JPS61259249A - High contrast developing method for photographic image - Google Patents
High contrast developing method for photographic imageInfo
- Publication number
- JPS61259249A JPS61259249A JP10240385A JP10240385A JPS61259249A JP S61259249 A JPS61259249 A JP S61259249A JP 10240385 A JP10240385 A JP 10240385A JP 10240385 A JP10240385 A JP 10240385A JP S61259249 A JPS61259249 A JP S61259249A
- Authority
- JP
- Japan
- Prior art keywords
- group
- silver halide
- formula
- compd
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
- G03C5/29—Development processes or agents therefor
- G03C5/305—Additives other than developers
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/061—Hydrazine compounds
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
Description
【発明の詳細な説明】
囚 産業上の利用分野
本発明は、ハロゲン化銀写真感光材料を用いた写真画像
の形成方法に関係し、ヒドラジン化合物を用いて超硬調
な画像を与える方法に関するものである。[Detailed Description of the Invention] Industrial Field of Application The present invention relates to a method for forming photographic images using a silver halide photographic light-sensitive material, and more particularly to a method for providing ultra-high contrast images using a hydrazine compound. be.
β) 従来技術及びその問題点
ハロゲン化銀写真乳剤にヒドラジン化合物を添加して、
硬調なネガティブ特性を得るための方法が米国特許2,
419,975号に記載されている。β) Prior art and its problems By adding a hydrazine compound to a silver halide photographic emulsion,
A method for obtaining sharp negative characteristics is disclosed in US Patent 2,
No. 419,975.
この明細書くに、塩臭化銀乳剤にヒドラジン化合物を添
加し、高いpH(12,8)の現像液で処理することK
よってγが10’(i越える超硬調な写真特性を得てい
る。しかし、高いpHのために現像液は空気酸化に対し
て弱く不安定であり、長期間使用することができない。In this specification, a hydrazine compound is added to a silver chlorobromide emulsion and treated with a developer having a high pH (12,8).
Therefore, ultra-high contrast photographic properties with γ exceeding 10' (i) are obtained. However, due to the high pH, the developer is weak and unstable against air oxidation, and cannot be used for a long period of time.
また、下記の成分(1)〜(4) ((1)ジヒドロキ
シベンゼン現像剤、(2)3−ピラゾリドン現像剤、(
3)亜硫[j!保恒剤、(4)アミノ化合物)を含む現
像液にてハロゲン化銀写真乳剤を処理し、迅速に硬調な
ネガティブ画像を得る方法も紹介されている。(特開5
6−106244)Lかし、人体に有害なアミノ化合物
を処理液中に含むため、長期間処理液を使用することは
人体に何らかの弊害を及ぼすと考えねばならない。In addition, the following components (1) to (4) ((1) dihydroxybenzene developer, (2) 3-pyrazolidone developer, (
3) Subsulfite [j! A method for quickly obtaining high-contrast negative images by processing a silver halide photographic emulsion with a developer containing a preservative and (4) an amino compound is also introduced. (Unexamined 5
6-106244) Since the treatment liquid contains amino compounds that are harmful to the human body, it must be considered that using the treatment liquid for a long period of time may cause some harm to the human body.
従って、品質上優れた網点画像金与え、かつ長期の保存
が可能であシ、人体に有害な物質を含−まないような処
理液を使用する硬調現像法がぜひとも必要になる。Therefore, there is a strong need for a high-contrast development method that provides halftone images of excellent quality, can be stored for a long time, and uses a processing solution that does not contain substances harmful to the human body.
(Q 発明の目的
本発明の目的のひとつは、安定な現像液を用いて優れた
網点画質を得るためのハロゲン化銀写真材料の現像方法
を提供することである。(Q. Purpose of the Invention One of the objects of the present invention is to provide a method for developing silver halide photographic materials to obtain excellent halftone image quality using a stable developer.
本発明の他の目的の一つは、人体に有害なアミン化合物
を取シ除いた処理液を用いて優れた網点画質を得るため
のハロゲン化銀写真感光材料の現像方法を提供すること
である。Another object of the present invention is to provide a method for developing a silver halide photographic material to obtain excellent halftone image quality using a processing solution that removes amine compounds harmful to the human body. be.
(至)発明の構成
本発明者らは、鋭意検討した所、下記一般式(I)で表
わされるヒドラジン化合物が、上記条件を満足する事を
見い出した。(To) Structure of the Invention The present inventors have made extensive studies and found that a hydrazine compound represented by the following general formula (I) satisfies the above conditions.
一般式(1)
%式%
式中、R1は、アリール基(例えば、フェニル基、ナフ
チル基等)を表わす。General formula (1) %Formula% In the formula, R1 represents an aryl group (eg, phenyl group, naphthyl group, etc.).
(ただしアリール基は、置換されていてもよく置換基と
して、例えば、アルキル基、アラルキル基、アルコキシ
基、アリールオキシ基、アミノ基、脂肪族アシルアミド
基、芳香族アシルアミド基、脂肪族スルホンアミド基、
芳香族スルホンアミド基、アルコキシカルボニル基、ハ
ロゲン原子、ニトロ基、カルボキシル基、スルホ基、シ
アノ基、カルバモイル基、スルファモイル基、セミカル
バジド基、チオセミカルバジド基、チオウレイド基、ウ
レイド基、アルキルチオ基、アリールチオ基、脂肪族チ
オアシルアミド基、芳香族チオアシルアミド基等)を表
わし、IL2はアリール基〔(例えは、フェニル基等)
を表わす。ただしアリール基は置換されていてもよく置
換基としては、例えば、アルキル基、ハロゲン原子、ア
ルコキシ基、シアノ基、ニトロ基、カルボキシル基、ア
ルコキシカルボニル基等〕又はアルキル基(ただしアル
キル基は置換されていてもよい)を表わす。(However, the aryl group may be substituted, and the substituents include, for example, an alkyl group, an aralkyl group, an alkoxy group, an aryloxy group, an amino group, an aliphatic acylamide group, an aromatic acylamide group, an aliphatic sulfonamide group,
Aromatic sulfonamide group, alkoxycarbonyl group, halogen atom, nitro group, carboxyl group, sulfo group, cyano group, carbamoyl group, sulfamoyl group, semicarbazide group, thiosemicarbazide group, thioureido group, ureido group, alkylthio group, arylthio group, aliphatic thioacylamide group, aromatic thioacylamide group, etc.), and IL2 represents an aryl group [(for example, phenyl group, etc.)
represents. However, the aryl group may be substituted, and examples of the substituent include an alkyl group, a halogen atom, an alkoxy group, a cyano group, a nitro group, a carboxyl group, an alkoxycarbonyl group, etc.) or an alkyl group (however, an alkyl group is not substituted). ).
本発明に用いられるヒドラジン化合物の具体例を以下に
記載するが、本発明は、これらに限定されるものではな
い。Specific examples of the hydrazine compound used in the present invention are described below, but the present invention is not limited thereto.
S CH。S CH.
CH。CH.
CH。CH.
一般式(1)で示される化合物は、一般にはヒドラジン
類とスルホニルハライド類との反応によって合成するか
、又は、相当する1−スルボニル−2−(4あるいa3
−二トロフェニル)ヒドラジンを通常の方法で還元し相
当するアミン体にかえた後、縮合、付加反応等を用い一
般的な反応によって合成することができる。The compound represented by the general formula (1) is generally synthesized by the reaction of hydrazines and sulfonyl halides, or the corresponding 1-sulfonyl-2-(4 or a3
-nitrophenyl)hydrazine is reduced by a conventional method to convert it into the corresponding amine compound, and then it can be synthesized by a general reaction using condensation, addition reaction, etc.
次に本発明の化合物の合成法を具体的に述べる。Next, a method for synthesizing the compound of the present invention will be specifically described.
化合物(1)の合成:
フェニルヒドラジン2.16F(0,02モル)トリエ
チルアミン2.02 f (0,02モル)をジオキサ
ン20mにとかし、内温を20℃以下に保ち、攪拌下に
メタンスルホニルクロライド2.29 t (0,02
モル)をジオキサン5mにとかした液を約4分間で加え
た後、同温に1時間攪拌した後室濃茶
で4時間攪拌し、析晶物を戸去した後p液を水溶上減圧
下に乾固し、残渣を水から再結晶し、白色結晶2.52
を得た。融点は、129.5℃〜131゜0℃であった
。Synthesis of compound (1): Phenylhydrazine 2.16 F (0.02 mol) and triethylamine 2.02 F (0.02 mol) were dissolved in 20 ml of dioxane, the internal temperature was kept below 20°C, and methanesulfonyl chloride was added under stirring. 2.29t (0,02
mol) dissolved in 5 m of dioxane was added over a period of about 4 minutes, stirred at the same temperature for 1 hour, then stirred in room koicha for 4 hours, and after removing the precipitated crystals, the p solution was dissolved in water under reduced pressure. The residue was recrystallized from water to give white crystals of 2.52
I got it. The melting point was 129.5°C to 131°0C.
化合物(3)の合成:
フェニルヒドラジン16.22f(0,15モル)とト
リエチルアミン15.18F(0,15モル)をメチレ
ンクロライド200−にとかし、内温ヲー30℃以下に
保ち、攪拌下にトリクロロメタンスルホニルクロライド
32.6El(0,15モル)をメチレンクロライド5
0−にとかした液を約25分間で加えた後、同温に3時
間攪拌した後、室温で3時間攪拌し、析品物’kF取し
、メチレンクロライドで洗滌し、白色結晶14fを得た
。融点は、237.0℃〜238.5℃(分解)であっ
た。Synthesis of compound (3): Phenylhydrazine 16.22F (0.15 mol) and triethylamine 15.18F (0.15 mol) were dissolved in methylene chloride 200-, keeping the internal temperature below 30°C, and adding trichloromethane while stirring. Methanesulfonyl chloride 32.6El (0.15 mol) methylene chloride 5
After adding the solution dissolved in 0- for about 25 minutes, stirring at the same temperature for 3 hours, stirring at room temperature for 3 hours, precipitate 'kF was collected and washed with methylene chloride to obtain white crystals 14f. . The melting point was 237.0°C to 238.5°C (decomposed).
本発明で用いるこれ等の化合物は処理剤又は感光材料の
乳剤側の任意の層に添加し1て用いることができる。These compounds used in the present invention can be used by being added to a processing agent or any layer on the emulsion side of a light-sensitive material.
本発明に用いられる表面潜像型ノ・ロゲン化銀乳剤は、
酸性法、中性法、又はアンモニア法のどの方法で製造さ
れても良い。本発明は、ノ・ロゲン化銀写真乳剤の性質
、例えばハロゲン化銀の組成(例えば・臭化銀、塩化銀
、塩臭化銀、沃臭化銀、塩沃臭化@)、ハロゲン化銀の
結晶形や晶癖の大きさに関係なく実施できるが、臭素3
0モルチ以下、沃素10モルチ以下の塩臭化銀乳剤が特
に好ましい。The surface latent image type silver halogenide emulsion used in the present invention is
It may be produced by any method including an acid method, a neutral method, or an ammonia method. The present invention relates to the properties of silver halide photographic emulsions, such as the composition of silver halide (for example, silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloride iodobromide), silver halide It can be carried out regardless of the crystal form or crystal habit size of bromine 3.
Silver chlorobromide emulsions containing 0 mole or less and 10 mole or less of iodine are particularly preferred.
本発明による乳剤中には各種の添加剤を含有することが
できる。例えば、化学増感剤(例えば、チオ尿素、ハイ
ポ等のイオウ増感剤、金、白金、イリジウム化合物等の
貴金属増感剤、還元増感剤)等も併用して用いることが
できる。また、分光増感剤、強色増感剤、安定剤、カプ
リ防止剤、界面活性剤、現像剤、現像促進剤、硬膜剤、
硬膜促進剤、カプラー、脱銀促進剤、色素液改良剤、増
白剤、増粘剤及びこれらのブレカーサ−等を、含有する
ことができる。The emulsion according to the invention can contain various additives. For example, chemical sensitizers (for example, sulfur sensitizers such as thiourea and hypo, noble metal sensitizers such as gold, platinum, and iridium compounds, and reduction sensitizers) can also be used in combination. In addition, spectral sensitizers, supersensitizers, stabilizers, anti-capri agents, surfactants, developers, development accelerators, hardeners,
It may contain a hardening accelerator, a coupler, a desilvering accelerator, a dye solution improver, a brightener, a thickener, a breaker thereof, and the like.
本発明に用いられるノ為ロゲン化銀乳剤の保護コロイド
としては、ゼラチン、変性ゼラチン、アルブミン、寒天
、アラビアゴム、アルギン酸等の天然物、ポリビニルア
ルコール、ポリビニルピロリドン、アクリルアマイドと
アクリル酸とビニルイミダゾールの共重合物等の水溶性
合成樹脂が挙げられる。Protective colloids for the silver halide emulsion used in the present invention include gelatin, modified gelatin, albumin, agar, gum arabic, natural products such as alginic acid, polyvinyl alcohol, polyvinylpyrrolidone, acrylamide, acrylic acid, and vinylimidazole. Examples include water-soluble synthetic resins such as copolymers.
本発明の乳剤は、適当な支持体、例えばガラス、酢酸セ
ルロースフィルム、ポリエチレンテレフタレートフィル
ム、紙、バライタ塗横紙、ポリオレフィン(例えば、ポ
リエチレン、ボリグロピレン等)破嶺紙の如きものの上
に塗布される。これらの支持体は、公知の方法でコロナ
処理されてもよく、又、必要に応じて公知の方法で下引
加工されても良い。The emulsions of the present invention are coated on a suitable support such as glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta-coated paper, polyolefin (e.g. polyethylene, polyglopylene, etc.) paper. . These supports may be corona treated by a known method, and may also be undercoated by a known method if necessary.
本発明の構成層には当業界周知の化合物例えば硬膜剤、
マット剤、螢光増白剤、帯電防止剤、増粘剤、ハロゲン
化銀、物理現像核、カブリ防止剤、分光増感剤、紫外線
吸収剤、ハレーシ1ン防止色素、カプラー、現像主薬、
これらのプレカーサー等を添加することができる。The constituent layers of the present invention include compounds well known in the art, such as hardeners,
Matting agent, fluorescent whitening agent, antistatic agent, thickener, silver halide, physical development nucleus, antifoggant, spectral sensitizer, ultraviolet absorber, antihalation dye, coupler, developing agent,
These precursors and the like can be added.
本発明によるハロゲン化銀写真乳剤は、必要に応じて保
護層、中間層、紫外線吸収層、下塗層あるいは他のハロ
ゲン化銀乳剤とともに塗設される・本発明において用い
られる水性アルカリ現像液は、良く知られている現像主
薬を含むことができる。現像主薬としては、ジヒドロキ
シベンゼン現像剤(例えばハイドロキノン)、3ピラゾ
リドン現像剤(例えば1−フェニル−3−ピラゾリドン
)が好ましい。The silver halide photographic emulsion according to the present invention is coated with a protective layer, an intermediate layer, an ultraviolet absorbing layer, an undercoat layer, or other silver halide emulsion as necessary.The aqueous alkaline developer used in the present invention is , well-known developing agents. As the developing agent, dihydroxybenzene developer (eg, hydroquinone) and 3-pyrazolidone developer (eg, 1-phenyl-3-pyrazolidone) are preferred.
本発明において用いられる水性アルカリ現像液は、空気
酸化から現像剤を保護する目的で、亜硫酸塩保恒剤を含
有している。好ましくは亜硫酸塩(例えば亜硫酸ナトリ
ウム)である。The aqueous alkaline developer used in the present invention contains a sulfite preservative for the purpose of protecting the developer from air oxidation. Preferred are sulfites (eg sodium sulfite).
一般に、ヒドラジン化合物を乳剤中あるいは処理液中に
温潤し、十分な網点品質の画像を得る場合、コントラス
)t−増大させるために、アミノ化合物が必要であると
されているが、本発明で提案されている化食物に関して
はその限シではない。Generally, when a hydrazine compound is warmed into an emulsion or a processing solution to obtain an image with sufficient halftone quality, an amino compound is required to increase the contrast. This is not the case with the proposed chemical foods.
アミノ化合物が必要とされる場合、好ましいものけ、次
式で表わされる化合物である。When an amino compound is required, a preferred compound is a compound represented by the following formula.
ここで R1は2〜lO個の炭素原子を有するヒドロキ
シアルキル基、R+は水素原子、Rは1〜lO個の炭素
原子を有するアルキル基、2〜10個の炭素原子を有す
るヒドロキシアルキル基、ベンジル基あるいは次式によ
って表わされる基である。Here, R1 is a hydroxyalkyl group having 2 to 10 carbon atoms, R+ is a hydrogen atom, R is an alkyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 2 to 10 carbon atoms, benzyl group or a group represented by the following formula.
上式においてX及びYは、それぞれ水素原子、1〜10
個の炭素原子を有するアルキル基あるいは、2〜10個
の炭素原子を有するヒドロキシアルキル基である。In the above formula, X and Y are each a hydrogen atom, 1 to 10
or a hydroxyalkyl group having from 2 to 10 carbon atoms.
また、次式で表わされるアミノ化合物も好ましい。Also preferred are amino compounds represented by the following formula.
R1は、1〜10個の炭素原子を有するアルキル基であ
シ、R2及びR3は、それぞれ水素原子あるいは1〜1
0個の炭素原子を有するアルキル基テする。R1 is an alkyl group having 1 to 10 carbon atoms, and R2 and R3 are each a hydrogen atom or 1 to 1 carbon atom.
An alkyl group having 0 carbon atoms.
好ましいアミノ化合物の例を挙げると、ジェタノールア
ミン
2−ジエチルアミノ−1−エタノール
2−メチルアミノ−1−エタノール
3−ジメチルアミノ−1,2−プロパンジオール3−ジ
エチルアミノ−1−/’ロバノール等である。Examples of preferred amino compounds include jetanolamine 2-diethylamino-1-ethanol 2-methylamino-1-ethanol 3-dimethylamino-1,2-propanediol 3-diethylamino-1-/'lovanol, etc. .
本発明に用いられる水性アルカリ現像液は、カブリの生
成1i−最小限度に抑えるために%また、好ましい網点
品質を得る目的で、必要な有機カブリ防止剤を含む、ベ
ンゾ)IJアゾールカブリ防止剤を使用するのが一般的
であシ、好ましくは、5−メチルベンゾトリアゾールで
ある。The aqueous alkaline developer used in the present invention contains a benzo)IJ azole antifoggant, in order to minimize the formation of fog, and also contains the necessary organic antifoggants for the purpose of obtaining favorable halftone dot quality. It is common to use 5-methylbenzotriazole, preferably 5-methylbenzotriazole.
本発明に用いられる水性アルカリ現像液は、一般式で表
わされるヒドラジン化合物を含む。現像液中に混入され
るヒドラジン化合物は、ハロゲン化銀写真乳剤の81類
、アミノ化合物、カブ1す防止剤の量等によって最適な
量を選択されることが望ましい。本発明の化合物の場合
、io−’〜1o−5モル/ I Agの濃度が最も好
ましい。The aqueous alkaline developer used in the present invention contains a hydrazine compound represented by the general formula. It is desirable that the optimum amount of the hydrazine compound mixed into the developer be selected depending on the amount of Type 81, amino compound, antifoggant, etc. of the silver halide photographic emulsion. For compounds of the invention, concentrations of io-' to 1o-5 mol/I Ag are most preferred.
〈実施例1〉
97.4チのBr 、 2.6俤の工を含むヨウ臭化銀
乳剤を銀量3.7帽の塗布量で100μmの厚さのポリ
エステルフィルム上に塗布し、Xenon PIash
’ir:光源として10 秒のウェッジ露光を与えた
。露光済のサンプルを表−1の様な組成からなる水性ア
ルカリ現像液中で処理した。<Example 1> A silver iodobromide emulsion containing 97.4 g of Br and 2.6 g of silver was coated on a 100 μm thick polyester film with a coating weight of 3.7 g of silver, and Xenon PIash was applied.
'ir: A 10 second wedge exposure was applied as a light source. The exposed samples were processed in an aqueous alkaline developer having the composition shown in Table 1.
表−1;水性アルカリ現像液の処方
0.8M +)7駿溶液 500 w
4/lNa 2 So 3
60 f/LEDTA−2Na
1.Of/L5メチルIHベンゾトリアゾール 0.1
FM’/lハイドロキノン 30
f/11フェニル−4−メチルーヒドロキシメーy−
″′−3zラゾ゛ノド’ 0.4t/1KBr
3.5 f/Lジエチルエ
タノールアミン 201/lさらに上記の処方
に1本発明における化合物(2)、(3)、(6)、(
7)をそれぞれ0.1f/lの濃度で加え、4種類の現
像液を作成した。現像液のpHは11・8とした。現像
温度は20℃、現像時間は150秒で行われた。現像後
、通常の写真処理法に基づいて、定着、水洗、乾燥の処
理を行なりた。現像されたサンプルを網点の性DK関し
て評価した。その結果t−表−2に示す。Table-1; Formula of aqueous alkaline developer 0.8M +) 7 Shun solution 500w
4/lNa 2 So 3
60 f/LEDTA-2Na
1. Of/L5 Methyl IH Benzotriazole 0.1
FM'/l Hydroquinone 30
f/11 phenyl-4-methyl-hydroxymery-
″'-3z Razor Nod' 0.4t/1KBr
3.5 f/L diethylethanolamine 201/l and 1 compound of the present invention (2), (3), (6), (
7) was added at a concentration of 0.1 f/l to prepare four types of developing solutions. The pH of the developer was 11.8. The development temperature was 20°C and the development time was 150 seconds. After development, fixing, washing, and drying were carried out according to conventional photographic processing methods. The developed samples were evaluated for dot quality DK. The results are shown in Table 2.
表−2
表−2から、本発明における化合物は、12以下の処理
液のpHでヨウ臭化銀に対して硬調化作用を持つことが
わかった。Table 2 From Table 2, it was found that the compounds of the present invention have a contrast enhancing effect on silver iodobromide at a pH of 12 or less in the processing solution.
〈実施例2〉
実施例1から、本発明における化合物は、12以下のp
Hで、ヨウ臭化銀乳剤に対して硬調化作用に対して有効
であることがわかったが、さらに低いpHでも十分な網
点品質を得る写真特性が得られるかどうかを調べるため
、次の実験を行なった。<Example 2> From Example 1, the compound in the present invention has a p of 12 or less.
H was found to be effective against the contrast-enhancing effect on silver iodobromide emulsions, but in order to investigate whether the photographic properties of obtaining sufficient halftone dot quality could be obtained even at lower pH, the following We conducted an experiment.
31%のBr、0.07%の工を含むヨウ塩臭化銀乳剤
を、3.6PAg〜の塗布量で厚さ100μのポリエス
テルフィルム上Km布されたちのK。A silver iodochlorobromide emulsion containing 31% Br and 0.07% Co was coated on a 100μ thick polyester film at a coating weight of 3.6PAg.
実施例1と同条件の露光を与え、実施例1における現像
液を使用して写真処理を行なった。また、現像液のpH
が写真特性に与える効果音調べるため、pH1−数段階
にg14節し九。現像されたサンプルt−網点の性能に
関して評価した。その結果を表−3に示す。Exposure was given under the same conditions as in Example 1, and photographic processing was performed using the developer in Example 1. In addition, the pH of the developer
In order to investigate the sound effect that it has on the photographic characteristics, the pH was adjusted to several levels from 1 to 14 times. The developed samples were evaluated for t-dot performance. The results are shown in Table-3.
(以下余白)
表−3
表−3から、本発明における化合物は、ヨウ塩臭化銀に
対してさらに低い処理液pHでも硬調化作用が得られる
ことがわかった。この結果は処理液の安定性向上のため
に、極めて重要な結果である。(The following is a blank space) Table 3 From Table 3, it was found that the compound of the present invention can obtain a high contrast effect even at a processing solution pH lower than that of silver iodochlorobromide. This result is extremely important for improving the stability of the processing solution.
〈実施例3〉
実施例(1)、(2)から、本発明における化合物は1
2以下のpHでハロゲン化銀写真感光材料に硬調化作用
を持たせることが判ったが、我々の興味は人体に有害な
アミノ化合物を含まずに十分な網点品質に必要な硬調化
効果が得られるかどうか、という所にある。そこで、次
の実験を行なった。実施例1の表−1に記されている処
方からジエチルエタノールアミンを取り除いて現像液を
調製し、実施例2と同様の方法でサンプルを作成した。<Example 3> From Examples (1) and (2), the compound in the present invention is 1
It has been found that a silver halide photographic light-sensitive material can have a high contrast effect at a pH of 2 or less, but we are interested in finding a way to achieve the high contrast effect necessary for sufficient halftone dot quality without containing amino compounds that are harmful to the human body. It depends on whether you can get it or not. Therefore, we conducted the following experiment. A developer was prepared by removing diethylethanolamine from the formulation shown in Table 1 of Example 1, and a sample was prepared in the same manner as in Example 2.
使用したヒドラジン化合物は本発明の化合物(3)であ
る。現像液f)pHFlll、0,11.5.12.0
+7)3点をとった。表−4に、サンダルの網点性能を
示す。The hydrazine compound used is the compound (3) of the present invention. Developer f) pHFllll, 0,11.5.12.0
+7) Scored 3 points. Table 4 shows the halftone dot performance of sandals.
表−4に示されるように、本発明で提案された化合物(
3)tlj:、ジエチルエタノールアミン’に取り除い
た現像液を使用しても、ハロゲン化銀感光材料ニ対シテ
十分良好な網点品質を与え得ることがわかった。As shown in Table 4, the compounds proposed in the present invention (
3) It has been found that even when a developer removed with tlj: diethylethanolamine' is used, sufficiently good halftone dot quality can be given to silver halide photosensitive materials.
この結果は、処理液の保存性あるいは人体に対する有害
性を考慮するうえで、極めて重要な結果である。This result is extremely important when considering the storage stability of the treatment liquid or its toxicity to the human body.
Claims (1)
記一般式( I )で表わされる化合物の存在下で現像す
ることを特徴とする写真画像の形成方法。 一般式( I ) R_1−NHNH−SO_2R_2 (式中R_1はアリール基を表わし、R_2はアリール
基又はアルキル基を表わす。)[Scope of Claims] A method for forming a photographic image, which comprises developing a silver halide photographic material having a latent image on its surface in the presence of a compound represented by the following general formula (I). General formula (I) R_1-NHNH-SO_2R_2 (In the formula, R_1 represents an aryl group, and R_2 represents an aryl group or an alkyl group.)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10240385A JPS61259249A (en) | 1985-05-13 | 1985-05-13 | High contrast developing method for photographic image |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10240385A JPS61259249A (en) | 1985-05-13 | 1985-05-13 | High contrast developing method for photographic image |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS61259249A true JPS61259249A (en) | 1986-11-17 |
Family
ID=14326477
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10240385A Pending JPS61259249A (en) | 1985-05-13 | 1985-05-13 | High contrast developing method for photographic image |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS61259249A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6332538A (en) * | 1986-07-25 | 1988-02-12 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material |
JPS63121838A (en) * | 1986-11-11 | 1988-05-25 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material |
JPH0627571A (en) * | 1992-07-07 | 1994-02-04 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material and processing method for the same |
US5695913A (en) * | 1995-02-28 | 1997-12-09 | Fuji Photo Film Co., Ltd. | Process for the formation of color image |
-
1985
- 1985-05-13 JP JP10240385A patent/JPS61259249A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6332538A (en) * | 1986-07-25 | 1988-02-12 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material |
JPS63121838A (en) * | 1986-11-11 | 1988-05-25 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material |
JPH0627571A (en) * | 1992-07-07 | 1994-02-04 | Fuji Photo Film Co Ltd | Silver halide photographic sensitive material and processing method for the same |
US5695913A (en) * | 1995-02-28 | 1997-12-09 | Fuji Photo Film Co., Ltd. | Process for the formation of color image |
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