyethyl cellulose, carboxymethyl hydroxyethyl cellulose sodium salt, poly (alkyl) oxazoline, polyethylene glycol Binders are preferably used, and among these, polyvinyl alcohol-based and pullulan-based ones are more preferably used from the viewpoint of coating or binding effects.
[0116]
Preferred polyvinyl alcohols are very good film forming materials and have good strength and flexibility under most conditions. Commercial polyvinyl alcohol compositions cast as films vary in molecular weight and degree of hydrolysis, but preferably have a molecular weight of about 10,000 to about 100,000. The degree of hydrolysis is the ratio at which the acetate group of polyvinyl alcohol is replaced with a hydroxyl group. For application to films, the range of hydrolysis is usually about 70% to 100%. Thus, the term polyvinyl alcohol usually includes polyvinyl acetate compounds.
[0117]
These water-soluble film production methods are described, for example, in JP-A-2-124945, JP-A-61-97348, JP-A-60-158245, JP-A-2-86638, JP-A-57-117867, JP-A-5-117867. No. 2-75650, JP-A-59-226018, JP-A-63-218741 and JP-A-54-13565, etc., and the like.
[0118]
Furthermore, as these water-soluble films, those commercially available under the names of SOLBRON (manufactured by Aicero Chemical Co., Ltd.), HYCELON (manufactured by Nichigo Film Co., Ltd.), or Pullulan (manufactured by Hayashibara Co., Ltd.) can be used. Also, the 7-000 series polyvinyl alcohol film available from the MONO-SOL division of Chris Craft Industries Inc. dissolves at a water temperature of about 34 degrees F to about 200 degrees F, is harmless, It exhibits a high chemical resistance and is particularly preferably used.
[0119]
The film thickness of the water-soluble film is preferably 10 to 120 μm, particularly 15 to 80 μm in terms of storage stability of the solid processing agent, dissolution time of the water-soluble film and crystal precipitation in the automatic processor. Particularly preferred are those of 20 to 60 μm.
[0120]
The water-soluble film is preferably thermoplastic. This is because the heat sealing process and the ultrasonic welding process are facilitated, and the covering effect is also improved.
[0121]
Furthermore, the tensile strength of water-soluble film is 0.5 × 10 ⁶ ~ 50 × 10 ⁶ kg / m ² Is preferred, especially 1 × 10 ⁶ ~ 25 × 10 ⁶ kg / m ² Are preferred, especially 1.5 × 10 ⁶ ~ 10 × 10 ⁶ kg / m ² Is preferred. These tensile strengths are measured by the method described in JIS Z-1521.
[0122]
Photographic processing agents that are packaged, bound, or coated with a water-soluble film or binder may also be used during storage, transportation, and handling, in atmospheric humidity such as high humidity, rain, and fog, and water splashes or In order to prevent damage from sudden contact with water by wet hands, it is preferably wrapped in a moisture-proof packaging material, and as the moisture-proof packaging material, a film with a film thickness of 10 to 150 μm is preferable, and the moisture-proof packaging material is Polyolefin film such as polyethylene terephthalate, polyethylene, polypropylene, Kraft paper, wax paper, moisture-resistant cellophane, glassine, polyester, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyamide, polycarbonate, acrylonitrile and A few selected from metal foils such as aluminum, metallized polymer films At least one is preferable, and a composite material using these may be used.
[0123]
In the practice of the present invention, it is also preferable that the moisture-proof packaging material is a degradable plastic, particularly a biodegradable or photodegradable plastic.
[0124]
The biodegradable plastic is composed of (1) natural polymer, (2) microorganism-producing polymer, (3) synthetic polymer with good biodegradability, (4) blending of biodegradable natural polymer into plastic, etc. Examples of the photodegradable plastic include (5) those having a group present in the main chain that is excited by ultraviolet rays and leads to cleavage. In addition to the polymers listed above, those having two functions of photodegradability and biodegradability can also be used favorably.
[0125]
Each of these specific representative examples is as follows.
[0126]
As a biodegradable plastic,
(1) Natural polymer
Polysaccharides, cellulose, polylactic acid, chitin, chitosan, polyamino acids, or modified products thereof
(2) Microbial production polymer
“Biopol” containing PHB-PHV (a copolymer of 3-hydroxybutyrate and 3-hydroxyvalerate) as a component, cellulose produced by microorganisms, etc.
(3) Synthetic polymer with good biodegradability
Polyvinyl alcohol, polycaprolactone, etc., or a copolymer or mixture thereof
(4) Blending of biodegradable natural polymer into plastic
Examples of natural biodegradable natural polymers include starch and cellulose, which have been given shape-disintegrating properties in addition to plastic.
[0127]
Examples of the photodegradability (5) include the introduction of a carbonyl group for photodegradability, and an ultraviolet absorber may be added to further promote the degradation.
[0128]
Such degradable plastics are generally described in “Chemical and Industrial”, Vol. 64, No. 10, pages 478-484 (1990), “Functional Materials”, July 1990, pages 23-34, etc. Can be used. In addition, Biopol (manufactured by ICI), Eco (manufactured by Union Carbide), Ecolite (manufactured by Eco Plastic), Ecostar (manufactured by St. Lawrence Starch), Commercially available degradable plastics such as knuckle P (manufactured by Nihon Unicar) can be used.
[0129]
The moisture-proof packaging material preferably has a moisture permeability coefficient of 10 g · mm / m ² 24 hr or less, more preferably 5 g · mm / m ² 24 hours or less.
[0130]
As the supply means for supplying the solid processing agent to the processing tank in the present invention, for example, when the solid processing agent is a tablet, Japanese Utility Model Laid-Open Nos. 63-137783, 63-97522, 1-85732 There are known methods such as a gazette, but in short, any method may be used as long as the function of supplying tablets to the processing tank is provided at a minimum. When the solid processing agent is a granule or a powder, Japanese Utility Model Laid-Open Nos. 62-81964, 63-84151, and Japanese Patent Application Laid-Open No. 1-292375, the gravity drop method described in Japanese Utility Model Laid-Open No. 63-105159, 63 -195345 and the like are known methods, but are not limited thereto.
[0131]
However, a preferable method is a method for supplying the solid processing agent to the processing tank, for example, a method in which a predetermined amount of the solid processing agent that has been weighed in advance and divided and packaged is opened and taken out according to the processing amount of the photosensitive material. Conceivable. Specifically, the solid processing agent is sandwiched and accommodated in a package composed of at least two packaging materials in a predetermined amount, preferably in a single replenishment amount, and the package is separated in two directions or the package Open a part to make it ready for removal. The solid processing agent in a state where it can be taken out can be easily supplied to a processing tank having a filtering means by natural dropping. Since a predetermined amount of the solid processing agent is stored in a separately sealed package so that the air permeability between the outside air and the adjacent solid processing agent is blocked, moisture resistance is guaranteed if it is not opened.
[0132]
As an embodiment, a configuration in which a package made of at least two packaging materials so as to sandwich the solid processing agent is in close contact with or adhered to each other so that the periphery of the solid processing agent can be separated is conceivable. By pulling the packaging materials sandwiching the solid processing agent in different directions, the contact surfaces that are in close contact with or bonded to each other are separated, and the solid processing agent can be taken out.
[0133]
As another embodiment, a configuration is conceivable in which at least one of the packaging bodies made of at least two packaging materials can be opened by an external force so as to sandwich the solid processing agent. The term “opening” as used herein refers to a cut or break leaving a part of the packaging material. As the unsealing method, the solid processing agent is forcibly pushed out by applying a compressive force from the unopened side package body to the openable package body through the solid processing agent, or the unpackable side packaging body. It is conceivable that the solid processing agent can be taken out by cutting with a sharp member.
[0134]
The supply start signal is obtained by detecting processing amount information. Further, the driving means for separating or opening is operated based on the obtained supply start signal. The supply stop signal is obtained by detecting information that a predetermined amount of supply has been completed. Further, based on the obtained supply stop signal, the drive means for separating or opening is controlled to stop.
[0135]
The solid processing agent supply means has a control means for supplying a fixed amount of the solid processing agent in accordance with the processing amount information of the photosensitive material, which is an important requirement in the present invention. That is, in the automatic processor of the present invention, it is necessary to keep the component concentration in each processing tank constant and stabilize the photographic performance. The processing amount information of the silver halide photographic light-sensitive material means the processing amount of the silver halide photographic light-sensitive material processed with the processing solution, the processing amount of the processed silver halide photographic light-sensitive material, or the silver halide photograph being processed. The value is proportional to the processing amount of the light-sensitive material, and indirectly or directly indicates the amount of reduction of the processing agent in the processing solution. The light-sensitive material may be detected at any timing before, after, or during immersion in the processing solution. Alternatively, the amount of photosensitive material printed by a printer may be used. Further, it may be the concentration or concentration change of the processing liquid stored in the processing tank. Further, it may be the amount discharged outside after the treatment liquid is dried.
[0136]
The place where the solid processing agent of the present invention is charged may be in the processing tank, but preferably the place where the processing solution is circulated between the processing part communicating with the processing part for processing the photosensitive material. Further, a structure in which a certain amount of processing liquid is circulated between the processing unit and the dissolved component moves to the processing unit is preferable. The solid processing agent is preferably introduced into a temperature-controlled processing solution.
[0137]
As the color developing agent used in the color developer in the present invention, a p-phenylenediamine compound having a water-soluble group is preferably used because it achieves the object effects of the present invention and generates less fog.
[0138]
A p-phenylenediamine compound having a water-soluble group is less contaminated with a light-sensitive material than a paraphenylenediamine compound having no water-soluble group such as N, N-diethyl-p-phenylenediamine. Not only has the advantage of being less susceptible to fogging, but the object of the present invention can be achieved more efficiently by combining with the color developer of the present invention.
[0139]
Examples of the water-soluble group include those having at least one on the amino group or benzene nucleus of the p-phenylenediamine compound, and specific water-soluble groups include:
− (CH ₂ ) _n −CH ₂ OH,
− (CH ₂ ) _m -NHSO ₂ − (CH ₂ ) _n CH _Three ,
− (CH ₂ ) _m −O− (CH ₂ ) _n −CH _Three ,
− (CH ₂ CH ₂ O) _n C _m H _{2m + 1} (M and n each represents an integer of 0 or more), —COOH group, —SO _Three The H group and the like are preferable.
[0140]
Specific examples of the color developing agent preferably used in the present invention include (C-1) to (C-16) described in Japanese Patent Application No. 2-203169, pages 26 to 31. .
[0141]
The color developing agent is usually used in the form of a salt such as hydrochloride, sulfate or p-toluenesulfonate.
[0142]
The color developing agents may be used alone or in combination of two or more, and optionally used in combination with black and white developing agents such as phenidone, 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone and metol. May be.
[0143]
In the present invention, it is more preferable that the compound represented by the following general formulas [A] and [B] is contained in the color developer according to the present invention.
[0144]
That is, when it is converted into a solid processing agent, it is effective not only in improving the storage stability of the solid processing agent such as a tablet but also maintaining the strength as compared with other compounds, and is stable in photographic performance and in an unexposed area. There is also an advantage that less fog occurs.
[0145]
[Chemical 1]

[0146]
In general formula [A], R ₁ And R ₂ Are simultaneously not hydrogen atoms, alkyl groups, aryl groups,
[0147]
[Chemical formula 2]

[0148]
Or represents a hydrogen atom, but R ₁ And R ₂ May be the same or different, and an alkyl group having 1 to 3 carbon atoms is preferable. Furthermore, these alkyl groups may have a carboxylic acid group, a phosphoric acid group, a sulfonic acid group, or a hydroxyl group.
[0149]
R ′ represents an alkoxy group, an alkyl group or an aryl group. R ₁ , R ₂ And the alkyl group and aryl group of R ′ include those having a substituent, ₁ And R ₂ May combine to form a ring, and for example, may form a heterocyclic ring such as piperidine, pyridine, triazine or morpholine.
[0150]
[Chemical 3]

[0151]
Where R ₁₁ , R ₁₂ , R ₁₃ Represents a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, or a heterocyclic group, and R ₁₄ Represents a hydroxy group, a hydroxyamino group, a substituted or unsubstituted alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, carbamoyl group, or amino group. The heterocyclic group is a 5- to 6-membered ring and is composed of C, H, O, N, S and a halogen atom, and may be saturated or unsaturated. R ₁₅ Is -CO-, -SO ₂ -Or
[0152]
[Formula 4]

[0153]
Represents a divalent group selected from: n is 0 or 1; Especially when n = 0 ₁₄ Represents a group selected from an alkyl group, an aryl group, and a heterocyclic group, and R ₁₃ And R ₁₄ May form a heterocyclic group together.
[0154]
Specific examples of the hydroxylamine compound represented by the general formula [A] are described in U.S. Pat. Nos. 3,287,125, 33,293,034, and 3,287,124. (A-1) to (A-39) described on pages 36 to 38 of the specification of 2-203169 and (1) to (53) described on pages 3 to 6 of specification of JP-A-3-33845 and (1)-(52) of 3-63646 specification 5-7 pages are mentioned.
[0155]
Next, specific examples of the compound represented by the general formula [B] include (B-1) to (B-33) described in Japanese Patent Application No. 2-203169, pages 40 to 43, and JP-A-3-33846. (1) to (56) described on pages 4 to 6 of the specification.
[0156]
These compounds represented by general formula [A] or general formula [B] are usually in the form of free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate, etc. Used.
[0157]
A small amount of sulfite can be used as a preservative in the color developer and black-and-white developer used in the present invention. Examples of the sulfite include sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite and the like.
[0158]
The color developer and black-and-white developer used in the present invention require the use of a buffer. Examples of the buffer include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, and phosphoric acid. Tripotassium, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (boric acid), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, 5- Examples include sodium sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate).
[0159]
As development accelerators, thioether compounds represented by JP-B-37-16088, JP-A-37-5987, JP-A-38-7826, JP-A-44-12380, JP-A-45-9019 and U.S. Patent 3,813,247, P-phenylenediamine compounds represented in JP-A-52-49829 and JP-A-50-15554, JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52- Quaternary ammonium salts represented by No. 43429, etc., p-aminophenols described in U.S. Pat.Nos. 2,610,122 and 4,119,462, U.S. Pat. No. 2, U.S. Pat.Nos. 2,482,546, 2,596,926, and 3,582,346, etc. 23883 and U.S. Pat.No. 3,532,501 etc., polyalkylene oxides, other 1-phenyl-3-pyrazolidones, hydrodins, mesoio An ionic compound, an ionic compound, imidazoles, and the like can be added as necessary.
[0160]
The color developer preferably contains substantially no benzyl alcohol. Substantially means 2.0 ml or less, more preferably not contained at all in terms of 1 liter of color developer. When it is not substantially contained, the variation in photographic characteristics during continuous processing, particularly the increase in stain is small, and a more preferable result can be obtained.
[0161]
In order to prevent fogging, chlorine ions and bromine ions are required in the color developer in the processing tank. In the present invention, from the viewpoint of fluctuations in development speed, stain, and minimum density, it is preferably 1.0 × 10 6 as chloride ions. ^-2 ~ 1.5 × 10 ^-1 Mol / l, more preferably 4 × 10 ^-2 ~ 1 × 10 ^-1 Contains mol / l. Therefore, the solid processing agent is preferably adjusted so that the color developer in the processing tank is in the above-mentioned concentration range.
[0162]
In the present invention, the color developer in the processing tank preferably contains bromide ions in terms of development speed, maximum density, sensitivity and minimum density, preferably 3.0 × 10. ^-3 ~ 1.0 × 10 ^-3 Contains mol / l. More preferably 5.0 × 10 ^-3 ~ 5 × 10 ^-Four Mol / l. Especially preferably 1 × 10 ^-Four ~ 3 × 10 ^-Four Mol / l. Similarly to chlorine ions, it is preferable to adjust the bromine concentration in the solid processing agent to be in the above range.
[0163]
When added directly to the color developer, the chloride ion supplying substances include sodium chloride, potassium chloride, ammonium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride. , Potassium chloride.
[0164]
Further, it may be supplied in the form of a salt against a color developer and a fluorescent brightener added to the developer. Sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Of these, potassium bromide and sodium bromide are preferred.
[0165]
An optional antifoggant can be added to the color developer and developer used in the present invention, if necessary, in addition to chlorine ions and bromine ions. As the antifoggant, alkali metal halides such as potassium iodide and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, 2-thiazolyl-benzimidazole, Nitrogen-containing heterocyclic compounds such as 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine can be given as representative examples.
[0166]
The color developer and developer used in the present invention preferably contain a triazinyl stilbene fluorescent whitening agent from the viewpoint of the object effect of the present invention. As the fluorescent brightening agent, a compound represented by the following general formula [E] is preferable.
[0167]
[Chemical formula 5]

[0168]
Where X ₂ , X _Three , Y ₁ And Y ₂ Are each a hydroxyl group, a halogen atom such as chlorine or bromine, an alkyl group, an aryl group,
[0169]
[Chemical 6]

[0170]
Or -OR _{twenty five} Represents. Where R _{twenty one} And R _{twenty two} Are each a hydrogen atom, an alkyl group (including a substituent), or an aryl group (including a substituent), R _{twenty three} And R _{twenty four} Represents an alkylene group (including a substituent), R _{twenty five} Represents a hydrogen atom, an alkyl group (including a substituent) or an aryl group (including a substituent), and M represents a cation.
[0171]
The details of each group of the general formula [E] or their substituents are the same as those described in Japanese Patent Application No. 2-240400 from page 63, line 8 to page 64, line 3 to line 3.
[0172]
Specific examples of the compound represented by the general formula [E] are given below.
[0173]
[Chemical 7]

[0174]
[Chemical 8]

[0175]
[Chemical 9]

[0176]
[Chemical Formula 10]

[0177]
Embedded image

[0178]
Embedded image

[0179]
Said compound is compoundable by a well-known method. Among the above exemplified compounds, E-4, E-24, E-34, E-35, E-36, E-37 and E-41 are particularly preferably used. It is preferable to adjust the solid processing agent so that the amount of these compounds added is in the range of 0.2 g to 10 g per liter of the color developer, and more preferably in the range of 0.4 g to 5 g.
[0180]
Further, the color developer and the black-and-white developer composition used in the present invention include, as necessary, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, other JP-B-47-33378 and 44- The compounds described in each publication No. 9509 can be used as an organic solvent for increasing the solubility of the developing agent.
[0181]
Further, an auxiliary developer can be used together with the developing agent. As these auxiliary developers, for example, metol, phenidone, N, N-diethyl-p-aminophenol hydrochloride, N, N, N ′, N′-tetramethyl-p-phenylenediamine hydrochloride and the like are known. Yes.
[0182]
Furthermore, various additives such as other stain inhibitors, sludge inhibitors, and multilayer effect accelerators can be used.
[0183]
The color developer and black-and-white developer composition is represented by the following general formula [K] described in Japanese Patent Application No. 2-240400, page 63, bottom line 8 to page 64, bottom line 3 It is preferable from the viewpoint of effectively achieving the object of the present invention that the chelating agent and its exemplified compounds K-1 to K-22 are added.
[0184]
Embedded image

[0185]
Among these chelating agents, K-2, K-9, K-12, K-13, K-17, K-19 are particularly preferably used, and in particular, K-2 and K-9 are particularly preferred in the present invention. The effect of is excellent.
[0186]
The addition amount of these chelating agents is preferably added to the solid processing agent so as to be in the range of 0.1 to 20 g per liter of the color developer and black-and-white developer, and more preferably in the range of 0.2 to 8 g.
[0187]
Furthermore, the color developer and the black-and-white developer can contain anionic, cationic, amphoteric, and nonionic surfactants.
[0188]
Moreover, you may add various surfactants, such as alkylsulfonic acid, arylsulfonic acid, aliphatic carboxylic acid, and aromatic carboxylic acid, as needed.
[0189]
A bleaching agent preferably used in the bleaching agent or bleach-fixing agent according to the present invention is a ferric complex salt of an organic acid represented by the following general formula [C].
[0190]
Embedded image

[0191]
[Where A ₁ ~ A _Four May be the same or different, and -CH ₂ OH, -COOM or -PO _Three M ₁ M ₂ Represents. M, M ₁ , M ₂ Each represents a hydrogen atom, an alkali metal or ammonium. X represents a substituted or unsubstituted alkylene group having 3 to 6 carbon atoms. ]
The compound represented by the general formula [C] is described in detail below.
[0192]
In the formula, A ₁ ~ A _Four No. 1-260628, page 15 from page 12 to line 15 from page 15 to line 3 ₁ ~ A _Four The detailed description will be omitted.
[0193]
The ferric complex salt of the organic acid represented by the general formula [C] has a high bleaching capacity, so it requires only a small amount to be used for solidification. There is an effect that the preservability of the treatment agent is improved, and it is preferably used in the present invention.
[0194]
Specific examples of preferable compounds represented by the general formula [C] are shown below.
[0195]
Embedded image

[0196]
Embedded image

[0197]
As the ferric complex salts of the compounds (C-1) to (C-12), sodium salts, potassium salts or ammonium salts of these ferric complex salts can be arbitrarily used. From the viewpoint of the object effect and solubility of the present invention, ammonium salts of these ferric complex salts are preferably used.
[0198]
Among the above compound examples, (C-1), (C-3), (C-4), (C-5), and (C-9) are particularly preferably used in the present invention. Particularly preferred is (C-1).
[0199]
In the present invention, for the bleaching agent or the bleach-fixing agent, a ferric complex salt of the following compound can be used as a bleaching main agent in addition to the iron complex salt of the compound represented by the above general formula [C].
[0200]
[A'-1] Ethylenediaminetetraacetic acid
[A'-2] trans-1,2-cyclohexanediaminetetraacetic acid
[A'-3] Dihydroxyethylglycine acid
[A'-4] Ethylenediaminetetrakismethylenephosphonic acid
[A'-5] nitrilotrismethylenephosphonic acid
[A'-6] Diethylenetriaminepentakismethylenephosphonic acid
[A'-7] Diethylenetriaminepentaacetic acid
[A'-8] Ethylenediaminedioltohydroxyphenylacetic acid
[A'-9] Hydroxyethylethylenediaminetriacetic acid
[A'-10] Ethylenediaminedipropionic acid
[A'-11] Ethylenediaminediacetic acid
[A'-12] Hydroxyethyliminodiacetic acid
[A'-13] nitrilotriacetic acid
[A'-14] nitrilotripropionic acid
[A'-15] Triethylenetetramine hexaacetic acid
[A'-16] Ethylenediaminetetrapropionic acid
[A'-17] β-alanine diacetate
The amount of the organic acid ferric complex salt added is preferably in the range of 0.01 mol to 2.0 mol, more preferably in the range of 0.05 to 1.5 mol / l, per liter of the bleaching solution or bleach-fixing solution. Therefore, the solid processing agent is preferably adjusted so that the concentration of the organic acid ferric complex salt in the bleaching solution or the bleach-fixing solution in the processing tank is within the above range.
[0201]
Examples of the bleaching agent, the bleach-fixing agent, and the fixing agent include imidazole and derivatives thereof described in JP-A No. 64-295258, or compounds represented by the general formulas [I] to [IX] described in the same specification and these compounds. By containing at least one of the exemplified compounds, an effect on rapidity can be obtained.
[0202]
In addition to the above accelerators, the exemplified compounds described on pages 51 to 115 of JP-A-62-123459 and the pages described on pages 22 to 25 of JP-A-63-17445 Exemplified compounds, compounds described in JP-A Nos. 53-95630 and 53-28426, and the like can be used in the same manner.
[0203]
In addition to the above, the bleaching agent or bleach-fixing agent may contain halides such as ammonium bromide, potassium bromide, and sodium bromide, various optical brighteners, antifoaming agents, and surfactants.
[0204]
As the main fixing agent used in the fixing agent or bleach-fixing agent in the present invention, thiocyanate and thiosulfate are preferably used. The content of thiocyanate is preferably at least 0.1 mol / l or more per liter of the fixing solution or bleach-fixing solution, more preferably 0.5 mol / l or more, particularly preferably 1.0 mol / l or more when processing a color negative film. It is. The content of thiosulfate is preferably at least 0.2 mol / l or more, and more preferably 0.5 mol / l or more when processing a color negative film. In the present invention, the object of the present invention can be achieved more effectively by using thiocyanate and thiosulfate together.
[0205]
The fixing agent or bleach-fixing agent used in the present invention may contain one or more pH buffering agents composed of various salts in addition to these fixing main agents. Further, it is desirable to contain a large amount of a rehalogenating agent such as an alkali halide or ammonium halide such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide. Further, compounds known to be added to normal fixing agents or bleach-fixing agents such as alkylamines and polyethylene oxides can be appropriately added.
[0206]
To the fixing agent or the bleach-fixing agent, it is preferable to add a compound represented by the following general formula [FA] described in JP-A No. 64-295258, page 56, and this exemplified compound. In addition to the better performance, there is another effect that sludge generated in a processing solution having fixing ability when processing a small amount of light-sensitive material over a long period of time is extremely small.
[0207]
Embedded image

[0208]
The compound represented by the general formula [FA] described in the specification can be synthesized by a general method as described in US Pat. No. 3,335,161 and US Pat. No. 3,260,718. These compounds represented by the general formula [FA] may be used alone or in combination of two or more.
[0209]
Further, good results can be obtained when the amount of the compound represented by the general formula [FA] is in the range of 0.1 g to 200 g per liter of the fixing solution or bleach-fixing solution.
[0210]
In the present invention, the stabilizing solution preferably contains a chelating agent having a chelate stability constant of 8 or more for ferric ions. Here, the chelate stability constant is “Stability Constants of Metal-ion Complexes” by LGSillen and AEMartell, The Chemical Society, London (1964). This means a constant generally known by S. Chaberek and AEMartell, "Organic Sequestering Agents", Wiley (1959), etc.
[0211]
Examples of the chelating agent having a chelate stability constant with respect to ferric ion of 8 or more include those described in Japanese Patent Application Nos. 2-234776 and 1-324507.
[0212]
The amount of the chelating agent used is preferably 0.01 to 50 g per liter of the stabilizing solution, more preferably 0.05 to 20 g, and good results are obtained.
[0213]
Moreover, an ammonium compound is mentioned as a preferable compound added to a stabilizer. These are supplied by ammonium salts of various inorganic compounds. The addition amount of the ammonium compound is preferably in the range of 0.001 mol to 1.0 mol, and more preferably in the range of 0.002 to 2.0 mol, per liter of the stabilizing solution.
[0214]
Further, the stabilizer preferably contains sulfite.
[0215]
Furthermore, the stabilizer preferably contains a metal salt in combination with the chelating agent. Such metal salts include Ba, Ca, Ce, Co, In, La, Mn, Ni, Bi, Pb, Sn, Zn, Ti, Zr, Mg, Al or Sr, halides, hydroxides Products, sulfates, carbonates, phosphates, acetates, and other inorganic salts or water-soluble chelating agents. The amount used is 1 x 10 per liter of stabilizer. ^-Four ~ 1 × 10 ^-1 The molar range is preferred, more preferably 4 × 10 ^-Four ~ 2 × 10 ^-2 The range of moles.
[0216]
An example of an automatic processor (hereinafter also simply referred to as a self-machine) to which the present invention can be applied will be described with reference to the drawings. FIG. 1 is a schematic diagram of a printer processor in which a self-printing machine A and a photographic printing machine B are integrally configured.
[0217]
In FIG. 1, in the lower left part of the photographic printing machine B, a magazine M in which photographic paper which is an unexposed silver halide photographic light-sensitive material is stored in a roll shape is set. The photographic paper drawn out from the magazine is cut into a predetermined size via the feed roller R and the cutter unit C, and becomes a sheet-like photographic paper. This sheet-like photographic paper is produced by belt conveying means B. ₁ And the image of the original image O is exposed in the exposure unit E. The exposed sheet-like photographic paper is further transported by a plurality of pairs of feed rollers R and is introduced into the automatic machine A. In the self-printing machine A, the sheet-like photographic paper is transported in the color developing tank 1A, the bleach-fixing tank 1B, and the stabilizing tanks 1C, 1D, and 1E (substantially three tanks) which are processing tanks. Are sequentially conveyed and subjected to color development processing, bleach-fixing processing, and stabilization processing, respectively. The sheet-like photographic paper subjected to the above-described processes is dried in the drying unit 35 and discharged outside the apparatus.
[0218]
In the figure, the alternate long and short dash line indicates the transport path of the silver halide photographic material. In the embodiment, the photosensitive material is guided into the self-machine A in a cut state, but may be guided into the self-machine as a strip. In that case, if an accumulator that temporarily retains the photosensitive material is provided between the self-printing machine A and the photographic printing machine B, the processing efficiency is increased. Needless to say, the self-machine according to the present invention may be integrated with the photographic printing machine B or may be a single self-machine. Further, the silver halide photographic light-sensitive material processed by the self-machine according to the present invention is not limited to the exposed photographic paper, and it goes without saying that it may be an exposed negative film or the like. Further, as an explanation of the present invention, a self-acting machine having a substantially three-tank configuration having a color developing tank, a bleach-fixing tank, and a stabilizing tank is used. However, the present invention is not limited to this. The present invention can be applied even to a self-supporting machine having substantially four tanks having a tank and a stabilizing tank.
[0219]
FIG. 2 is a schematic view of a color developing tank 1A which is a processing tank in the II section of the self-machine A of FIG. The bleaching / fixing tank 1B and the stabilizing tanks 1C, 1D, and 1E have the same configuration as the color developing tank 1A. Therefore, in the following description, as the processing tank 1, the color developing tank 1A, the bleaching / fixing tank 1B, The tanks 1C, 1D, and 1E are all referred to here. In the drawing, in order to make the configuration easy to understand, a conveying means for conveying the photosensitive material is omitted. In this example, the case where the tablet 13 is used as the solid processing agent will be described.
[0220]
The processing tank 1 includes a processing unit 2 that processes a photosensitive material, and a solid processing agent charging unit 11 that supplies a tablet 13 that is integrally provided outside a partition wall that forms the processing unit. The processing unit 2 and the solid processing agent charging unit 11 are partitioned by a partition wall 12 in which a communication window is formed so that the processing liquid can flow. Since the input section 11 is provided with the section 14 for receiving the processing agent, it does not move to the processing section 2 while remaining solid.
[0221]
The cylindrical filter 3 is replaceably provided below the solid processing agent charging unit 11 and functions to remove insoluble matters such as paper waste in the processing liquid. The filter 3 communicates with the suction side of the circulation pump 5 (circulation means) via a circulation pipe 4 provided so as to penetrate the lower wall of the solid processing agent charging part 11.
[0222]
The circulation system is composed of a circulation pipe 4, a circulation pump 5, a treatment tank 1, and the like that form a liquid circulation passage. The other end of the circulation pipe 4 communicating with the discharge side of the circulation pump 5 passes through the lower wall of the processing unit 2 and communicates with the processing unit 2. With such a configuration, when the circulation pump 5 operates, the processing liquid is sucked from the solid processing agent charging unit 11 and discharged to the processing unit 2 so that the processing liquid is mixed with the processing liquid in the processing unit 2 and again the solid processing agent. The circulation to enter the input unit 11 is repeated. The flow rate of the circulating flow is preferably 0.1 (rotation = circulation amount / tank capacity) or more with respect to the tank capacity per minute, and more preferably 0.5 to 2.0 rotations. Moreover, the circulation direction of the processing liquid is not necessarily limited to the direction shown in FIG. 2 and may be in the opposite direction.
[0223]
The waste (waste) liquid pipe 6 is for overflowing the processing liquid in the processing section 2, keeps the liquid level constant, and is brought into contact with the photosensitive material from other processing tanks, It helps to prevent components that ooze out of the photosensitive material from accumulating and increasing.
[0224]
The rod-shaped heater 7 is disposed so as to penetrate the upper wall of the solid processing agent charging unit 11 and be immersed in the processing liquid in the solid processing agent charging unit 11. The heater 7 heats the processing liquid in the processing tank 1. In other words, the heater 7 is a temperature adjusting unit that holds the processing liquid in the processing tank 1 in a temperature range suitable for processing (for example, 20 to 55 ° C.). is there.
[0225]
The processing amount information detecting means 8 is provided at the entrance of the automatic machine and is used for detecting the processing amount of the photosensitive material to be processed. The processing amount information detection means 8 is provided with a plurality of detection members in the left-right direction, and functions as an element for detecting the width of the photosensitive material and counting the detected time. Since the conveyance speed of the photosensitive material is mechanically preset, the processing area of the photosensitive material can be calculated from the width information and the time information. The processing amount information detecting means may be any means capable of detecting the width and transport time of a photosensitive material such as an infrared sensor, a microswitch, and an ultrasonic sensor. Further, in the case of a printer processor that can indirectly detect the photosensitive material processing area, for example, a printer processor as shown in FIG. 1, the amount of photosensitive material that has been baked, or the number of photosensitive material processing that has a predetermined area, It may be detected. Further, the detection timing is before processing in this example, but it may be after processing or while being immersed in the processing liquid (in such a case, the position where the processing amount information detecting means 8 is provided). Can be appropriately changed to a position that can be detected after processing or a position that can be detected during processing). Furthermore, as the information to be detected, the processing area of the photosensitive material has been described in the above description, but the present invention is not limited to this, and the processing amount of the photosensitive material to be processed, processed, or being processed is determined. The value may be a proportional value, and may be the concentration or concentration change of the processing liquid stored in the processing tank. Further, it is not necessary to provide the processing amount information detecting means 8 for each of the processing tanks 1A, 1B, 1C, 1D, and 1E, and it is preferable to provide one for each self-machine.
[0226]
The processing agent supply means 17 for feeding the solid processing agent stored in the cartridge 15 as the storage means into the processing tank is disposed above the filtration unit (section) 14 and encloses the tablet 13 as the solid processing agent. A cartridge 15 and an extruding member 10 configured to extrude one or a plurality of tablets 13 are provided. This processing agent supply means 17 is controlled by a processing agent supply control means 9 described later, and in conjunction with a supply signal issued from the processing agent supply control means 9, the tablet 13 that has been waiting is pushed out by the extrusion member 10, The tablets 13 are supplied to the filtration unit (section) 14 in the solid processing agent charging unit 11. In the present invention, the solid processing agent 13 is supplied to the filtration unit (section) 14 in the solid processing agent charging (receiving) unit 11, but the supply location is anywhere in the processing tank 1. That is, in the present invention, it suffices if the solid processing agent can be dissolved using the processing solution, the components corresponding to the processing amount information of the photosensitive material are surely introduced, and the processing characteristics of the processing solution in the processing tank 1 are kept constant. More preferably, the solid processing agent is preferably supplied into the circulation path of the processing liquid. In addition, the processing agent supply means 17 is configured so that the moisture in the processing tank of the self-machine and the moisture of the outside air and the dispersion of the processing liquid do not come into contact with the solid processing agent before being supplied to the processing tank. Is preferred.
[0227]
The filtration unit (section) 14 is immersed in the processing liquid in the solid processing agent charging unit 11 and is insoluble by the tablet 13 supplied by the processing agent supply means 17, for example, an insoluble component mixed in the tablet 13, If the tablet 13 is disintegrated and a solid processing agent-derived material adheres to the photosensitive material, the resulting image may be damaged, resulting in insufficient processing of the attached part, etc. Is to be removed. This filtration part (section) 14 is processed with resin. The filtration unit (section) 14 is not necessarily provided in the solid processing agent supply unit 11, and the tablet 13 supplied by the processing agent supply means 17 is transported by the photosensitive material shown in FIG. It is sufficient that it is introduced into the processing liquid in 2.
[0228]
The processing agent supply control means 9 controls the processing agent supply means 17, and the processing amount information (processing area in this embodiment) of the photosensitive material detected by the processing amount information detection means 8 becomes a predetermined constant value. When it reaches, the processing agent supply means 17 issues a processing agent supply signal. Note that the processing agent supply control unit 9 may control the processing agent supply unit 17 so as to supply a necessary amount of processing agent to the solid processing agent input unit 11 according to the processing amount information.
[0229]
Next, the operation of the present invention will be described with reference to FIG. With respect to the exposed photosensitive material, the processing amount information is detected by the processing amount information detecting means 8 at the entrance of the automatic machine A. When the accumulated area of the photosensitive material to be processed reaches a predetermined area according to the processing amount information detected by the processing amount information detection unit 8, the processing agent supply control unit 9 supplies a supply signal to the processing agent supply unit 17. To emit. Receiving the supply signal, the processing agent supply means 17 pushes out the tablet 13 by the extruding member 10 and supplies the tablet 13 to the filtration unit (section) 14 in the solid processing agent charging unit 11. The supplied tablet 13 is dissolved by the processing liquid in the solid processing agent charging unit 11, but the solid processing agent charging unit 11 → circulation pump 5 → processing unit 2 → communication window → solid processing agent charging unit 11 by the circulation means Dissolution is accelerated by the circulating processing solution. On the other hand, the detected photosensitive material is sequentially conveyed by the roller conveying means in the color developing tank 1A, the bleach-fixing tank 1B, and the stabilizing tanks 1C, 1D, and 1E (see the self-machine A in FIG. 1). Each of the color developing tank 1A, the bleach-fixing tank 1B, and the stabilizing tanks 1C, 1D, 1E, which are processing tanks, may be provided with a processing agent supply means 17 and supplied simultaneously. Moreover, the timing supplied by each supply means may be different from each other, and the predetermined area for the treatment agent supply means to be controlled by the treatment agent supply control means 9 is the processing tanks 1A and 1B. , 1C, 1D, and 1E may be the same, but may be different from each other.
[0230]
In the example described below without being limited to this example, the bleach-fixing tank 1B and the stabilization tanks 1C, 1D, and 1E have the same configuration as the color developing tank 1A. The developing tank 1A, the bleach-fixing tank 1B, and the stabilizing tanks 1C, 1D, and 1E are all referred to. In the figure, those having the same functions as those in FIG. Further, in order to make the configuration easy to understand, a conveying means for conveying the photosensitive material is omitted. Although the filtering means is described as a preferred example in the present example, the present invention can sufficiently exhibit the effects of the present invention without the filtering means.
[0231]
As described above, according to the present invention, the replenishment tank, which has been necessary in the past, is no longer necessary, and it is not necessary to secure a space therefor, so that the self-acting machine becomes compact and the solid processing agent is supplied to the processing tank. There is no need for liquid preparation, there is no liquid splashing during liquid preparation, no adhesion or contamination to the human body, clothes, and peripheral devices, and handling is simple. There is an excellent effect of having stable processing characteristics without deterioration.
[0232]
Next, as another example of the present invention, FIG. 3 is a schematic view of the color developing tank 1A in the II section of the self-machine A in FIG. It is sectional drawing with an agent supply means. FIG. 4 is a schematic plan view showing the self-machine A of FIG. 1 from above (however, the route of the water replenishing means is described for explanation). FIG. 5 is a block diagram relating to control according to this example. FIG. 6 is a block diagram in which a pre-programmed evaporative replenishment setting means 23 is added to the control means. In FIGS. 3 and 4, a supplementary water tank 43 for storing supplementary water is shown. In this example, a case where a tablet is used as the solid processing agent 13 will be described.
[0233]
First, a different part from FIG. 2 in FIG. 3 and FIG. 4 is demonstrated.
[0234]
The replenishing water supply means 42 is means for replenishing replenishing water (replenishing water) from the replenishing tank 43 for storing replenishing water to the treatment agent charging unit 11, and comprises a hot water replenishing device 32 comprising a pump, a temperature controller, etc. And a water replenishment pipe 36. The replenishing water supply means 42 is for diluting the cumulative suppression component eluted by the reaction while supplementing the water taken out by the photographic material and the water evaporated from the tank surface. Further, a replenishment tank or a replenishment pump may be provided for each of the treatment tanks 1A, 1B, 1C, 1D, and 1E. If the self-acting machine becomes compact, more preferably, only one replenishing tank and water replenishing pump are installed in the self-acting machine, and a solenoid valve is provided in the water replenishing path (pipe 41, etc.) and each treatment tank is required. Only one supplementary water tank 43 and one supplementary pump are provided in the self-acting machine by adjusting the diameter of the diameter of the supplementary water pipe to adjust the supplementary quantity. Can be more compact. In addition, regarding the stabilization tanks 1C and 1D, which are treatment tanks, respectively, it is possible to omit the replenishing water supply means by supplying the stable liquid overflowed from the stabilization tanks 1D and 1E, respectively. Moreover, it is preferable that the temperature of the supplementary water in the supplementary water tank is adjusted.
[0235]
Water to be replenished includes not only general water such as well water and tap water, but also contains antifungal agents such as isothiazoline and chlorine-releasing compounds, and some sulfite chelating agents, including ammonia and inorganic salts Known compounds and methods can be used as long as they do not affect photographic performance.
[0236]
This replenishing water control means controls the replenishing water supply means 42 by means of evaporative replenishing water setting means 23 (FIGS. 5 and 6) preliminarily programmed according to the environmental temperature / humidity (relative humidity) of the installation site and / or the processing amount. It is a control means for controlling the replenishment water supply means 42 in accordance with the processing amount information detected by the information detection means 8. The replenishing water supply control means is not limited to responding to the processing amount information detected by the processing amount information detecting means 8, but is controlled according to the information that the processing agent is supplied by the processing agent supply means 17. Also good.
[0237]
3 and FIG. 2 other than those described above will be described (the functions and the like are the same as those in FIG. 2).
[0238]
The heater 7 is disposed at the bottom of the processing unit 2 and heats the processing liquid in the processing unit 2. In other words, the processing liquid in the processing unit 2 and the solid processing agent charging unit 11 is suitable for processing. A temperature control function for maintaining the temperature range (for example, 20 to 55 ° C.) is performed.
[0239]
As the circulation means, the circulation pipe 4 and the circulation pump 5 are provided in the same manner as in FIG. 2, but the difference from FIG. 2 is that the direction in which the treatment liquid circulates is reversed. It circulates with circulation pump 5-> solid processing agent input part 11-> communication window-> processing part 2.
[0240]
The processing agent supply means 17 supplies the tablet 13, which is a solid processing agent enclosed in the cartridge 15, to the filtration unit (section) 14 in the solid processing agent charging unit 11 by the push claw 18. The difference from FIG. 2 is that the cam 19 is actuated by the one-rotation stop mechanism of the shaft, the push claw 18 is actuated, and the tablet 13 that has been waiting is supplied to the processing tank 1, and the next tablet 13 is the tablet pushing spring. Since the spring is biased downward from 21 by 21, it quickly enters a standby state. At this time, the processing agent supply means 17 may be horizontally placed or pushed up from below, and may be any means as long as the solid processing agent can be introduced into the processing tank 1.
[0241]
Next, the operation of the present invention will be described based on FIG. 1, FIG. 3, FIG. 4 and FIG. With respect to the exposed photosensitive material, the processing amount information is detected by the processing amount information detecting means 8 at the entrance of the automatic machine A. When the accumulated area of the photosensitive material to be processed reaches a predetermined area according to the processing amount information detected by the processing amount information detection unit 8, the processing agent supply control unit 9 supplies a supply signal to the processing agent supply unit 17. To emit. Receiving the supply signal, the processing agent supply means 17 pushes out the tablet 13 by the extruding member 10 and supplies the tablet 13 to the filtration unit 14 in the solid processing agent charging unit 11. The supplied tablet 13 is dissolved by the processing liquid in the solid processing agent charging unit 11, but is circulated in the processing unit 2 → circulation pump 5 → solid processing agent charging unit 11 → communication window → processing unit 2 by the circulation means. Dissolution is promoted by the processing solution. On the other hand, when the accumulated area of the photosensitive material to be processed reaches a predetermined area in accordance with the processing amount information detected by the processing amount information detection unit 8, the replenishing water supply control unit 42 (warm water supply unit 42) A rehydration signal is issued to the replenishing device 32 and the electromagnetic valve 33). The replenishing water supply means 42 that has received the replenishing water signal controls the hot water replenishing device 32 and the electromagnetic valve 33 to supply a predetermined amount of replenishing water stored in the replenishing tank 43 to each treatment tank or to a treatment tank that becomes necessary. Or replenish the required amount of water. The predetermined area in this case is the same amount as that in the processing agent supply control means 9, but is not limited thereto, and may be different predetermined areas. On the other hand, the detected photosensitive material is sequentially conveyed by the roller conveying means in the color developing tank 1A, the bleach-fixing tank 1B, and the stabilizing tanks 1C, 1D, and 1E, which are processing tanks.
[0242]
Next, the solid processing agent supply apparatus of the present invention will be described. FIG. 7A shows a cross-sectional view of the powdery processing agent supply apparatus, and FIG. 7B is a perspective view of the package. The supply device 50 includes a hopper or package 51 for storing the powdery processing agent, a measuring hole 53 for measuring the powdery processing agent, and a rotary drum 52 for supplying a fixed amount. The rotary drum 52 has a moisture-proof function by shifting the positions of the measuring hole 53 and the discharge portion 56. Package 51 was sealed and loaded on top of the feeder. A certain amount of powder chemical is metered into the metering hole 53, and when the drum 52 rotates and communicates with the discharge unit 56 according to the command of the photosensitive material processing amount detection means, the powder chemical stops and passes through the discharge unit 56. Is supplied to the constant temperature section (filter tank) of the automatic processor. After the supply is completed, when the drum 52 rotates and the measurement hole 53 and the supply unit 57 communicate with each other, the drum 52 is stopped and the measurement of the powdered chemical is started.
[0243]
FIG. 8 is a perspective view of another supply device of the powdery processing agent.
[0244]
The supply device 60 is devised so that the powdery chemical storage unit 63 is separated into a plurality of parts and is stored separately for each part as in the conventional concentration kit. There is a dehumidifier 65 for improving the storage stability of the powdered chemical in the storage section.
[0245]
Based on the processing information of the photosensitive material, the rotating body 67 transports and supplies the powdery processing agent received by the table 66 to the discharge unit 68 for each component.
[0246]
FIG. 9 is a cross-sectional view of another powder processing agent supply apparatus.
[0247]
The supply device 70 puts the powdery processing agent in the hopper 71 and moves the piston 75 in the horizontal direction (to the right) according to the processing amount of the photosensitive material. To the left), and the discharging unit 74 supplies the metered powder agent to the thermostat (filter tank).
[0248]
FIG. 10 is a cross-sectional view showing still another apparatus for supplying a powdery treatment agent.
[0249]
The supply device 80 has a function of mounting (loading) the package 81 containing the powdery processing agent 85 and automatically opening it with the roller 83, and supplying the powdery chemical by the discharge unit 84 by controlling the rotation speed of the screw 82. Device.
[0250]
Since it has a function of automatically opening the package, fine powder does not fly when opening and mounting.
[0251]
FIG. 11 is related to a PTP (Pressure Through Package) packaged solid processing agent charging device, (A) is a sectional view of the processing agent supply device, (B) is a perspective view of packaging breaking means, and (C) is packaging breaking means. (D) is sectional drawing which shows the loading state of the solid processing agent by which PTP packaging was carried out.
[0252]
The processing agent storage container stores the PTP-packed solid processing agent and may be stored individually in the storage container or may be a cartridge type in which the solid processing agent is stored in advance. A known material can be used for PTP packaging, and the solid processing agent is preferably packaged in the form of a tablet.
[0253]
The solid processing agent packed in PTP is supplied from below the storage container, and when a certain amount of photosensitive material is processed, information on the processing amount detection means is sent to the processing agent supply control means, and the solid processing agent packed in PTP by the motor is supplied. The lower part of the PTP package (mainly using aluminum) is peeled off by pressing and crushing onto a wedge-shaped fixing plate, and the solid processing agent is put into the treatment tank from the inlet. The PTP package that has been emptied after being thrown in is further pushed out and discarded from the waste outlet. As a means for crushing, there is a method using a roller in addition to using a wedge, which can be arbitrarily selected.
[0254]
FIG. 12 shows an example of a part feeder type supply device for tablets (preliminarily divided weighing) that are packaged together.
[0255]
The packaged A or B of tablet chemicals packaged in a lump is opened and placed in the hopper 101. At that time, no fine powder was generated, and there was no caking and the handleability was good. The stirrer 106 is rotated by a signal from the remaining amount detecting means 109, and the tablets 105 are aligned with the tablet aligning unit 110. The processing agent supply control means 103 operates according to the processing amount of the photosensitive material, and the rotary table 107 conveys the tablets and supplies them from the discharge unit 108 to the input unit. The rotary table 107 rotates once and stops by an instruction from the rotary table control means (tablets can be supplied several times by one instruction). The tablet enters the hole of the rotary table 107.
[0256]
The packaging material is inexpensive, easy to handle, can be put in with high precision, and the tablet alignment unit 110 has the advantage that there is no empty supply by a rotary table and the efficiency is very high. It is preferable for environmental suitability by reducing the number of plastic containers. Further, since the fine powder is not present, the inside of the supply device is not contaminated and is maintenance-free.
[0257]
FIG. 13 shows an example of a part feeder type supply device 120 for tablets (preliminarily divided weighing) that are packaged together.
[0258]
The batch-wrapped packaging material (A) or (B) of packaged chemicals was opened and placed in the hopper 133. At that time, no fine powder was generated, and there was no caking and the handleability was good. The movable member 124 is rotated by the signal from the remaining amount detecting means 125, and the tablet chemicals are aligned with the tablet aligning unit 129. After a certain amount of alignment, the movable member 124 stops. At this time, the sweeper 123 is very effective for the tablet entering the pocket 122 of the movable part 124 and aligning with the tablet aligning part 129.
[0259]
The processing agent supply means 126 operates according to the processing amount of the photosensitive material, and the first shutter 131 rotates to lower the tablet chemical. Next, the first shutter 131 rotates in the reverse direction so that one tablet is sandwiched between the shutters 131 and 132. The shutter 132 rotates and the tablet chemical passes through the discharge unit 128 and is supplied to the input unit. Next, the shutter 132 rotates in the reverse direction and the shutter 131 is closed.
[0260]
The packaging material is inexpensive, easy to handle, can be input with high accuracy, and in particular, there is no empty supply due to the tablet alignment part 129. It is preferable for environmental suitability by reducing the number of plastic containers. Further, since the fine powder is not present, the inside of the supply device is not contaminated and is maintenance-free.
[0261]
FIG. 14 is a perspective view showing an example of the solid processing agent supply device 140, in which the solid processing agent is put into the processing tank by peeling off the solid processing agent package in the packaging body.
[0262]
The tip of the storage packaging material in which the solid processing agent is wrapped with a four-side seal is set on a winding shaft 142 as a fixing means via a roller 141, and when the photosensitive material is processed, it is detected by the processing amount information detecting means. When a certain amount is reached, a signal is sent by the processing agent supply control means, and the winding shaft 142, which is also the processing agent supply means, is moved to move the package containing the solid processing agent by a certain length. The required number of solid processing agents are charged. Any method can be used to move the package, such as detecting a notch provided in the package in advance, printing pattern detection, processing agent detection of the package, etc. These are moved by a roller 141 and a take-up shaft 142. The roller 141 is installed for the purpose of fixing and positioning the package, and is peeled off by two take-up shafts and charged with a solid processing agent.
[0263]
In such a system, the solid processing agent may be a granule, a pill, a tablet, or a powder. Preferably, the tablet has an advantage that it does not adhere to the seal so that it can be put in with high accuracy and contamination is less likely to occur. After the winding is completed, it can be taken directly from the winding shaft, or it can be rewound and the package can be discarded together with the cartridge.
[0264]
FIG. 15 shows an example of a supply device according to a preferred embodiment of the present invention, in which (A) is a plan view, (B) is a perspective view, and (C) is a plan view of various packages.
[0265]
The treatment agent 151 is packaged in a form as shown in FIG. 15C in a four-side sealed package 152.
[0266]
The packaging form in FIG. 15C is an example of the present invention. The material used for the packaging may be a generally used polymer resin packaging, aluminum, or a composite material, but the material may be any material that has good moisture resistance and low oxygen permeability.
[0267]
The processing agent 151 that has been sealed in all directions is peeled off through the cylinder 153, and the processing agent 151 is charged into the charging unit 155 through the charging port 154. Here, the cylinder 153 and the take-up shaft 156 function as a processing agent supply means. The package 152 is wound around a winding shaft 156, and the winding control is controlled by a processing agent supply means that receives a signal from the photosensitive material processing amount detection means. When winding, the knob is opened, the tip of the package 151 is set to the winding shaft 156 that is a fixing means of the processing agent storage packaging material through the cylinder, and the knob 157 is twisted to be fixed by the clamper 158. Rolled up.
[0268]
FIGS. 16A and 16B show an example of the supply device 160 when the solid processing agent 161 is stick-wrapped. FIG. 16A is a side sectional view and FIG. 16B is a front sectional view.
[0269]
The solid processing agent 161 packaged in a stick is put into a storage container 162 which is a storage means.
[0270]
The stick-packed solid processing agent 161 contained in the container 162 is sent to the turret 164 by a roller that also serves as a bridge prevention roller 163 and a turret. Both ends of the stick packaging solid processing agent 161 sent to the turret 164 are fixed by the clamper 165, and then sent to the cutter portion by a rotational motion, and the center portion of the stick packaging is cut (or cut) by the cutter 166 and further rotated. Is sent to the double folded plate 167, the stick packaging solid processing agent 161 is bent, and the solid processing agent 161 filled in the stick packaging is put into the chute 168 from the portion where the cut is made by the rotary cutter 166. After the feeding, it is further rotated to the scrap drop bar 169, and the clamper 165 is released by the clamp opening / closing cam 170. Scrap packaging scrap 171 is discarded in a collection chute 172.
[0271]
FIG. 17 is a sectional view and a perspective view showing one embodiment of the present invention.
[0272]
The processing unit 181 and the charging unit 185 in the thermostatic chamber 182 constituting a part of the processing tank communicate with each other, and the liquid is forcibly circulated by the circulation pump 183 from the lower part of the processing tank and discharged to the filter unit. And enters the processing unit 181.
[0273]
When the photosensitive material is processed, the processing amount is detected by the processing amount detecting means 192. When the processing amount reaches a certain processing amount, the motor M2 is driven via the processing amount supply control, and the pre-weighed tablets are stored in the thermostatic chamber 182. It is supplied to the input unit 185.
[0274]
The tablets are directly put into the storage container 187. After the filling, the aligning means 188 is driven by the motor M1 in accordance with a signal from the aligning amount control means 186, aligns the tablets, and is supplied to the aligning unit 189. When the tablet M supplied to the aligning unit 189 receives a signal from the processing amount supply control unit 190 and the motor M2 is driven, the tablet is carried to the upper part of the input unit by the rotation of the supply unit and is input to the input unit 185. In this case, it is a preferred embodiment from the viewpoint of moisture resistance of the tablet that the treatment agent supply means 191 is substantially blocked from the thermostatic chamber 182.
[0275]
In addition, the tablets to be put into the storage container 187 are broken into those shown in FIGS. 17A and 17B and put into the input container 187. The containers shown in FIGS. 17 (A) and 17 (B) can use known materials such as paper and polymeric resin aluminum, but preferably use materials with good moisture resistance and low oxygen permeability. .
[0276]
FIG. 18 is a cross-sectional view showing an example of a supply device 200 for a solid processing agent packaged in blister pieces.
[0277]
The individual package 202 containing the solid processing agent is loaded into the storage unit 203.
[0278]
The disc 201 rotates 180 ° according to the processing amount of the photosensitive material, and then the needle 205 passes through the individual package 202 and passes through the discharge unit 204 in the individual package 202 to be supplied to the input unit. The empty individual package 202 is discarded from the disposal port.
[0279]
The solid processing agent may be a powder or a granule, but a granule is preferred because the powder adheres to the container.
[0280]
It is easy to handle and maintenance free because there is no fine powder contamination of the supply device 200.
[0281]
FIG. 19 is a cross-sectional view showing an example of the present invention.
[0282]
According to the processing amount of the photosensitive material, it is supplied directly from the tablet chemical storage unit 211 to the input unit 215 inside the processing tank. The input unit 215 has a solid processing agent filter 216 so that the undissolved processing agent does not directly adhere to the photosensitive material. The material of the filter 216 is not particularly limited. The mesh is not particularly limited, but is preferably 10 to 100 μm because of the liquid flow and the filter effect.
[0283]
The effect is almost the same as when the solid processing agent is supplied to the constant temperature bath 212 constituting a part of the processing bath. The compactness is inferior because there is only a separate charging unit 215 in the processing tank.
[0284]
Next, specific examples of 4-way seal and 3-way seal packaging are shown in FIGS. However, the present invention is not limited to these. In the sealed packaging shown in FIG. 20A, several kinds of tablets are contained in one packaging unit. In FIG. 20B, tablets of different types and sizes are individually packaged. FIG. 20 (C) is a package of granules or powder. FIG. 20D contains one of the same size. In FIG. 20 (E), a plurality of the same chemicals of the same size are contained as small tablets.
[0285]
FIGS. 21A, 21B, and 21C are plan views showing examples of four-way seals. FIG. 21 (D) shows an example of a three-way seal. 22A and 22B show specific examples of stick packaging, but the invention is not limited to these.
[0286]
FIG. 23 is a cross-sectional view showing a state in which tablets, granules, or powders are sealed and heat-sealed and heat-sealed, and then folded and accommodated in a container.
[0287]
FIG. 24 shows a specific example of PTP packaging. However, it is not limited to these. FIG. 24A shows a pill-shaped solid processing agent packaged in PTP, and FIG. 24B shows a state in which a plurality of processing agent tablets are contained and packaged. FIG. 24C shows a state in which tablets, granules or powders are arranged in tandem. FIG. 24 (D) shows these packages connected in a horizontal row. Alternatively, it may be a blister type as shown in FIG.
[0288]
FIG. 25 shows a specific example of batch packaging. However, it is not limited to these. FIG. 25 (A) shows a case where the solid processing agent is contained in a cylindrical container, FIG. 25 (B) shows a case where the solid processing agent is contained in a flexible two-side seal or three-side sealed bag, FIG. ) Indicates one sealed bag containing a solid processing agent.
[0289]
26 and 27 are perspective views showing a specific example of the cartridge.
[0290]
These cartridges can be mounted on the supply device of the present self-machine according to the present invention as a packaging material containing a solid processing agent. Any of the compounds described above can be used as the material. When the amount of the solid processing agent is reduced, it should not be crushed so as not to hinder the supply.
[0291]
FIG. 26A shows the case where the tablet is accommodated in the cylindrical cartridge, and FIG. 26B shows the case where the granule or powder is accommodated in the cartridge.
[0292]
26C and 26D are a perspective view and a cross-sectional view showing a form in which the solid processing agent is accommodated in a box-type cartridge having an opening / closing lid.
[0293]
In FIG. 27, a tablet, granule, or powder is accommodated in a rotatable container having a partition wall and further accommodated in an outer cylinder (main body), and a predetermined amount is dropped from the opening. FIG. 27A shows a type in which the rotating shaft is horizontally supported, and FIG. 30B shows a type in which the rotating shaft is vertically supported.
[0294]
The present invention is not limited to these specific examples.
[0295]
Further, the embodiments of FIGS. 28A and 28B, FIGS. 29A and 29B, FIGS. 30, 31, and 32 will be described.
[0296]
28 (a) and 28 (b) show a "U-shaped" type half punching method.
[0297]
When the photosensitive material is processed, it is detected by the processing amount information detecting means, and when a certain amount is reached, a signal is sent by the processing agent supply control means, and the conveying roller 100 is rotated to enter the solid processing agent 107. The package 801 shown in 29 (a) is moved to the position shown in FIG. 28 (a) and stopped. The method of moving the package 801 may be any method such as a method of detecting a notch provided in the package 801 in advance, detection of a printed pattern or eye mark, detection of the solid processing agent 107 of the package 801, but the necessary number is necessary. The solid processing agent 107 may be detected with high accuracy. Next, as shown in FIG. 28 (b), the punch male mold 300 moves downward to cut the package body 801, and the solid processing agent 107 is put into the processing tank of the automatic processor through the inlet 901 of FIG. 29 (a). The The cut cut by the punch male die 300 becomes a U-shape like a punch shape 601 as shown in FIG.
[0298]
In the case of such a system, the solid processing agent 107 may be any of powder, granule, and tablet, but is preferably a tablet that does not easily adhere to the punch male mold. Further, the tablet does not adhere to the package so much, so that it is difficult for the tablet to be contaminated and is safe for the user to handle. The used package 801 can enter the disposal box 102 and be discarded together. As the disposal box 102, it is preferable to reuse the used package storage box 701.
[0299]
30 and 31 show a method of cutting off the package 110. FIG.
[0300]
When the photosensitive material is processed, it is detected by the processing amount information detecting means, and when a certain amount is reached, a signal is sent by the processing agent supply control means, the conveying roller 201 rotates, and the packaging containing the solid processing agent 107 The body 110 is moved and stopped until the solid processing agent 107 reaches the upper position of the processing tank filter unit 702. At this time, the leading end of the package 110 is in the ironing roller 401.
[0301]
The method of moving the package is to detect notches provided in the package 110 in advance, print pattern detection, processing detection of the package, etc. Just do it. Next, the ceramic cutter 2011 cuts the package 110. When the cutting is completed, the ironing roller 401 and the conveying roller 501 rotate, and the solid processing agent 107 passes through the discharge port by the ironing roller 401 and is put into the processing tank filter unit 702 of the automatic processor. The cut waste packaging body 802 is discharged from the transport roller 501 and enters the waste box 602. The waste box 602 is preferably reused from the used package storage box 301.
[0302]
In the case of such a system, the solid processing agent 107 may be any of powder, granule, and tablet, but preferably a tablet in which no chemicals adhere to the ceramic cutter 201. In addition, the tablet has an advantage that it does not adhere to the package 110 so that it is difficult to cause dirt.
[0303]
The used package 110 can enter the disposal box 602 and be discarded together.
[0304]
32 (a) and 32 (b) show a two-part cut method for the continuous package 603. FIG.
[0305]
When the photosensitive material is processed, it is detected by the processing amount information detection means, and when a certain amount is reached, a signal is sent by the processing agent supply means, and the conveying roller 502 rotates, and at the same time, the round blade 301 made of ceramic or stainless steel Rotate, cut the lower part of the continuous package 603 into two parts, and put the solid processing agent 107 into it. When the two parts are divided, the continuous package 603 is spread on the suction guide 202 on both sides by suction, so that the solid processing agent 107 inside easily falls. The empty packaging body 603 without the solid processing agent 107 is moved by the transport roller 401 when the next solid processing agent 107 is charged, and is discarded into the packaging body storage box 101.
[0306]
In this two-part division, a notch or the like may be attached to the continuous package in addition to the above method, and it may be torn while being wound with a roller.
[0307]
In the case of such a system, the solid processing agent 107 may be any of powder, granule, and tablet, but preferably a tablet in which no chemicals adhere to the punch male mold. Further, the tablet has an advantage that it does not adhere to the seal of the package so that it is difficult to cause dirt.
[0308]
The used continuous package 603 can enter the package storage box 101 and be discarded.
[0309]
【Example】
(Example 1)
After imagewise exposure of Konica QA paper type A5 (manufactured by Konica Corporation), the replenisher-added portion of Konica Big Minilab BM-101 (manufactured by Konica Corporation) was remodeled and the solid processing agent shown in FIG. The supply device was remodeled, and further remodeling was performed so that the processing steps shown in Table 1 were followed.
[0310]
[Table 1]

[0311]
The stability was a counter-current system from 3 to 1, and the entire amount of the stable-1 overflow liquid was introduced into the bleach-fixing tank. In addition, photosensitive material 1m ² The carry-over per hit is 50ml / m in all tanks ² Met.
[0312]
Evaporation correction is performed every hour for color development, bleach-fixing, stable, 9.0 ml / hr, 7.2 ml / hr, 14.1 ml / hr during temperature control, and 3.8 when temperature control is not performed. ml / hour, 3.1 ml / hour, and 6.1 ml / hour were accumulated and collected at the start of temperature control.
[0313]
The tank solution at the start is Konica Color QA Paper Color Development Starter 82P-1B, (Konica Color QA Paper Bleach Fixing Starter 82P-2B (same as above), Konica Color QA Paper Stabilization Starter 82P- It was prepared using 3B (same as above).
[0314]
Color paper processed tablets were prepared according to the following operations (A to G).
[0315]
1) Color development tablet for color paper
Operation (A)
Crushing 1200g of developing agent CD-3 [4-amino-3-methyl-N-ethyl-N- [β- (methanesulfonamido) ethyl] aniline sulfate] in a commercially available bandam mill to an average particle size of 10 μm To do. This fine powder was granulated by adding 50 ml of water for about 7 minutes at room temperature in a commercially available stirring granulator, and then the granulated product was dried at 40 ° C. for 2 hours in a fluid bed dryer. Remove the moisture from the granulate almost completely. In this way, polyethylene glycol 6000 (150 g) is uniformly mixed with the adjusted granulated material for 10 minutes using a mixer in a room where the humidity is adjusted to 25 ° C. and 40% RH or less. Next, 4 g of sodium N-lauroylalanine was added and mixed for 3 minutes. The resulting mixture was adjusted to 1.0 g per tablet using a tableting machine modified from Kikusui Seisakusho's Tough Presto Collect 1527HU. Then, compression tableting was carried out to prepare 400 A tablets with a diameter of 15 mm for color development replenishment for color paper.
[0316]
Operation (B)
In the same manner as in the operation (A), 120 g of disulfoethylhydroxylamine disodium salt is pulverized and granulated. The amount of water added is 6.0 ml, and after granulation, it is dried at 50 ° C. for 30 minutes to almost completely remove moisture from the granulated product. Thus, the N-lauroylalanine sodium 4 is added to the adjusted granulated material, and it mixes for 3 minutes using a mixer in the room | humidity adjusted to 25 degreeC and 40% RH or less. Next, the resulting mixture was compressed into tablets using a tableting machine modified with Tough Presto Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 1.0 g per tablet, and 100 color developments for color paper were replenished. A tablet B preparation having a diameter of 15 mm was prepared.
[0317]
Operation (C)
Tinopearl SFP (Ciba Geigy) 30.0g, sodium sulfite 3.7g, potassium bromide 0.3g, diethylenetriaminepentaacetic acid 25g, sodium p-toluenesulfonate 280g, potassium hydroxide 20g, mannitol 10.6g were ground as in (A). Then, it mixes uniformly with a commercially available mixer. Next, granulation is carried out in the same manner as in (A) with the addition amount of water being 20 ml. After granulation, the granulated product is dried at 60 ° C. for 30 minutes to remove the moisture of the granulated product almost completely. In this way, 4 g of sodium N-lauroylalanine is added to the prepared granulated product, and mixed for 3 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. Next, the resulting mixture was compressed into tablets using a tableting machine modified with Tough Presto Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 3.2 g per tablet, and 100 color developments for color paper were replenished. Tablet C preparation with a diameter of 20 mm was prepared.
[0318]
Operation (D)
In the same manner as in the operation (A), 350 g of potassium carbonate is pulverized and granulated. The amount of water added is 20 ml, and after granulation, it is dried at 700 ° C. for 30 minutes to almost completely remove moisture from the granulated product. In this way, 15 g of polyethylene glycol 6000 is uniformly mixed for 10 minutes using a mixer in a room where the humidity is adjusted to 25 ° C. and 40% RH or less. Next, 4 g of sodium N-lauroylalanine was added and mixed for 3 minutes, and the resulting mixture was filled to 3.0 g with a tableting machine modified from Kikusui Seisakusho's Tough Presto Collect 1527HU. Then, compression tableting was carried out to produce 110 D tablets having a diameter of 20 mm for color paper replenishment for color paper.
[0319]
2) Bleach fixing supplement tablets for color paper
Operation (E)
1250 g of diethylenetriaminepentaacetic acid ferric ammonium monohydrate, 25 g of ethylenediaminetetraacetic acid, 250 g of maleic acid and 46 g of Pine Flow (Matsutani Chemical) are pulverized, mixed and granulated in the same manner as in the operation (C). The amount of water added is 80 ml, and after granulation, it is dried at 60 ° C. for 2 hours to almost completely remove moisture from the granulated product. In this way, 15 g of sodium N-lauroyl sarcosine is added to the granulated material thus prepared, and mixed for 3 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. Next, the resulting mixture was compressed into tablets using a tableting machine modified with Tough Presto Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 8.6 g per tablet, and 170 pieces of bleach-fixing for color paper were replenished. A tablet A preparation having a diameter of 30 mm was prepared.
[0320]
Operation (F)
In the same manner as in the operation (C), 1640 g of ammonium thiosulfate, 750 g of sodium sulfite, 40 g of potassium bromide and 50 g of p-toluenesulfinic acid are pulverized, mixed and granulated. The amount of water sprayed is 100 ml, and after granulation, it is dried at 60 ° C. for 120 minutes to almost completely remove moisture from the granulated product. In this way, 20 g of sodium N-lauroyl sarcosine is added to the prepared granulated product, and mixed for 3 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. Next, the mixture obtained was compressed into tablets using a tableting machine modified with Tough Presto Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd. with a filling amount of 13.4 g per tablet. A tablet B preparation having a diameter of 30 mm was prepared.
[0321]
3) Tablet for stable replenishment for color paper
Operation (G)
Sodium carbonate monohydrate 10g, 1-hydroxyethane-1,1-diphosphonate disodium 200g, Tinopal SFP 150g, sodium sulfite 300g, zinc sulfate heptahydrate 20g, ethylenediaminetetraacetic acid disodium 150g, ammonium sulfate 200g, o-phenyl 10g of phenol and 25g of pine flow are pulverized, mixed and granulated in the same manner as in the operation (C). The amount of water added is 60 ml, and after granulation, it is dried at 70 ° C. for 60 minutes to almost completely remove moisture from the granulated product. In this manner, 10 g of sodium N-lauroyl sarcosine is added to the granulated material thus prepared, and mixed for 3 minutes using a mixer in a room adjusted to 25 ° C. and 40% RH or less. Next, the resulting mixture was compressed into tablets with a filling amount of 3.1 g per tablet using a tableting machine modified from Tough Presto Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., for stable replenishment of 360 color papers. Tablets with a diameter of 20 mm were prepared. The tableting pressure in operations (A) to (G) is 650 kg / cm each. ² It was.
[0322]
Next, for the above color development replenishing tablets, one tablet each of A, B, C and D was prepared, and a total of 4 tablets were packaged in 1 minute, and a continuous 20 minute package was packaged in a four-sided seal system. . Regarding the bleach-fixing replenishment tablets, 1 tablet of A agent and 2 tablets of B agent were packaged in total, 3 tablets in 1 minute, and the continuous 20-minute package was packaged in the same manner as the color development supplement tablet.
[0323]
Furthermore, about the tablet for stable replenishment, each one tablet was packaged in the same manner as described above.
[0324]
The four-side seal packaging material was prepared by laminating on the non-stretched polypropylene film surface of unstretched polypropylene film / stretched polypropylene film.
[0325]
The produced unstretched polypropylene / stretched polypropylene film was heat-sealed, and the tablets were packaged.
[0326]
Processing is 5m of color paper per day ² And the amount of accumulation of the insoluble tablets in each treatment tank at 2.0 R was measured until the overflow amount was twice that of the tank liquid (2.0 R). Furthermore, the solubility of each tablet was observed.
[0327]
The solubility of the tablet was measured by visually remodeling the tablet supply part in the treatment tank and installing a transparent acrylic plate in the treatment tank part until the tablet was completely dissolved immediately after it was put into a 1-pack package.
[0328]
Moreover, evaluation is shown below.
[0329]
○: No problem
Δ: Slightly precipitated and oil-out products are generated in the processing solution.
X: A large amount of precipitates are generated in the processing solution
XX: A large amount of precipitate is generated in the processing solution and adheres to the photosensitive material.
Also, a sample subjected to wedge exposure was developed immediately after the solid treatment agent was introduced once and immediately before the next solid treatment agent was introduced, and the difference in maximum reflection density (ΔDmax (B)) of blue was measured. The average value from the start of running until each solid treatment agent was introduced 16 times was calculated.
[0330]
The results are shown in Table 2.
[0331]
[Table 2]

[0332]
As is clear from Table 2, the S / R value of the present invention is closely related to the dissolution state of the solid processing agent. If the S / R value is large, the solid processing agent accumulates in the processing tank and the insoluble phenomenon occurs. I will.
[0333]
Further, it was found that when the S / R value is small, a thick portion is locally generated in the treatment liquid, and precipitation occurs and grows therefrom. Further, it has been found that color development has a problem that processing variation increases as S / R decreases.
[0334]
These phenomena 4 ≦ S / R ≦ Four It can be seen that a good result is shown without any problem within the range of 0.
[0335]
(Example 2)
In Example 1, the tableting pressure in operations (A) to (D) of the color developer and the amount of potassium carbonate in operation (D) were changed as shown in Table 3, and the color developer was the same as in Example (1). The experiment was conducted.
[0336]
The results are shown in Table 3.
[0337]
[Table 3]

[0338]
As apparent from Table 3, the effects of the present invention can also be clearly achieved by controlling the raw material and tableting pressure in the tablet.
[0339]
(Example 3)
In Example 1, a granular processing agent was prepared for each except the tableting steps of operations (A) to (G).
[0340]
Moreover, the powdery processing agent was produced about each except the tableting process and granulation process of operation (A)-(G).
[0341]
The same experiment as in Example 1 was performed on the obtained tablets, granules, powder processing agents, and the respective color developers.
[0342]
The results are shown in Table 4.
[0343]
[Table 4]

[0344]
As is clear from Table 4, the solid processing agent dissolution situation and the improvement in processing dispersion, which are the effects of the present invention, are preferable when the solid processing agent is a granule, and more preferably when the solid processing agent is a tablet. I understand that
[0345]
(Example 4)
After the Konica Color Negative Film Super DD-100 film was imagewise exposed, the color negative film processor CL-KP-50QA was modified to a system that can use a four-sided seal wrapping material and subjected to continuous processing.
[0346]
[Table 5]

[0347]
Fixing was from 2 to 1, stable was from 3 to 2, and 2 to 1, and the bleaching tank was aerated with an air pump.
[0348]
Evaporation correction is 10 ml, 6.5 ml, 7 ml, 7 ml, and 8.6 ml per hour for color development, bleaching, fixing-1, fixing-2, stable-1, stable-2, and stable-3 tanks during temperature control. , 8.6 ml, 9.3 ml of evaporation replenishment program was used to correct the evaporation. In addition, during non-operation, the non-operation time is accumulated, and evaporative correction water is added to each of color development, bleaching, fixing-1, fixing-2, stable-1, stable-2, and stable-3, 7.5 ml, 5 ml, The amount of 6 ml, 6 ml, 5 ml, 5 ml, and 5 ml was collectively replenished at the start of operation. The tank liquid at the start was prepared using a replenisher of a Konica color negative film processing agent (process CNK-4-52) and a starter.
[0349]
A processed film for color negative film was prepared according to the following operation.
[0350]
1) Color development replenishment tablets for color negatives
Operation (1)
150 g of the developing agent CD-4 [4-amino-3-methyl-N-ethyl-β- (hydroxy) ethylaniline sulfate] is pulverized in a commercial bandam mill to an average particle size of 10 μm. This fine powder was granulated in a commercially available stirred granulator at room temperature for about 7 minutes by adding 10 ml of water, and then the granulated product was dried in a fluidized bed dryer at 40 ° C. for 2 hours. Remove the moisture from the granulate almost completely. In this way, 0.3 g of sodium N-lauroylalanine and 1.9 g of polyethylene glycol 6000 were added to the granulated material thus prepared, and the mixture was used in a room conditioned at 25 ° C. and 40% RH or less using a mixer. Mix evenly for minutes. Next, the mixture was compressed with a tableting machine modified with Tough Presto Collect 1527HU manufactured by Kikusui Seisakusho with a filling amount of 1.1 g per tablet, and 126 color development replenishing tablets A for color negatives It was created.
[0351]
Operation (2)
69.4 g of hydroxylamine sulfate and 4 g of Pine Flow (Matsuya Chemical) are pulverized in the same manner as in the operation (1), and then mixed and granulated. The amount of water added is 3.5 ml, and after granulation, it is dried at 60 ° C. for 30 minutes to almost completely remove moisture from the granulated product. In this way, 0.3 g of sodium N-lauroylalanine is added to the prepared granulated product, and mixed for 3 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. Further, using a tableting machine in the same manner as in the operation (1), the tableting amount was set to 0.56 g per tablet, and compression tableting was performed to prepare 120 color negative replenishing tablets B for color development.
[0352]
Operation (3)
1-Hydroxyethane-1,1-diphosphonate disodium 15g, potassium sulfite 72.8g, potassium carbonate 375g, sodium hydrogen carbonate 3g, sodium bromide 3.7g and mannit 22g were ground and mixed in the same manner as in operation (1). Granulate with water added to 40ml. After granulation, the granulated product is dried at 70 ° C. for 60 minutes to remove moisture of the granulated product almost completely. In this way, 2 g of sodium N-lauroylalanine is added to the granulated material thus prepared, and mixed for 3 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. Further, using a tableting machine in the same manner as in the operation (1), the tableting amount was 3.9 g and tablet compression was performed using a tableting machine to prepare 120 color negative color development replenishing tablets C.
[0353]
2) Bleach replenishment tablets for color negatives
Operation (4)
175 g of 1,3-propanediaminetetraacetic acid ferric ammonium monohydrate, 2 g of 1,3-propanediaminetetraacetic acid, and 17 g of pineflow (Matsuya Chemical) were pulverized and mixed in the same manner as in the operation (1). Granulate with 8ml addition. After granulation, the granulated product is dried at 60 ° C. for 30 minutes to remove the moisture of the granulated product almost completely.
[0354]
Operation (5)
In the same manner as in the operation (1), 133 g of succinic acid, 200 g of ammonium bromide and 10.2 g of pine flow are pulverized, mixed and granulated. The amount of water added is 17 ml, and after granulation, it is dried at 70 ° C. for 60 minutes to almost completely remove moisture from the granulated product.
[0355]
Operation (6)
In the same manner as in the operation (1), 66.7 g of potassium sulfate, 60 g of potassium hydrogen carbonate and 8 g of mannitol are pulverized, mixed and granulated. The amount of water added is 13 ml, and after granulation, it is dried at 60 ° C. for 60 minutes to almost completely remove moisture from the granulated product.
[0356]
Operation (7)
The granulated material prepared in the above operations (4) to (6) is uniformly mixed for 10 minutes using a mixer in a room conditioned at 25 ° C. and 40% RH or less. Next, 6 g of sodium N-lauroyl sarcosine is added to this mixed granulated product and mixed for 3 minutes. Next, the mixture was compressed into tablets with a filling amount of 6.5 g per tablet using a tablet press modified from Tough Presto Collect 1527HU manufactured by Kikusui Seisakusho Co., Ltd., and 80 color negative bleach supplement tablets were prepared. .
[0357]
3) Fixing and replenishing tablets for color negatives
Operation (8)
In the same manner as in the operation (1), 2500 g of ammonium thiosulfate, 150 g of sodium sulfite, 150 g of potassium carbonate, 20 g of ethylenediaminetetraacetic acid disodium salt and 65 g of Pine Flow (manufactured by Matsutani Chemical) are pulverized, mixed and granulated. The amount of water added is 50 ml, and after granulation, it is dried at 60 ° C. for 120 minutes to almost completely remove moisture from the granulated product.
[0358]
Operation (9)
The granulated product prepared in the above operation (8) and 13 g of sodium N-lauroyl sarcosine are mixed for 3 minutes in a room conditioned at 25 ° C. and 40% RH or less using a mixer. Next, the mixture was compressed into tablets with a filling amount of 9.3 g per tablet using a tablet press modified from Kikusui Seisakusho Tough Presto Collect 1527HU, and 280 color negative fixing supplement tablets were prepared. .
[0359]
4) Tablets for stable replenishment for color negatives
Operation (10)
150 g of m-hydroxybenzaldehyde, 20 g of sodium lauryl sulfate, 60 g of disodium ethylenediaminetetraacetate, 65 g of lithium hydroxide monohydrate and 10 g of pine flow are pulverized, mixed and granulated in the same manner as in the operation (1). The amount of water added is 10 ml. After granulation, the granulated product is dried at 50 ° C. for 2 hours to remove moisture of the granulated product almost completely.
[0360]
Operation (11)
The granulated product prepared in the above operation (10) was adjusted to 25 ° C and 40% RH or less, and the filling amount per tablet was adjusted by a tableting machine modified with Kikusui Seisakusho Tough Presto Collect 1527HU. Compression compression was performed at 0.48 g, and 280 stable replenishing tablets for color negatives were prepared.
[0361]
Next, 2 tablets, 1 tablet, and 1 tablet each for A, B, and C for color development supplement tablets, 2 tablets for bleach supplement tablets, 3 tablets for fixing supplement tablets, and stable supplements As for tablets, each tablet was divided into one package, and each continuous 20-minute package was packaged by a four-side seal method. The same packaging material as that used in Example 1 was used.
[0362]
The processing is carried out until the overflow from the color developing tank tank reaches 5% of the tank liquid per day, and the overflow amount becomes twice that of the tank liquid (2.0R). An experiment was conducted on the number of insoluble tablets accumulated in each treatment tank and the dissolution status.
[0363]
Also, a Konica Color Super DD-100 film subjected to wedge exposure was developed immediately after the solid processing agent was introduced once and immediately before the next solid processing agent was introduced, and the difference in maximum blue transmission density (ΔDmax ( B)) was measured, and the average value from the start of running until each solid treatment agent was introduced 10 times was calculated.
[0364]
The results are shown in Tables 6 and 7.
[0365]
[Table 6]

[0366]
[Table 7]

[0367]
As is clear from Tables 6 and 7 4 ≦ S / R ≦ Four When 0, the effect of the present invention is clearly shown.
[0368]
(Example 5)
A color developing tablet was prepared according to the following operation.
[0369]
Operation (H)
40 g of disulfoethylhydroxylamine disodium salt, 200 g of sodium p-toluenesulfonate, 30 g of Tinopearl SFP (manufactured by Ciba Geigy), 30 g of sodium diethylenetriaminepentaacetate, 30 g of Pine Flow (manufactured by Matsutani Chemical Co., Ltd.) Water was added in small portions with a granulator and granulated. The amount of water added was 20 ml. Then, it dried at 40 degreeC for 12 hours in the dryer, and made the moisture content 1% or less. Finally, it was passed through a 16 mesh screen.
[0370]
Operation (I)
Color developing agent CD-3 150g, polyethylene glycol # 6000 100g, D-mannit 20g, water is added in small portions with a commercially available mixing granulator and granulated.
[0371]
The amount of water added was 20 ml. Then, it dried at 40 degreeC for 12 hours in the dryer, and made the moisture content 1% or less. Finally, it was passed through a 16 mesh screen.
[0372]
Operation (J)
100 g of sodium p-toluenesulfonate, 4.0 g of sodium sulfite, 30 g of potassium hydroxide, 100 g of polyethylene glycol (average molecular weight 6000), 330 g of potassium carbonate, 60 g of D-mannitol. Add and granulate. The amount of water added was 33 ml. Then, it dried at 40 degreeC for 12 hours in the dryer, and made the moisture content 1% or less. Finally, it was passed through a 16 mesh screen.
[0373]
Operation (K)
All the granulated products granulated in the above operations (H) to (J) and 10 g of sodium N-myristoyl-N-methyl-β-alanine are mixed in a mixer for 10 minutes.
[0374]
Next, the mixture is made into tablets using a tableting machine modified from Tough Press Collect 1527HU manufactured by Kikusui Seisakusho. The tablet was filled with 11.0 g and made into a cylindrical shape with a diameter of 30 mm, and the compression pressure was changed so that the bulk density was as shown in Table 8, and the same experiment as in Example 1 was performed on the color developer. One tablet was loaded for each loading operation. In addition, in adjusting the bulk density, it was changed by tableting after adding an appropriate amount of pine flow or potassium sulfate to the mixture in addition to the compression pressure.
[0375]
The results are shown in Table 8.
[0376]
[Table 8]

[0377]
As apparent from Table 8, the solubility, which is one of the effects of the present invention, is that the bulk density of the tablet is 1.0 to 2.5 g / cm. ^Three It can be seen that it becomes more prominent when.
[0378]
(Example 6)
In Example 5, the granulated product obtained in the same manner as in the operation (H) except that the chinopal SFP during the operation (H) was changed as shown in Table 9, and the same as in the operations (I) and (J) 11g and the bulk density of 1.4g / cm. ^Three A tablet with a diameter of 30 mm was prepared, and the color development was performed in the same manner as in Example 1.
[0379]
The results are shown in Table 9.
[0380]
[Table 9]

[0381]
As can be seen from Table 9, by adding the triazinyl stilbene fluorescent whitening agent represented by the general formula [E] to the color developer, the effects of the present invention can be further improved in terms of solubility and processing stability. It turns out that it plays remarkably.
[0382]
【The invention's effect】
First, eliminating liquid chemicals that pose a risk in transportation and handling, eliminating complicated operations for the user; Second, eliminating the user's own manual work of dissolving the concentration kit and completing a fully automated replenishment system Third, the solid processing agent that is directly charged into the processing solution does not impair the processing stability and dissolves without causing precipitation in the processing tank. Fourth, there is no need to store the liquid replenisher. It is possible to provide a solid processing agent with improved processing stability. Fifth, it is possible to achieve a low pollution system that reduces the use of plastic packaging material that eliminates the use of liquid plastic bottles.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram of a printer processor in which an automatic processor A and a photographic printing machine B are integrally configured.
2 is a schematic view of a color developing tank 1A which is a processing tank in the II section of the self-machine A of FIG.
FIG. 3 is a cross-sectional view of a processing agent supply unit and a processing agent supply unit to which a replenishing water supply unit of an automatic processor is added.
FIG. 4 is a plan view of the automatic processor.
FIG. 5 is a block diagram including control means of an automatic developing machine.
FIG. 6 is a block diagram in which pre-programmed evaporative replenishment setting means is added to the control means.
FIG. 7 is a cross-sectional view of a powdery processing agent supply device and a perspective view of a package.
FIG. 8 is a perspective view of a powdery processing agent supply apparatus.
FIG. 9 is a cross-sectional view of another powdery processing agent supply apparatus.
FIG. 10 is a cross-sectional view showing still another apparatus for supplying a powdery treatment agent.
FIG. 11 is a cross-sectional view and a perspective view of a PTP packaging processing agent supply apparatus.
FIG. 12 is a cross-sectional view showing an example of a parts feeder type supply device.
FIG. 13 is a cross-sectional view showing still another example of a parts feeder type supply device.
FIG. 14 is a perspective view showing still another example of the solid processing agent supply apparatus.
FIG. 15 is a plan view and a perspective view of a supply device, and a plan view of a package.
FIG. 16 is a side sectional view and a front sectional view of a supply device.
FIG. 17 is a cross-sectional view of a supply device and a perspective view of a package.
FIG. 18 is a cross-sectional view of a supply device for a solid processing agent packaged in blister pieces.
FIG. 19 is a cross-sectional view showing an example of the present invention (adding a solid processing agent directly to a processing tank).
FIG. 20 is a plan view of seal packaging.
FIG. 21 is a plan view showing a specific example of seal packaging of a three-side seal and a four-side seal.
FIG. 22 is a plan view showing a specific example of stick packaging.
FIG. 23 is a cross-sectional view showing a state in which the sealed package is folded and accommodated in a container.
FIG. 24 is a diagram showing a specific example of PTP packaging.
FIG. 25 is a diagram showing a specific example of batch packaging.
FIG. 26 is a diagram showing a specific example of a cartridge.
FIG. 27 is a perspective view showing another specific example of the cartridge.
FIG. 28 is a device for cutting a package by half-cutting it into a U-shape.
29 is a perspective view of an apparatus for half-cutting the U-shaped package of FIG. 28. FIG.
FIG. 30 shows an apparatus for cutting a package.
31 is a perspective view of an apparatus showing the cutting method of FIG. 30. FIG.
FIG. 32 is an apparatus showing a two-part cut method for a continuous package.
[Explanation of symbols]
1 treatment tank
1A-1E treatment tank
R Feed roller
2 processing section
3 Filter
4 Circulation pipe
5 Circulation pump
6 Drainage pipe
7 Heater
8 Throughput information detection (knowledge) means
9 Treatment agent supply control means
10 Extruded member
11 Solid processing agent input part
12 Partition wall
13 tablets
14 Filtration section (classification)
15 cartridges
17 Treatment agent supply means
18 Push nails
19 cam
21 Tablet press spring
23 Preprogrammed evaporative replenishment setting means
32 Hot water supply device
33 Solenoid valve
35 Drying section
36 Refill pipe
41 Pipe (for water replenishment)
42 Replenishment water supply means
43 Refill tank

Claims (5)

In a method for processing a silver halide photographic light-sensitive material in which a solid processing agent is directly charged into a processing solution of an automatic developing machine for silver halide photographic light-sensitive material, a complete dissolution time S (1 weight unit) of the solid processing agent is used. min ) And the amount R of silver halide photographic material processed per weight unit of the solid processing agent R ( m ² )But
4 ≦ S / R ≦ 40 ( min / m ² )
A method for processing a silver halide photographic light-sensitive material, wherein 2. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the solid processing agent is a granulated or tableted tablet formed by a granulation step. 3. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the solid processing agent, which is pre-weighed, is used. The solid processing agent has a bulk density. 1.0 ~ 2.5 g / cm ² A method for processing a silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein a solid processing agent is used. 5. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the solid processing agent contains a fluorescent sensitizer.

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