JPH039450B2 - - Google Patents
Info
- Publication number
- JPH039450B2 JPH039450B2 JP59147109A JP14710984A JPH039450B2 JP H039450 B2 JPH039450 B2 JP H039450B2 JP 59147109 A JP59147109 A JP 59147109A JP 14710984 A JP14710984 A JP 14710984A JP H039450 B2 JPH039450 B2 JP H039450B2
- Authority
- JP
- Japan
- Prior art keywords
- silver halide
- emulsion
- silver
- desensitizer
- sensitivity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000839 emulsion Substances 0.000 claims description 41
- 229910052709 silver Inorganic materials 0.000 claims description 31
- 239000004332 silver Substances 0.000 claims description 31
- -1 silver halide Chemical class 0.000 claims description 30
- 229940090898 Desensitizer Drugs 0.000 claims description 24
- 230000035945 sensitivity Effects 0.000 claims description 20
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 17
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 17
- 239000000463 material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 description 9
- 150000003283 rhodium Chemical class 0.000 description 9
- 238000000586 desensitisation Methods 0.000 description 7
- 239000012496 blank sample Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 108010010803 Gelatin Proteins 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- LJTMQHALPVCERW-UHFFFAOYSA-N 4-methyl-5-nitro-3h-1,3-thiazole-2-thione Chemical compound CC=1NC(=S)SC=1[N+]([O-])=O LJTMQHALPVCERW-UHFFFAOYSA-N 0.000 description 2
- AVXJAQDWWJILLN-UHFFFAOYSA-N 5-[(3-nitrophenyl)methylidene]-2-sulfanylidene-1,3-thiazolidin-4-one Chemical compound [O-][N+](=O)C1=CC=CC(C=C2C(NC(=S)S2)=O)=C1 AVXJAQDWWJILLN-UHFFFAOYSA-N 0.000 description 2
- TWKKZGQGZHLROJ-UHFFFAOYSA-N 6-chloro-4,5-dinitro-2h-benzotriazole Chemical compound [O-][N+](=O)C1=C([N+](=O)[O-])C(Cl)=CC2=NNN=C21 TWKKZGQGZHLROJ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000011033 desalting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- SOUHUMACVWVDME-UHFFFAOYSA-N safranin O Chemical compound [Cl-].C12=CC(N)=CC=C2N=C2C=CC(N)=CC2=[N+]1C1=CC=CC=C1 SOUHUMACVWVDME-UHFFFAOYSA-N 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- QHVZYSIEYHLOJN-UHFFFAOYSA-M 2,3-dimethyl-6-nitro-1,3-benzothiazol-3-ium;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.[O-][N+](=O)C1=CC=C2[N+](C)=C(C)SC2=C1 QHVZYSIEYHLOJN-UHFFFAOYSA-M 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
- RTRVNVACCLONPE-UHFFFAOYSA-N 3-ethyl-2-[2-(2-nitrophenyl)ethenyl]-1,3-benzothiazol-3-ium Chemical compound S1C2=CC=CC=C2[N+](CC)=C1C=CC1=CC=CC=C1[N+]([O-])=O RTRVNVACCLONPE-UHFFFAOYSA-N 0.000 description 1
- ZXQHSPWBYMLHLB-BXTVWIJMSA-M 6-ethoxy-1-methyl-2-[(e)-2-(3-nitrophenyl)ethenyl]quinolin-1-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC2=CC(OCC)=CC=C2[N+](C)=C1\C=C\C1=CC=CC([N+]([O-])=O)=C1 ZXQHSPWBYMLHLB-BXTVWIJMSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 238000003969 polarography Methods 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000011079 streamline operation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
Description
(A) 産業上の利用分野
本発明は、ハロゲン化銀写真乳剤に関し、より
詳しくは高感度の明室用感光材料に用いるハロゲ
ン化銀写真乳剤に関する。
(B) 従来技術及びその問題点
近年、印刷分野においては、印刷物の複雑さ、
スキヤナーの発達などにより、返し作業工程の能
率向上が要望されている。そのために従来から使
用されてきた返し用フイルムに比べて10-4〜10-5
程度の超低感度の写真フイルムが開発され、明室
（紫外線を除いた白色螢光灯下）で取扱いが可能
な返しフイルム、即ち明室用感光材料として実用
され始めてきた。このような明室感光材料に要求
される性能は、硬調で十分な最大濃度を有し、明
室で長時間の取扱いが可能であり、プリンター光
源に対しては高い感度を有していること等であ
る。しかし、これまでの明室用感光材料は、上述
したような性能を十分満足しているとは言い難
い。
一般に、明室用感光材料として利用できる程度
の超低感度の乳剤は、ロジウム塩の如き無機減感
剤あるいはピナクリプトール・イエローの如き有
機減感剤を用いることによつて得られる。例え
ば、多量のロジウム塩を用いて明室用感光材料を
製造する方法としては、特開昭56−125734、同昭
56−149030、同昭56−149031、同昭58−190943等
があり、主として塩化銀からなるハロゲン化銀乳
剤にその乳剤の感度を約1/300〜約1/500減少させ
る量のロジウム塩を使用するものである。しか
し、ロジウム塩を用いて低感度にした塩化銀乳剤
は、明室光下で取扱うとカブリを生じ易く、特に
感度を高くするに従つて著しいカブリの増大をも
たらす欠点がある。
一方、本出願人は、ロジウム塩を使用し製造し
た上述の如き超低感度の塩化銀を主体とするハロ
ゲン化銀乳剤とほぼ同じ感度のハロゲン化銀乳剤
を有機減感剤を使用して製造すれば、ロジウム塩
の欠点が生じない明室用感光材料が得られるとい
う事実を確認している。しかしまた有機減感剤を
使用して製造したハロゲン化銀乳剤は、塩化銀を
主体としているため、硬調で高い最大濃度が得ら
れ易い反面、画像露光を施こした後、現像するま
での間、同様に明室光下に放置すると著しい感度
の低下を生じるという新たな問題があることが判
明し、この新たな問題を解決する方法を種々提案
（例えば、特願昭58−31413、同昭58−33600、同
昭58−54536、同昭59−39413等）したが、安定的
に解決できる完全な方法とは言えないものであつ
た。
(C) 発明の目的
本発明の目的は、塩化銀を主体とする明室用感
光材料のハロゲン化銀乳剤における前述した諸問
題を解決し、硬調で最大濃度が高く、飛躍的な増
感を図ると共に明室光下でのカブリの発生や減感
のないハロゲン化銀写真乳剤を提供することであ
る。
(D) 発明の構成
本発明は、少なくとも70モル％の塩化銀と減感
剤を含有するネガ型微粒子ハロゲン化銀写真乳剤
であつて、前記減感剤はポーラログラフの陽極電
位と陰極電位の和が正である有機減感剤であり該
有機減感剤の量が前記乳剤の感度をlogE＝1.3（但
し、塩化銀の場合にはlogE＝1.0）を越えない値
で減少させるに必要な量であることを特徴とする
ハロゲン化銀写真乳剤である。
以下、さらに本発明を詳しく説明する。
本発明に用いられる有機減感剤は、一般に直接
ポジ用ハロゲン化銀乳剤に用いることが知られて
いるものである。すなわち本発明において用いら
れる有機減感剤は、そのポーラログラフ半波電位
即ち、ポーラログラフイーで決定されるその酸化
還元電位によつて特徴づけられる。
本発明に有用な有機減感剤は、ポーラログラフ
陽極電位とポーラログラフ陰極電位の和が正であ
るものである。これらの酸化還元電位の測定法に
ついては、例えば、米国特許第3501307号明細書
に記載されている。
そのような有機減感剤の具体例は、数多くの特
許明細書、文献に記載されており、それらはいず
れも本発明において同じ作用をもつているもので
あつて、たとえば特公昭36−17595、同昭39−
20261、同昭40−26751、同昭43−13167、同昭45
−8833、同昭47−8746、同昭47−10197、同昭50
−37530、特開昭48−24734、同昭49−84639、同
昭56−152525、米国特許第2271229号、同第
2541472号、同第3035917号、同第3062651号、同
第3124458号、同第3326687号、同第3671254号等
の明細書に記載の化合物が使用できる。
以下に例を示している。
（Ｄ−１）１，３−ジエチル−1′−メチル−2′−
フエニルイミダゾ〔４，５−ｂ〕−キ
ノキサリノ−3′−インドロカルボシア
ニン・アイオダイド
（Ｄ−２） ピナクリプトール・イエロー
（Ｄ−３）１，1′，３，３，3′3′−ヘキサメチル
−５，5′−ジニトロインドカルボシア
ニン・Ｐ−トルエンスルホネート
（Ｄ−４）５，5′−ジクロロ−３，3′−ジエチル
６，6′−ジニトロチアカルボシアニ
ン・アイオダイド
（Ｄ−５）１，1′−ジメチル−２，2′−ジフエニ
ル−３，3′−インドロカルボシアニ
ン・プロマイド
（Ｄ−６）１，1′，３，3′−テトラエチルイミダ
ゾ〔４，５−ｂ〕キノキサリノカルボ
シアニン・クロライド
（Ｄ−１） ５−ｍ−ニトロベンジリデンローダ
ニン
（Ｄ−８）６−クロロ−４−ニトロ−ニトロベン
ゾトリアゾール
（Ｄ−９）１，1′−ジブチル−４，4′−ピピリジ
ニウム・ジプロマイド
（Ｄ−10）１，1′−エチレン−２，2′−ピピリジ
ニウム・ジプロマイド
（Ｄ−11）４−（Ｐ−ｎ−アミロキシフエニル）−
２，６−ジ（Ｐ−エチルフエニル）
チアピリリウム・パークロレート
（Ｄ−12）２−メルカプト−４−メチル−５−ニ
トロチアゾール
（Ｄ−13）２−（ｏ−ニトロスチリル）−３−エチ
ルベンゾチアゾリウム・Ｐ−トルエ
ンスルホネート
（Ｄ−14）２−（Ｐ−ニトロスチリル）−キノリ
ン・Ｐ−トルエンスルホネート
（Ｄ−15） フエノサフラニン
（Ｄ−16） ピナクリプトール・グリーン
（Ｄ−17）２，３−ジメチル−６−ニトロ−ベン
ゾチアゾリウム・Ｐ−トルエンスル
ホネート
有機減感剤の量は、本発明の重要な特徴であ
り、従来使用されてきた量よりも著しく少量であ
る。典型的な例においてはハロゲン化銀１モル当
り１mg以下の有機減感剤の量であることを理解す
べきである。有機減感剤の種類、ハロゲン化銀乳
剤の性質などによつて異なるため一概には特定で
きないが、一般的にはハロゲン化銀１モル当り約
0.01〜約30ミリグラム、好ましくは約0.1〜約10
ミリグラムである。しかし、有機減感剤の量は、
本発明に用いられるハロゲン化銀乳剤の固有感度
をlogE＝1.3（但し、塩化銀乳剤の場合にはlogE＝
1.0）を越えない値で減少させる、即ち1/20以下
（塩化銀乳剤の場合には1/10以下）に減少させな
いために必要な量であると特定することが適切で
ある。
一般的にはlogE≒0.2〜logE＝1.3（塩化銀乳剤
は1.0）、好ましくはlogE≒0.3〜logE＝1.0（塩化
銀乳剤は0.9）の範囲で減少させるに必要な量で
ある。
有機減感剤は、ハロゲン化銀乳剤を塗布するま
での任意の時期に添加することができる。
本発明に用いられるハロゲン化銀乳剤は、少な
くとも70モル％、好ましくは80モル％の塩化銀を
含む塩化銀、塩臭化銀、塩沃化銀、塩臭沃化銀の
ネガ乳剤である。ネガ乳剤とは、直接ポジ用ハロ
ゲン化銀乳剤と区別される、ポジ原稿に対してネ
ガ画像を形成する通常タイプのハロゲン化銀乳剤
である。沃化銀は０〜約３モル％、好ましくは０
〜1.5モル％である。
本発明に用いられるハロゲン化銀乳剤は、平均
粒径0.1〜0.4μｍのものである。また全粒子数の
90％以上が平均粒径の±10％の範囲の粒径を有す
るものが好ましい。ハロゲン化銀乳剤の調製方法
は、順混合、逆混合、同時混合など公知の方法い
ずれであつてもよい。
物理熟成を終えた乳剤は、脱塩した後に、必要
な添加剤を加えて塗布されることが好ましいが脱
塩処理は省略することもできる。
化学増感は実質的に行なわない方が好ましい
が、所望により施こしてもよい。
本発明により得られるハロゲン化銀乳剤は、安
定剤、カブリ防止剤、カバリングパワー向上剤、
イラジエーシヨン防止剤、膜物性改良剤、界面活
性剤、硬膜剤、マツト剤、現像主薬等々の一般の
写真用乳剤に用いられる添加剤を含むことがで
き、公知の支持体上に塗布される。保護層、下塗
層など他の親水性コロイド層を有していてもよ
い。
本発明により得られる明室用感光材料は、主と
して印刷用分野で用いられる紫外光に富んだ光
源、例えば超高圧水銀灯、メタルハライド等によ
り露光されるが、従来の明室用感光材料に比べて
約10倍以上も高感度であるため露光時間を短かく
したり、照度を低くすることができるので省電
力、作業時間の短縮など合理化を図ることができ
る。
(E) 実施例
実施例 １
塩化銀92モル％を含む塩臭化銀乳剤を同時混合
法により調製し、平均粒径0.2μｍで単分散の乳剤
を得た。使用したゼラチンは、不活性ゼラチンで
ある。この乳剤を脱塩し、再溶解した後に安定
剤、硬膜剤、界面活性剤を加えて、ポリエステル
フイルム上に硝酸銀として５ｇ／m2となるように
保護層用ゼラチン液と共に塗布し、乾燥した。こ
れをブランク試料Ａとする。ハロゲン化銀１モル
当り５×10-4モルのロジウム塩を混合時に用いる
以外はブランク試料Ａと同様にして作製した試料
をＢとする。又、ブランク試料Ａのハロゲン化銀
乳剤に有機減感剤（Ｄ−２）又は（Ｄ−９）をハ
ロゲン化銀１モル当り下記第１表の通り変化する
以外はブランク試料Ａと同様にして試料Ｃ〜Ｐを
作製した。
(A) Industrial Application Field The present invention relates to a silver halide photographic emulsion, and more particularly to a silver halide photographic emulsion used in a high-sensitivity light-sensitive light-sensitive material. (B) Prior art and its problems In recent years, in the printing field, the complexity of printed matter,
Due to the development of scanners, there is a need to improve the efficiency of the return process. For this reason, it is 10 -4 to 10 -5 compared to the conventional return film.
Photographic films with extremely low sensitivity have been developed and have begun to be put into practical use as return films that can be handled in bright rooms (under white fluorescent lamps excluding ultraviolet rays), that is, as photosensitive materials for bright rooms. The performance required of such bright room photosensitive materials is that they have high contrast and sufficient maximum density, can be handled for long periods of time in a bright room, and have high sensitivity to printer light sources. etc. However, it cannot be said that conventional light-sensitive materials for use in bright rooms fully satisfy the above-mentioned performance. Generally, emulsions with ultra-low sensitivity that can be used as light-sensitive materials can be obtained by using inorganic desensitizers such as rhodium salts or organic desensitizers such as pinacryptol yellow. For example, as a method for producing photosensitive materials for bright room use using a large amount of rhodium salt, there are
56-149030, 1982-149031, 1982-190943, etc., which contain rhodium salt in a silver halide emulsion mainly composed of silver chloride in an amount that reduces the sensitivity of the emulsion by about 1/300 to about 1/500. It is what you use. However, silver chloride emulsions whose sensitivity has been lowered by using rhodium salts tend to cause fog when handled under bright room light, and have the disadvantage that fog increases significantly as the sensitivity is increased. On the other hand, the applicant has produced a silver halide emulsion using an organic desensitizer that has almost the same sensitivity as the above-mentioned super-low sensitivity silver halide emulsion mainly composed of silver chloride produced using a rhodium salt. It has been confirmed that by doing so, it is possible to obtain a photosensitive material for bright room use that does not have the drawbacks of rhodium salts. However, since silver halide emulsions produced using organic desensitizers mainly contain silver chloride, they tend to have high contrast and high maximum density; Similarly, it was discovered that there was a new problem of a significant decrease in sensitivity when left in bright room light, and various methods were proposed to solve this new problem (for example, Japanese Patent Application No. 58-31413; 58-33600, 1982-54536, 1983-39413, etc.), but these methods could not be said to be a perfect method that could provide a stable solution. (C) Purpose of the Invention The purpose of the present invention is to solve the above-mentioned problems in silver halide emulsions for bright room photosensitive materials containing silver chloride as a main ingredient, and to provide high contrast, high maximum density, and dramatic sensitization. It is an object of the present invention to provide a silver halide photographic emulsion which does not cause fogging or desensitization under bright room light. (D) Structure of the Invention The present invention provides a negative-working fine-grain silver halide photographic emulsion containing at least 70 mol% of silver chloride and a desensitizer, wherein the desensitizer is is a positive organic desensitizer, and the amount of the organic desensitizer is necessary to reduce the sensitivity of the emulsion by a value not exceeding logE = 1.3 (however, in the case of silver chloride, logE = 1.0) This is a silver halide photographic emulsion characterized by the following. The present invention will be explained in further detail below. The organic desensitizer used in the present invention is generally known to be used in direct positive silver halide emulsions. That is, the organic desensitizer used in the present invention is characterized by its polarographic half-wave potential, that is, its redox potential determined by polarography. Organic desensitizers useful in the present invention are those in which the sum of polarographic anode potential and polarographic cathode potential is positive. Methods for measuring these redox potentials are described, for example, in US Pat. No. 3,501,307. Specific examples of such organic desensitizers are described in numerous patent specifications and documents, all of which have the same effect in the present invention. Showa 39-
20261, 1973-26751, 13167-13167, 1972
-8833, 1974-8746, 1977-10197, 1972
-37530, JP-A-48-24734, JP-A-49-84639, JP-A-56-152525, U.S. Patent No. 2271229, No.
Compounds described in specifications such as No. 2541472, No. 3035917, No. 3062651, No. 3124458, No. 3326687, and No. 3671254 can be used. An example is shown below. (D-1) 1,3-diethyl-1'-methyl-2'-
Phenylimidazo[4,5-b]-quinoxalino-3'-indolocarbocyanine iodide (D-2) Pinacriptol yellow (D-3) 1,1',3,3,3'3'-hexamethyl-5 , 5'-dinitroindocarbocyanine P-toluenesulfonate (D-4) 5,5'-dichloro-3,3'-diethyl 6,6'-dinitrothiacarbocyanine iodide (D-5) 1,1 '-Dimethyl-2,2'-diphenyl-3,3'-indolocarbocyanine bromide (D-6) 1,1',3,3'-tetraethylimidazo[4,5-b]quinoxalinocarbo Cyanine chloride (D-1) 5-m-nitrobenzylidene rhodanine (D-8) 6-chloro-4-nitro-nitrobenzotriazole (D-9) 1,1'-dibutyl-4,4'-pi Pyridinium dipromide (D-10) 1,1'-ethylene-2,2'-pipyridinium dipromide (D-11) 4-(P-n-amyloxyphenyl)-
2,6-di(P-ethylphenyl)
Thiapyrylium perchlorate (D-12) 2-Mercapto-4-methyl-5-nitrothiazole (D-13) 2-(o-nitrostyryl)-3-ethylbenzothiazolium P-toluenesulfonate (D- 14) 2-(P-nitrostyryl)-quinoline P-toluenesulfonate (D-15) Phenosafranin (D-16) Pinacryptol green (D-17) 2,3-dimethyl-6-nitro-benzothia Zolium P-toluenesulfonate The amount of organic desensitizer is an important feature of the present invention and is significantly lower than the amounts previously used. It should be understood that typical examples include amounts of organic desensitizer of less than 1 mg per mole of silver halide. Although it cannot be determined unambiguously because it varies depending on the type of organic desensitizer and the properties of the silver halide emulsion, it is generally about
0.01 to about 30 milligrams, preferably about 0.1 to about 10
It's milligrams. However, the amount of organic desensitizer
The intrinsic sensitivity of the silver halide emulsion used in the present invention is logE=1.3 (however, in the case of a silver chloride emulsion, logE=
1.0), that is, the amount necessary to prevent the reduction to 1/20 or less (1/10 or less in the case of silver chloride emulsions) is appropriate. Generally, the amount is necessary to reduce logE≈0.2 to logE=1.3 (1.0 for silver chloride emulsions), preferably logE≈0.3 to logE=1.0 (0.9 for silver chloride emulsions). The organic desensitizer can be added at any time before coating the silver halide emulsion. The silver halide emulsion used in the present invention is a negative emulsion of silver chloride, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide containing at least 70 mol %, preferably 80 mol % of silver chloride. A negative emulsion is a normal type of silver halide emulsion that forms a negative image on a positive original, which is distinguished from a direct positive silver halide emulsion. Silver iodide is 0 to about 3 mol%, preferably 0
~1.5 mol%. The silver halide emulsion used in the present invention has an average grain size of 0.1 to 0.4 μm. Also, the total number of particles
It is preferable that 90% or more of the particles have a particle size within ±10% of the average particle size. The silver halide emulsion may be prepared by any known method such as forward mixing, back mixing, or simultaneous mixing. It is preferable that the emulsion that has undergone physical ripening is desalted and then coated with necessary additives, but the desalting treatment can also be omitted. Although it is preferable not to substantially carry out chemical sensitization, it may be carried out if desired. The silver halide emulsion obtained by the present invention contains stabilizers, antifoggants, covering power improvers,
It can contain additives used in general photographic emulsions such as irradiation inhibitors, film property improvers, surfactants, hardeners, matting agents, developing agents, etc., and is coated on a known support. It may have other hydrophilic colloid layers such as a protective layer and an undercoat layer. The photosensitive material for bright room use obtained by the present invention is exposed to light using a light source rich in ultraviolet light mainly used in the printing field, such as an ultra-high pressure mercury lamp, metal halide, etc., but compared to conventional photosensitive materials for bright room use, Because it is more than 10 times more sensitive, it is possible to shorten exposure time and lower illuminance, making it possible to streamline operations by saving power and shortening work time. (E) Examples Example 1 A silver chlorobromide emulsion containing 92 mol % of silver chloride was prepared by a simultaneous mixing method to obtain a monodisperse emulsion with an average grain size of 0.2 μm. The gelatin used is inert gelatin. After desalting and redissolving this emulsion, stabilizers, hardeners, and surfactants were added, and the mixture was coated on a polyester film with a gelatin solution for a protective layer at a concentration of 5 g/m 2 of silver nitrate, and dried. . This is designated as blank sample A. Sample B was prepared in the same manner as blank sample A except that 5×10 -4 mol of rhodium salt per mol of silver halide was used during mixing. In addition, the same procedure as blank sample A was carried out except that the organic desensitizer (D-2) or (D-9) was added to the silver halide emulsion of blank sample A as per mol of silver halide as shown in Table 1 below. Samples C to P were prepared.
【表】
これらの試料を1.5KW超高圧水銀灯光源の明
室用プリンターを用いてセンシトメトリー用の露
光を施こし、Ｄ−85現像液で20℃、２分間現像
し、定着し、乾燥した。階調ガンマ（γ）、最大
透過濃度（Dmax）、相対感度（Ｓ）を第２表に
示した。尚、最低透過濃度（Dmin）はいずれの
試料とも0.02であつた。また、相対感度（Ｓ）は
ブランク試料Ａを10，000としたときに相対値で
示している。
さらに、これらの試料を500ルツクスの紫外線
を除去した明室光すなわち東芝FL40SW NUの
螢光灯下で１時間照射した後に前記と同一の現像
処理後に得られたカブリ値（Ｆ）を第２表に示し
た。（Dminを含む）。また、これらの試料にセン
シトメトリー露光を与えた後に前記の明室光下で
10分間照射してから同様に現像処理した場合の減
感率（それぞれの試料におけるセンシトメトリー
露光後直ちに現像処理したときの感度を100とす
る減感の割合；△Ｓ）を第２表に示した。[Table] These samples were exposed for sensitometry using a bright room printer with a 1.5KW ultra-high pressure mercury lamp light source, developed with D-85 developer at 20℃ for 2 minutes, fixed, and dried. . The gradation gamma (γ), maximum transmission density (Dmax), and relative sensitivity (S) are shown in Table 2. Note that the minimum permeation density (Dmin) was 0.02 for all samples. Moreover, relative sensitivity (S) is shown as a relative value when blank sample A is set to 10,000. Furthermore, Table 2 shows the fog values (F) obtained after irradiating these samples for 1 hour under a bright room light with 500 lux of ultraviolet rays removed, that is, under a Toshiba FL40SW NU fluorescent lamp, and after the same development process as above. It was shown to. (Including Dmin). In addition, after giving these samples sensitometric exposure, they were exposed under the bright room light described above.
Table 2 shows the desensitization rate when the samples were irradiated for 10 minutes and then developed in the same way (the rate of desensitization when the sensitivity of each sample was taken as 100 when developed immediately after sensitometric exposure; △S). Indicated.
【表】
ロジウム塩を用いた比較試料Ｂは明室光下での
カブリが著しく生じ、このカブリはロジウム塩を
減量するに従つて増加するものである。
有機減感剤（Ｄ−２）又は（Ｄ−９）を使用し
てブランク試料の感度をlogE＝1.3を越えた値に
減少させた試料Ｃ，Ｄ，Ｅ，Ｊ，Ｋ，Ｌ及びＭは
明室光下での減感が著しいことが判る。それに対
して本発明の試料Ｆ，Ｇ，Ｈ，Ｉ，Ｎ，Ｏ及びＰ
は、極めて高感度であるにも拘らず明室光下での
カブリ発生と減感が実質的になく、また階調、最
大濃度も高く、非常に優れた高感度の明室用感光
材料であることが理解できる。
実施例 ２
有機減感剤として（Ｄ−７）、（Ｄ−10）（Ｄ−
11）、（Ｄ−13）または（Ｄ−16）をハロゲン化銀
１モル当り各々１mg添加する以外は実施例１に従
つた（試料はＱ，Ｒ，Ｓ，Ｔ，Ｕとする。）[Table] Comparative sample B using a rhodium salt causes significant fogging under bright room light, and this fogging increases as the amount of the rhodium salt is reduced. Samples C, D, E, J, K, L, and M, in which the sensitivity of the blank sample was reduced to a value exceeding logE = 1.3 using organic desensitizers (D-2) or (D-9), were It can be seen that the desensitization under bright room light is significant. In contrast, samples F, G, H, I, N, O and P of the present invention
Despite its extremely high sensitivity, there is virtually no fogging or desensitization under bright room light, and the gradation and maximum density are high, making it an extremely high-sensitivity photosensitive material for bright rooms. I can understand something. Example 2 As organic desensitizers (D-7), (D-10) (D-
Example 1 was followed except that 1 mg of each of 11), (D-13), or (D-16) was added per mole of silver halide (the samples were Q, R, S, T, and U).
【表】
実施例 ３
平均粒径0.3μｍの塩化銀を用いる以外は実施例
１と同様にして下記の通り試料を作製した。[Table] Example 3 A sample was prepared as described below in the same manner as in Example 1 except that silver chloride having an average particle size of 0.3 μm was used.
【表】
以後、実施例１と同様に試験した結果を第４表
に示す。[Table] Table 4 below shows the results of tests conducted in the same manner as in Example 1.
【表】
第４表では、logE＝1.0を越えない値で感度
（Ｓ）を減少させた試料ｇ及びｈが高感度で明室
光下のカブリ、減感のないものであることが理解
される。
(F) 発明の効果
本発明のハロゲン化銀写真乳剤は、硬調で高い
最大濃度を有し、従来の明室用感光材料に比べて
著しい高感度であり、且つ画像露光の前後に亘る
明室光下でのカブリの発生ならびに減感の欠点も
ないため長時間の取扱い安全性が確保でき、更に
プリンターの省電力や作業性の向上をもたらすこ
とができるものである。[Table] In Table 4, it is understood that samples g and h, whose sensitivity (S) was decreased by a value not exceeding logE = 1.0, have high sensitivity and no fogging or desensitization under bright room light. Ru. (F) Effects of the Invention The silver halide photographic emulsion of the present invention has high contrast and high maximum density, has significantly higher sensitivity than conventional photosensitive materials for bright room use, and is suitable for use in bright room use before and after image exposure. Since there is no drawback of fogging or desensitization under light, long-term handling safety can be ensured, and furthermore, it can save power and improve workability of the printer.
Claims (1)
するネガ型微粒子ハロゲン化銀写真乳剤であつ
て、前記減感剤はポーラログラフの陽極電位と陰
極電位の和が正である有機減感剤であり、該有機
減感剤の量がハロゲン化銀１モル当り約0.01〜約
30ミリグラムの範囲で前記乳剤の固有感度を
logE＝1.3（但し、塩化銀の場合にはlogE＝1.0）
を越えない値で減少させるに必要な量であること
を特徴とする明室用感光材料に用いるハロゲン化
銀写真乳剤。1. A negative-working fine-grain silver halide photographic emulsion containing at least 70 mol % of silver chloride and a desensitizer, wherein the desensitizer is an organic desensitizer in which the sum of the anodic potential and cathodic potential of the polarogram is positive. Yes, the amount of the organic desensitizer is from about 0.01 to about 1 mole of silver halide.
The inherent sensitivity of the emulsion in the range of 30 mg
logE=1.3 (logE=1.0 in case of silver chloride)
1. A silver halide photographic emulsion for use in light-sensitive materials for bright rooms, characterized in that the silver halide emulsion is in an amount necessary to reduce the amount by a value not exceeding .
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14710984A JPS6126040A (en) | 1984-07-16 | 1984-07-16 | Silver halide photographic emulsion |
| US06/755,310 US4666827A (en) | 1984-07-16 | 1985-07-15 | Silver halide photographic emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14710984A JPS6126040A (en) | 1984-07-16 | 1984-07-16 | Silver halide photographic emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6126040A JPS6126040A (en) | 1986-02-05 |
| JPH039450B2 true JPH039450B2 (en) | 1991-02-08 |
Family
ID=15422720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14710984A Granted JPS6126040A (en) | 1984-07-16 | 1984-07-16 | Silver halide photographic emulsion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6126040A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63220130A (en) * | 1987-03-09 | 1988-09-13 | Mitsubishi Paper Mills Ltd | Silver halide photographic emulsion |
| JPH01177082A (en) * | 1987-12-28 | 1989-07-13 | Casio Comput Co Ltd | Electronic musical instrument |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56142525A (en) * | 1980-03-07 | 1981-11-06 | Ciba Geigy Ag | Photographic negative material having layer containing at least one desensitized halogenated silver emulsion |
-
1984
- 1984-07-16 JP JP14710984A patent/JPS6126040A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56142525A (en) * | 1980-03-07 | 1981-11-06 | Ciba Geigy Ag | Photographic negative material having layer containing at least one desensitized halogenated silver emulsion |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6126040A (en) | 1986-02-05 |
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