JPS632045A - Photographic light absorbing dye - Google Patents
Photographic light absorbing dyeInfo
- Publication number
- JPS632045A JPS632045A JP14564286A JP14564286A JPS632045A JP S632045 A JPS632045 A JP S632045A JP 14564286 A JP14564286 A JP 14564286A JP 14564286 A JP14564286 A JP 14564286A JP S632045 A JPS632045 A JP S632045A
- Authority
- JP
- Japan
- Prior art keywords
- dye
- layer
- solution
- photographic
- emulsion
- 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.)
- Granted
Links
- 239000000975 dye Substances 0.000 abstract description 50
- 239000000839 emulsion Substances 0.000 abstract description 21
- 239000010410 layer Substances 0.000 abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000243 solution Substances 0.000 abstract description 13
- -1 silver halide Chemical class 0.000 abstract description 12
- 239000007864 aqueous solution Substances 0.000 abstract description 10
- 229910052709 silver Inorganic materials 0.000 abstract description 10
- 239000004332 silver Substances 0.000 abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- 239000000084 colloidal system Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 150000002334 glycols Chemical class 0.000 abstract description 2
- 239000011229 interlayer Substances 0.000 abstract description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 abstract description 2
- 239000011259 mixed solution Substances 0.000 abstract description 2
- 239000011241 protective layer Substances 0.000 abstract description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 2
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 abstract description 2
- 230000001419 dependent effect Effects 0.000 abstract 1
- 230000031700 light absorption Effects 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 5
- 229920000159 gelatin Polymers 0.000 description 5
- 239000008273 gelatin Substances 0.000 description 5
- 235000019322 gelatine Nutrition 0.000 description 5
- 235000011852 gelatine desserts Nutrition 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000000586 desensitisation Methods 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 230000002265 prevention Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DROSEJRQKIQKQY-UHFFFAOYSA-N 1-methyl-5-oxo-4h-pyrazole-3-carboxylic acid Chemical compound CN1N=C(C(O)=O)CC1=O DROSEJRQKIQKQY-UHFFFAOYSA-N 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010067482 No adverse event Diseases 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- XCFIVNQHHFZRNR-UHFFFAOYSA-N [Ag].Cl[IH]Br Chemical compound [Ag].Cl[IH]Br XCFIVNQHHFZRNR-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 210000001217 buttock Anatomy 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- ZQUVDXMUKIVNOW-UHFFFAOYSA-N n,n'-diphenylmethanimidamide Chemical compound C=1C=CC=CC=1NC=NC1=CC=CC=C1 ZQUVDXMUKIVNOW-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 229920003169 water-soluble polymer Polymers 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
- G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
- G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation
- G03C1/83—Organic dyestuffs therefor
- G03C1/832—Methine or polymethine dyes
Abstract
Description
【発明の詳細な説明】
（Ａ＞産業上の利用分野
本発明は写真用吸光染料に関し、さらに詳しくは、ハロ
ゲン化銀写真感光材料に用いる光吸収染料として有用な
染料に関するものでおる。DETAILED DESCRIPTION OF THE INVENTION (A>Field of Industrial Application) The present invention relates to a photographic light-absorbing dye, and more particularly to a dye useful as a light-absorbing dye for use in silver halide photographic light-sensitive materials.
（Ｂ）従来の技術
ハロゲン化銀写真感光材料において、その感光乳剤層中
での有害な反射、散乱、拡散光などを吸収したり、ある
いは、乳剤層と支持体ベース境界面および支持体背面か
らの望ましくない反則光を吸収することによって、イラ
ジェーションおよびハレーションを防止して、仕上がっ
た写真画像の鮮鋭度を向上させることはよく知られてい
る。(B) Prior Art In silver halide photographic light-sensitive materials, harmful reflections, scattering, and diffused light in the light-sensitive emulsion layer are absorbed, or from the interface between the emulsion layer and the support base and the back surface of the support. It is well known to prevent irradiation and halation and improve the sharpness of finished photographic images by absorbing undesired reflected light from the surface.
また、乳剤層の上や、重層カラー写真感光材料のように
写真乳剤層が複数存在する時には、それらの中間に着色
層（フィルター層）を設けることにより、写真乳剤層に
人則すぺぎ分光組成を制御させることもよく知られてい
る。In addition, when there are multiple photographic emulsion layers such as a multilayer color photographic light-sensitive material, a colored layer (filter layer) is provided on top of the emulsion layer or between them, so that the photographic emulsion layer can be Controlling the composition is also well known.
イラジェーションおよびハレーションを防止するために
、感光乳剤層や乳剤層と支持体の間、おるいは、支持体
裏塗層に投与したり、フィルター層中に投与される染料
は、溶液調製中や感光乳剤製造中および保存中に、変退
色等の経時変化を起してはならないことは当然であるが
、カブリや減感等の写真時［ｊ目こ悪影響をおよぼして
はいけない。In order to prevent irradiation and halation, dyes applied to the light-sensitive emulsion layer, between the emulsion layer and the support, to the backing layer of the support, or into the filter layer are used during solution preparation. Of course, changes over time such as discoloration and fading must not occur during the production and storage of photosensitive emulsions, but they must also not have any negative effects on photography such as fog or desensitization.
また、現像処理工程中、完全かつ速やかに脱色するか、
または、写真感光材料中から溶出除去されなければなら
ない。好ましくは、染料が脱色タイプであり、かつ、脱
色した該染料が溶出性で処理液を着色しないものが望ま
しい。ざらに、それぞれの目的に合致した分光吸収特性
を有し、イラジェーション防止、ハレーション防止およ
び分光フィルターの効果を有していなければならない。In addition, during the development process, it is necessary to completely and quickly decolorize or
Alternatively, it must be eluted and removed from the photographic material. Preferably, the dye is of a bleaching type, and the bleached dye is eluting and does not color the processing solution. In general, it must have spectral absorption characteristics that meet each purpose, and must have irradiation prevention, halation prevention, and spectral filter effects.
しかるに、今日までかなり多数の染料が提案されている
が、脱色性、溶出性および写真特性等、上記条件を満足
させるものは数少ないのが実状である。However, although a considerable number of dyes have been proposed to date, the reality is that there are only a few that satisfy the above conditions such as decolorization properties, dissolution properties, and photographic properties.
（Ｃ）発明の目的
したがって、本発明の目的は上記諸条件を満足したすぐ
れたイラジェーションおよびハレーションおよびフィル
ター効果を有する写真用吸光染料を提供することにある
。(C) Object of the Invention Therefore, an object of the present invention is to provide a photographic light-absorbing dye that satisfies the above conditions and has excellent irradiation, halation and filter effects.
（Ｄ＞発明の構成
本発明者らは種々の検討の結果、下記−般式で示される
染料が上記目的を満足させるすぐれた染料であることを
見い出した。(D> Structure of the Invention As a result of various studies, the present inventors have discovered that the dye represented by the following general formula is an excellent dye that satisfies the above object.
一般式
上記一般式において、Ｒはカルボキシ基、スルホ基を除
く基で置換されていてもよい低級アルキル基（例えば、
メチル、エチル、プロピル、ブチル、アミル、ヒドロキ
シエチル、メトキシエチル、クロロエチル、シアノエチ
ル、エトキシカルボニルプロビル等）を、Ｌは低級アル
キル基（例えば、メチル、エチル等）で置換されてもよ
いメチン基を表わし、ｌは整数１．２および３を表わす
。上記−般式で表わされる染料はアルカリ金属塩（例え
ば、カリウム、ナトリウム等）やアンモニウム塩（例え
ば、トリエチルアンモニウム、ビワジニウム等）の型を
とることができる。General Formula In the above general formula, R is a lower alkyl group which may be substituted with a group other than a carboxy group or a sulfo group (for example,
methyl, ethyl, propyl, butyl, amyl, hydroxyethyl, methoxyethyl, chloroethyl, cyanoethyl, ethoxycarbonylprobyl, etc.), and L is a methine group which may be substituted with a lower alkyl group (e.g., methyl, ethyl, etc.). where l represents the integers 1.2 and 3. The dye represented by the above general formula can take the form of an alkali metal salt (for example, potassium, sodium, etc.) or an ammonium salt (for example, triethylammonium, biwadinium, etc.).
上記−般式で示される本発明の染料で着色されたハロゲ
ン化銀写真感光材料は、目的とする波長ｍＨにおいて、
幅広い吸収帯を有しているにも拘らず、仙の波長領域に
はほとんど不要な副吸収がなく、また、本発明の染料は
いずれも高い分子吸光係数を有しており、カブリ、減感
等の写真特性への悪影響をひきおこすことなく、少ない
使用量ですぐれたイラジェーション防止、ハレーション
防止おにびフィルター効果を十分に発揮することができ
る。また、現像処理工程後には感光材料中から完全かつ
迅速に染料が脱色、溶出するので、仕上った写真画像に
は前記目的で含有させた染料の残存はもちろんのこと、
脱色染料の復色による色汚染、ざらには現像処理液の着
色による再染着は見受けられない。また、本発明の染料
は染料溶液調製時の変退色等の変化は起らず、感光乳剤
製造中や、その後の保存中における湿熱等の外的条件に
対しても影響を受けることなく安定でおるという利点を
有している。The silver halide photographic light-sensitive material colored with the dye of the present invention represented by the above general formula has the following properties at the target wavelength mH:
Despite having a wide absorption band, there is almost no unnecessary side absorption in the wavelength range, and all of the dyes of the present invention have high molecular extinction coefficients, causing no fogging or desensitization. It is possible to fully demonstrate the excellent anti-irradiation and anti-halation Onibi filter effect with a small amount of use, without causing any adverse effects on photographic properties such as. In addition, after the development process, the dye is completely and quickly decolorized and eluted from the photosensitive material, so the finished photographic image not only retains the dye contained for the above purpose.
There is no color contamination caused by the recoloring of the decolorizing dye, and no re-dying caused by the coloring of the developing solution. Furthermore, the dye of the present invention does not undergo any changes such as discoloration or fading during the preparation of the dye solution, and is stable without being affected by external conditions such as moist heat during the production of the photosensitive emulsion or during subsequent storage. It has the advantage of being
次に本発明の前記−般式で示される染料のうち、代表的
な例を挙げる。Next, typical examples of the dyes represented by the above general formula of the present invention will be listed.
染料１ 染料２ 染料３ Ｃ１１３Ｃｔ１３ 染料４ ｎｃ３１１ｔ ｎｃ３１１７染料５ 染料６Ｃ１＋３ Ｃｔｈ ｅＩ＋３ 染料７ 染料８ 次に染料の合成法について代表例を具体的に述べる。dye 1 dye 2 dye 3 C113Ct13 dye 4 nc311t nc3117 dye 5 dye 6C1+3 Cth eI+3 dye 7 dye 8 Next, typical examples of dye synthesis methods will be specifically described.
染料１の合成：
３−カルボキシ−１−メチル−５−ピラゾロン’５．６
８ｇとＮ、 Ｎ’−ジフェニルホルムアミジン３．９２
ｇにメタノール４０ｒｒＩｌに加え、加熱速流する中へ
、トリエチルアミン６．０６９を加えた。１時間加熱還
流後、塩酸酸性とした。減圧溢稲後エタノールで処理し
て乾燥後、融点３００’Ｃ以上の黄色粉末３．５０７を
（ｑだ。水溶液の吸収極大値は４１２ｎｍであった。Synthesis of dye 1: 3-carboxy-1-methyl-5-pyrazolone'5.6
8g and N,N'-diphenylformamidine 3.92
In addition to 40 rrIl of methanol, 6.069 g of triethylamine was added to the mixture under rapid heating. After heating under reflux for 1 hour, the mixture was acidified with hydrochloric acid. After being flooded under reduced pressure and treated with ethanol and dried, a yellow powder with a melting point of 300'C or more (3.507 q) was obtained.The maximum absorption value of the aqueous solution was 412 nm.
染料５の合成：
１−ｎ−アミル−３−エトキシカルボニル−５−ピラゾ
ロン２．２６ ！７、プロベンジアニル塩ｆ１１．３０
ｇ、エタノール１０ｄおにび１・１ノエチルアミン１．
０１９を混合し、３０分間加熱還流した。Synthesis of dye 5: 1-n-amyl-3-ethoxycarbonyl-5-pyrazolone 2.26! 7, Probendianil salt f11.30
g, ethanol 10d rice 1.1 noethylamine 1.
019 was mixed and heated under reflux for 30 minutes.
冷却後２Ｎ−ＮａＯトドＯ威を加え、室温で３時間かく
はんを行った。酢酸酸性後、エタノール１００戒を加え
、析晶を濾取した。エタノールで洗しよう後乾燥して、
融点３００°Ｃ以上の）農紫色粉末１．３５ｙを得た。After cooling, 2N-NaO was added and stirred at room temperature for 3 hours. After acidification with acetic acid, 100 ml of ethanol was added, and the precipitated crystals were collected by filtration. After washing with ethanol, dry it.
1.35y of agricultural purple powder (with a melting point of 300°C or higher) was obtained.
水溶液の吸収極大値は５３４ｎｍでおった。The maximum absorption value of the aqueous solution was at 534 nm.
染料８の合成
３−カルボキシ−１−（２−じドロキシエチル）−５−
ピラゾロン３．５４Ｖとペンタジェンシアニル塩駿塩２
．８４９にエタノール２０彪を加え、ざらに、１〜リエ
チルアミン３．０３９を加えて室温で１時間かくはんし
た。析晶を濾取し、エタノールで洗浄後乾燥して、融点
３００’Ｃ以上のうぐいず色粉末３．４２ｙを１ｑた。Synthesis of dye 8 3-carboxy-1-(2-didroxyethyl)-5-
Pyrazolone 3.54V and pentadiencyanyl salt Shunshio 2
．． 849 was added with 20 ml of ethanol, 1 to 3.039 ml of ethylamine were added to the colander, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were collected by filtration, washed with ethanol, and dried to obtain 1 q of 3.42 y of russet-colored powder with a melting point of 300'C or higher.
水溶液の吸収極大値は６２６ｎｍであった。The maximum absorption value of the aqueous solution was 626 nm.
他の本発明の一般式で示される染料も上記合成例に準じ
て容易に合成することができる。Other dyes represented by the general formulas of the present invention can also be easily synthesized according to the above synthesis examples.
前記−般式で示される本発明の染料をハロゲン化銀写真
乳剤または保護コロイド溶液中に添加するには、水溶液
または、メタノール、エタノール、セロソルブ類、グリ
コール類、ジメチルホルムアミド、ジメヂルスルホキシ
ド、ピリジン等の溶液として、またこれらの有機溶媒と
水との混合溶液として乳剤層、裏塗層、下引層、中間層
、保護層、紫外線吸収層中に添加し、存在Ｖしめること
かできる。In order to add the dye of the present invention represented by the above general formula into a silver halide photographic emulsion or a protective colloid solution, an aqueous solution, methanol, ethanol, cellosolves, glycols, dimethylformamide, dimethyl sulfoxide, pyridine, etc. They can be added to emulsion layers, backing layers, subbing layers, interlayers, protective layers, and ultraviolet absorbing layers as a solution of these organic solvents or as a mixed solution of these organic solvents and water to confirm their presence.
これら染料の使用量は適用する写真層によって異るが、
−般には感光月利の面積１尻あたり５・〜１．０００ｍ
３になるように塗イ１丁される。The amount of these dyes used varies depending on the photographic layer to be applied.
-Generally 5.~1.000m per area of monthly photosensitive area
One piece is painted so that it becomes 3.
本発明の染料が用いられるハロゲン化銀写真乳剤として
は、例えば塩化銀、臭化銀、塩臭化銀、沃臭化銀、塩沃
臭化銀などの乳剤がある。Examples of silver halide photographic emulsions in which the dyes of the present invention are used include emulsions of silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like.
また、本発明の染料が用いられるハロゲン化銀写真乳剤
は、通常用いられるシアニン、メロシアニン色素等で分
光増感される。ざらに公知の方法により、アミノ基、あ
るいはアンモニウム基を含むポリマー、含窒素複素環を
含むポリマー等の塩基性媒染剤、安定剤、およびその前
駆体、界面活性剤、硬膜剤、紫外線吸収剤、蛍光増白剤
、現像主薬およびその前駆体等のような添加剤を含有せ
しめることができる。ハロゲン化銀写真乳剤がカラー感
光材料に用いられる時には、カラーカプラーやその分散
剤を含有させることもできる。Further, the silver halide photographic emulsion in which the dye of the present invention is used is spectrally sensitized with a commonly used cyanine or merocyanine dye. Basic mordants such as polymers containing amino groups or ammonium groups, polymers containing nitrogen-containing heterocycles, stabilizers and their precursors, surfactants, hardeners, ultraviolet absorbers, Additives such as optical brighteners, developing agents and their precursors can be included. When a silver halide photographic emulsion is used in a color light-sensitive material, it can also contain a color coupler or a dispersant thereof.
ハロゲン化銀乳剤の保護コロイドとしては、ゼラチンの
ほかにフタル化ゼラヂンやマロン化ピラチンのようなゼ
ラチン誘導体、ポリビニルアルコールやポリビニルピロ
リドンのような水溶性ポリマー、そして寸法安定性のた
めの可塑剤、ラテックスポリマーなどを加えることがで
きる。In addition to gelatin, protective colloids for silver halide emulsions include gelatin derivatives such as phthalated geladine and malonated pyratine, water-soluble polymers such as polyvinyl alcohol and polyvinylpyrrolidone, and plasticizers and latex for dimensional stability. Polymers etc. can be added.
ざらに、本発明の染料が用いられるハロゲン化銀写真乳
剤はバライタ紙、レジンコート紙、合成紙、セルローズ
トリアセテート系おるいはポリエステル系などの天然ま
たは合成の高分子フィルムなどの支持体に塗布すること
ができる。In general, the silver halide photographic emulsion in which the dye of the present invention is used is coated on a support such as baryta paper, resin coated paper, synthetic paper, natural or synthetic polymer film such as cellulose triacetate or polyester. be able to.
次に実施例によって本発明をざらに詳しくのべる。Next, the present invention will be described in detail with reference to examples.
実施例１：
ゼラチン１．５５ＳＦを水１５．０ｄに加えて膨潤させ
た後、４０．０ ’Ｃに加温してピラチンを溶解した。Example 1: 1.55 SF of gelatin was added to 15.0 d of water to swell it, and then heated to 40.0'C to dissolve piratin.
このゼラチン溶液に本発明の染料と後記比較染料の水溶
液（２，０Ｘ１０”’モル／水２． Ｏｒｎｌ＞と硬膜
剤、界面活性剤を加え、ざらに水を加えて全量を２０、
０ ｄにした。次にこの着色溶液を下引きを施したポリ
エステルフィルムベース上に塗７５徂が８５９／Ｔｒｔ
になるように塗布し、５０．ｏ’ｃで２４時間加温して
、ａ、ｏｘ １１．５ｃｉの長方形に裁断して試料とし
た。To this gelatin solution, add an aqueous solution of the dye of the present invention and a comparative dye described below (2.0 x 10'' mol/water 2.0 mm), a hardener, and a surfactant, and add water to a colander to bring the total amount to 20.
I set it to 0 d. Next, this colored solution was coated on a polyester film base coated with an undercoat and 75 sides were coated with 859/Trt.
Apply it so that it becomes 50. The sample was heated at o'c for 24 hours and cut into a rectangular shape of 11.5 ci at a, ox to prepare a sample.
試料を３０．０ ’ＣのＤ−７２現像液に５秒および１
５秒間浸漬した後、流水中で１０秒間水洗し、附看した
水滴を濾紙ではさんで吸いとり、乾燥して処理済の試料
とした。試料および処理済試料はマクベス透過濃度計Ｔ
Ｄ−５０４を用いて５点を測定し、その平均値を各々の
濃度とした。Place the sample in D-72 developer at 30.0'C for 5 seconds and 1
After being immersed for 5 seconds, the sample was washed under running water for 10 seconds, and the water droplets were absorbed with filter paper and dried to obtain a treated sample. Macbeth transmission densitometer T for samples and processed samples
Measurements were made at 5 points using D-504, and the average value was taken as the respective concentration.
得られた結果を表−１に示す。The results obtained are shown in Table-1.
比較染料Ａ 比較染料Ｂ ５０３Ｎａ ＳＯ，Ｎａ 比較染料Ｃ （以下余白） 表−１ ＊ベース濃度を表わす。Comparative dye A Comparative dye B 503Na SO, Na Comparative dye C (Margin below) Table-1 *Represents base concentration.
表−１より明らかなように、本発明の染お１は初期濃度
の高いのに加えて、処理後の濃度との差も大きい。As is clear from Table 1, the dye 1 of the present invention not only has a high initial concentration, but also has a large difference in concentration after treatment.
すなわち、染料の脱色、溶出性のずぐれていることがよ
くわかる。In other words, it is clear that the decolorization and dissolution properties of the dye were poor.
実施例２：
染料の１％水溶液を１０％ゼラヂン水溶液に加え、８５
３／尻の塗布層とした場合の光学濃度が１．０となるよ
うに調整し、１０％ザポニン水溶液をゼラチン水溶液１
５０ｄに対し５ｍ！、１０％ホルマリンを１．５ｄ加え
て得られた着色したピラチン水溶液を用いて実施例１と
同様な操作により硬膜された光学濃度１．０の塗布層を
得る。この塗イト層の上に純臭化銀乳剤を塗布し、下記
組成の現像液を用いて２０’Ｃで１分３０秒間現像した
後常法に従い定着、水洗、乾燥した。Example 2: Add a 1% aqueous solution of dye to a 10% aqueous geladine solution and add 85
3/ Adjust the optical density to be 1.0 when used as a coating layer on the buttocks, and add 10% zaponin aqueous solution to gelatin aqueous solution 1
5m for 50d! A hardened coating layer having an optical density of 1.0 is obtained by the same operation as in Example 1 using a colored aqueous piratin solution obtained by adding 1.5 days of 10% formalin. A pure silver bromide emulsion was coated on this coated layer and developed at 20'C for 1 minute and 30 seconds using a developer having the following composition, followed by fixing, washing with water, and drying according to a conventional method.
実施例１で行った方法を用いて、得られた処理済のフィ
ルムの光学濃度を測定したところ、本発明の染料を含む
各試料の処理後濃度は全て０．０２であった。（但し、
ベース濃度０．０２＞現像液の組成
メトール ３９亜硫酸ナトリウ
ム ４５Ｉｊハイドロキノン
１２ｇ炭酸ナトリウム（１水塩）
８０ｇ臭化カリウム ２ｇ水を加
えて全量１１とする。When the optical density of the obtained treated film was measured using the method performed in Example 1, the post-processing density of each sample containing the dye of the present invention was all 0.02. (however,
Base concentration 0.02>Developer composition Metol 39 Sodium sulfite 45 Ij Hydroquinone
12g sodium carbonate (monohydrate)
Add 80g potassium bromide and 2g water to make a total volume of 11.
また、本発明の染料を含む各試料は水溶液調製中、乳剤
調製中および保存中に変退色等の経時変化を起さずカブ
リや減感等の写真特性に悪影響もなく、極めてすぐれた
ハレーション防止効果を有する感光材料であった。In addition, each sample containing the dye of the present invention does not cause changes over time such as discoloration or fading during aqueous solution preparation, emulsion preparation, or storage, and has no adverse effects on photographic properties such as fogging or desensitization, and has extremely excellent halation prevention. It was an effective photosensitive material.
Claims (1)
れていてもよい低級アルキル基を、Ｌは低級アルキル基
で置換されてもよいメチン塁を表わし、ｌは整数１、２
および３を表わす。）(1) A photographic light-absorbing dye represented by the general formula below. General formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ represents the base, l is an integer 1, 2
and 3. )
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14564286A JPS632045A (en) | 1986-06-21 | 1986-06-21 | Photographic light absorbing dye |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14564286A JPS632045A (en) | 1986-06-21 | 1986-06-21 | Photographic light absorbing dye |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS632045A true JPS632045A (en) | 1988-01-07 |
| JPH0555057B2 JPH0555057B2 (en) | 1993-08-16 |
Family
ID=15389730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14564286A Granted JPS632045A (en) | 1986-06-21 | 1986-06-21 | Photographic light absorbing dye |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS632045A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63264745A (en) * | 1986-12-25 | 1988-11-01 | Fuji Photo Film Co Ltd | Sliver halide photographic sensitive material |
| JPH01233439A (en) * | 1988-03-14 | 1989-09-19 | Konica Corp | Silver halide photographic sensitive material |
| WO2020158225A1 (en) * | 2019-01-28 | 2020-08-06 | 株式会社バイオラジカル研究所 | Antioxidant and use thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55120660A (en) * | 1979-03-02 | 1980-09-17 | Agfa Gevaert Nv | Novel light absorbing methine dyes and photograph material containing them |
| JPS5824139A (en) * | 1981-07-02 | 1983-02-14 | Konishiroku Photo Ind Co Ltd | Oxonol dye for photography |
-
1986
- 1986-06-21 JP JP14564286A patent/JPS632045A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55120660A (en) * | 1979-03-02 | 1980-09-17 | Agfa Gevaert Nv | Novel light absorbing methine dyes and photograph material containing them |
| JPS5824139A (en) * | 1981-07-02 | 1983-02-14 | Konishiroku Photo Ind Co Ltd | Oxonol dye for photography |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63264745A (en) * | 1986-12-25 | 1988-11-01 | Fuji Photo Film Co Ltd | Sliver halide photographic sensitive material |
| JPH01233439A (en) * | 1988-03-14 | 1989-09-19 | Konica Corp | Silver halide photographic sensitive material |
| WO2020158225A1 (en) * | 2019-01-28 | 2020-08-06 | 株式会社バイオラジカル研究所 | Antioxidant and use thereof |
| JPWO2020158225A1 (en) * | 2019-01-28 | 2021-11-18 | 株式会社 バイオラジカル研究所 | Antioxidants and their uses |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0555057B2 (en) | 1993-08-16 |
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