US3687673A

US3687673A - Color photographic light-sensitive materials containing a cyan dye for silver dye bleaching method

Info

Publication number: US3687673A
Application number: US74342A
Authority: US
Inventors: Makoto Yoshida; Shinichi Imai
Original assignee: Fuji Photo Film Co Ltd
Current assignee: Fujifilm Holdings Corp
Priority date: 1969-09-22
Filing date: 1970-09-22
Publication date: 1972-08-29
Anticipated expiration: 1989-08-29
Also published as: JPS4910695B1; DE2046684A1; DE2046684C3; CH566579A5; GB1287173A; DE2046684B2; BE756410A

Abstract

A COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIAL FOR THE SILVER DYE BLEACHING METHOD COMPRISING A SUPPORT HAVING THEREON A PHOTOGRAPHIC EMULSION LAYER CONTAINING A MEMBER SLECTED FROM THE GROUP CONSISTING OF A CYAN DYE HAVING THE FOLLOWING GENERAL FORMULA

2-((1-HO,3,6-DI(HO3S-),8-(C6H5-CO-NH-)NAPHTH-2-YL)-N=N-

(2,5-DI(CH3-O-)-1,4-PHENYLENE)-N=N-),3,6-DI(HO3S-),

8-((4-Y,6-X-S-TRIAZIN-2-YL)-NH-),1-HO-NAPHTHALENE

WHEREIN X IS SELECTED FROM THE GROUP CONSISTING OF A HALOGEN ATOM, A HYDROXYL GROUP, AN AMINO GROUP AND AN ANILINO GROUP, AND AND WHEREIN Y IS A RESIDUAL GROUP OF A COMPOUND CAPABLE OF REACTING WITH THE MOST READILY REACTIVE CHLORINE ATOM OF CYANURIC CHLORIDE, AND THE SODIUM AND AMMONIUM SALTS THEREOF, IS DISCLOSED.

Description

Aug. 29, 1912 OPTICAL DENSITY MAKOTO YOSHIDA F-TAL 3,687,673 COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIALS CONTAINING A CYAN DYE FOR SILVER DYE BLEACHING METHOD Filed Sept. 22, 1970 600 WAVE LENGTH (nuno meter) INVENTORS MAKDTO YOSHIDA SHINICHI IMAI f j lyre! fJ/KM, M h 4" MCPQK ATTORNEYS United States Patent ice 3,687,613

Patented Aug. 29, 1972 dye does not diffuse into other photographic layers and 3,687,673

does not adversely affect the photographic properties of COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MA- TERIALS CONTAINING A CYAN DYE FOR the photographic emulsion, such as the formation of fog VER DYE BLEACHING METHOD and desensitization. Still further, it is necessary for the dye Makoto Yoshida and Shinichi Imai, Kanagawa, Japan, 5 formed from such an azo dye to have such properties as gssighofs j Photo Film Kallagawa, desirable absorption spectral characteristics as a cyan dye apan Filed Sept 22, 1970, Ser. No. 74,342 and a stability t; the severe chemical treatlments of the Claims priority, application Japan Sept. 22, 1969, silver dye bleac mg method, such as deve opment, dye 44/75,466 bleaching, and silver bleaching, as well as have suflicient G03! 1/10 fastness to light, heat, and humidity. US. C]. 96-99 7 Claims Therefore, an object of this invention is to improve the color reproducibility of color photographs by using a cyan ABSTRACT OF THE DISCLOSURE dye satisfying the above-described characteristics required A color photographic lighbsensifive material for the for the dye to be used in color photographic light-sensitive Silver dye bleaching method comprising a support having materials for the silver dye bleaching method and also thereon a photographic emulsion layer containing a memhah'hg a maximum absorption Wave length at the longer ber selected from the group consisting of a cyan dye hav- Wave length sldeing the following general formula 2 Another object of this invention is to provide a color H0 8 SOgH OCH; H0 5 SOaH wherein X is selected from the group consisting of a photographic light-sensitive material for the silver dye halogen atom, a y y p, an amino group and an bleaching method containing an improved cyan dye. anilino group, and wherein Y is a residual group of a compound capable of reacting with the most readily reac- OF INVENTION tive chlorine atom of cyanuric chloride, and the sodium The ohlects of thls mventlon h h YF y Q d ammonium salts thereof i di l d porating in a color photographic light-sensitive material for the silver dye bleaching method a cyan dye represented 40 by the following general Formula I:

N=N -N=N SOQH OH: 11038 $0311 BACKGROUND OF THE INVENTION wherein X represents a halogen atom, a hydroxyl group, an amino group, or an anilino group and Y represents a (1) Fleld of the mventlon residual group of a compound capable of being reacted The PWSent invention relates to a Color P g p with the first chlorine atom of cyanuric chloride. light-sensitive material for the silver dye bleaching method, wherein a cyan dye is incorporated in a photo- DESCRIPTION OF THE INVENTION sensitive silver halide emulsion layer. It is known that the three chlorine atoms of cyanuric (2) Description of the prior art chloride can result in a three-step replacement reaction in accordance with the reaction temperatures, that is to say, A20 y are usually 156d as the cyan dyes in color the first chlorine atom reacts at about 0 C., the second Photographic hghhsehsitive materials for the Silver dye chlorine atom at about 40 C., and the third chlorine atom bleaching method. It is necessary that the azo dye be at about 90 C bleached in response to the silver image formed on devel- E l f th id l group f a compound whi h opment to form a positive image of a cyan dye. Therefore, can be reacted with the first chlorine atom of cyanuric in order that the dye be used for the purpose, the azo chloride, the most readily replaceable chlorine atoms group of the dye must be readily reduced and decomposed described above are a hydroxyl group, :an alkoxyl in response to the amount of silver present, thereby the group, an aryloxy group, a mono-substituted amino group, dye is completely bleached. Also, when the dye is incora di-substituted amino group, a nitrogen-containing cyclic porated in a silver halide emulsion, it is necessary that the group, a sulfoamino group, a thioalkyl group, and the like.

In order to obtain a cyan dye having absorption at a longer wave length region, one of the amino groups of the H-acid which is the nuclei of a cyan dye can be in an unsubstituted state. That is to say, the maximum absorption wave elngth of an aqueous solution of dye A having the following formula Dye A:

N=NQN=N 803E CH3 H033 is 674 mu, which is almost the same as that of the dye used in this invention. However, because the dye is not substituted at the amino group, the dye difiuses into other photographic layers when it is incorporated in a photographic emulsion layer of a color photographic lightsensitive material. This makes the utilization of the dye in color photographic light-sensitive materials difficult.

Therefore, substitutions of the amino group of the H-acid might provide a diffusion resisting property to the dye. Dye B having the following formula prepared by substituting the amino group of H-acid with, for instance, benzoyl chloride Dye B OH NH:

in the silver dye bleaching method but also for color photographic light-sensitive materials used in the silver dye bleaching method for forming single color images and two color images.

The cyan dyes of this invention can be synthesized in the following manner. First, the first chlorine atom of the SOzH three chlorine atoms of cyanuric chloride is replaced with the residual group Y to prepare a 2-Y substituted-4,6-dichloro-S-triazine. Then, the N-substituted H-acid is synthesized by utilizing the reaction of the second chlorine atom of the substituted triazine prepared above and the amino group of H-acid. Then the N-substituted H-acid is reacted with the diazo component of a monoazo dye to obtain the cyan dye.

As the cyan dyes to be used in this invention, suitable ones are those having, for example, the following structures although they are not limited to them only. In addition, the sulfone group of each of the cyan dyes shown @ocrm )11 porn on sumo-Q 803E hon, sour does no diffuse into other photographic emulsion layers when it is incorporated in a photographic emulsion layer of a color photographic light-sensitive material. However, this dye shows no absorption at a longer wave region. Thus, such a type of a diifusion resisting dye is therefore inadequate for a color photographic light-sensitive material. That is to say, the maximum absorption wave length of an aqueous solution of Dye B is 606 mp, which is extremely shorter than that of the dye used in this invention.

The inventors have investigated a cyan dye in which the amino group of the H-acid is substituted and which has the maximum absorption wave length at the wave length region of as long as possible, and have discovered that the purposes are fulfilled by the dye having the structure shown by general Formula I. In other words, by substituting the amino group of H-acid with an S-triazine group, a cyan dye satisfying the above purposes can be obtained.

The cyan dyes to be used in this invention, for instance dye 1 and dye 2, shown hereinafter, having extremely desirable absorption characteristics as shown in the accompanying drawing, are readily bleached, and have no adverse influence on the photographic properties of a silver halide photographic emulsion when the dye is added to the emulsion. Also, the cyan dyes have sufi'icient fastness. Thus, the cyan dyes of this invention are quite desirable as cyan dyes for color photographic light-sensitive materials in silver dye bleaching method.

DESCRIPTION OF THE ACCOMPANYING DRAWING The accompanying drawing is a graph showing comparatively the spectral absorption curves of an aqueous solution of two dyes used in the instant invention [Dyes 1 and 2] and an aqueous solution of known dyes {-Dyes A and B].

DETAILED DESCRIPTION OF THE INVENTION The cyan dyes of this invention can be used not only for natural color photographic light-sensitive materials below can be substituted by a sodium atom, potassium or an ammonium group. In the structural formulae shown below, the following grouping is denoted as A:

H 035 S 03H 0 H3 C! N\ or: NH \N I 0H Nn- N A NHQ H038 scan N on NH N 1 A OH H038 --SO3H Now, typical examples of the synthesis of the cyan dyes of this invention are illustrated below.

SYNTHESIS 1 Synthesis of the dye having structural Formula 2 '(1l) Synthesis of diazo component-198 parts by weight of 1-amino-2,5-dimethoxy-4-nitrobenzene are diazotized in a strong hydrochloric acid suspension. The diazotized liquid is added to 423 parts by weight of a solution of 1-benzoylamino-8-hydroxynaphthalene-3,6-disulfonic acid made alkaline with sodium carbonate to cause coupling. By reducing the nitroazo dye thus obtained with sodium sulfide in an alkaline solution, the corresponding amino-azo dye is obtained and then the dye is isolated (see the specification of Japanese patent publication No. 25,768/ 1964) (1-2) Synthesis of coupling component-A solution of 18.5 parts of cyanuric chloride in 100 parts of acetone is added in a mixture of 300 parts of water and 300 parts of ice and then 6.7 parts of aqueous ammonia having a specific gravity of 0.89 are added to the mixture at temperatures of lower than C. When the ammonia is consumed, 6.7 parts of aqueous ammonia are further added to the system, and the mixture is stirred for about 1 hour at temperatures below 0 C. Thereafter, the solution is acidified slightly by adding l-N hydrochloric acid.

A solution of 36.3 parts of sodium '1-amino-8-naphthol- 3,6-disulfonate in 200 parts of water is added to the suspension of 2-amino 4,6 dichloro S triazine prepared above. The solution is heated for 45 minutes at 55 C. and then the solution is further stirred at the same temperature until the 1-amino-8-naphthol-3,6-disulfonic acid is consumed. Thereafter, the solution is neutralized by adding an aqueous 2 N sodium carbonate solution and then cooled, thereby the desired material is deposited. The product is then collected by filtration and dried.

(1-3) Synthesis of dye (2).The diazonium solution of the diazo component obtained in synthesis (1-1) is coupled with the coupling component obtained in synthesis (1-2) in an aqueous pyridine solution at 20 C. The dye obtained above is dissolved again in water and purified by a repeated s-alting out operation until the purple impurities are completely removed. Then, the product solution is subjected to a salting out by sodium acetate.

The precipitates are collected by filtration, washed with ethanol and dried.

6 SYNTHESIS 2 Synthesis of the dye of structural Formula 1 The same procedure as used in Synthesis (1-2) described above is followed using 2-hydroxy-4,6-dichloro-S- triazine to obtain a coupling component, which is coupled with the diazo component obtained in synthesis (1-1) described above. Thereafter, by following the same procedure as used in Synthesis (1-3) described above, the dye having the structural Formula I is obtained.

SYNTHESIS 3 Synthesis of the dye of structural Formula 3 EXAMPLE 1 1 g. of the cyan dye shown by the structural Formula 2 was dissolved in 100 ml. of a 5% aqueous sodium hydroxide solution and a mixture of ml. of the dye solution thus obtained and g. of a silver bromide emulsion (containing about 30 g. of silver bromide per kilogram of the emulsion) was coated on a film base. The light-sensitive film prepared was exposed under a step wedge and then developed for 10 minutes using a developing solution having the following composition:

G. N-methyl-p-aminophenol 1/2 sulfate 2 Anhydrous sodium sulfite 30 Hydroquinone 8 Sodium carbonate 20 Potassium bromide 4 Water added to make the total volume to 1 liter.

The film developed was then washed with water and fixed for 4 minutes using a solution having the following composition:

G. Anhydrous sodium thiosulfate 350 Anhydrous sodium sulfite 10 Water added to make the total volume to 1 liter.

The film was then washed with water, hardened, using a 4% aqueous formaldehyde solution, washed with water, and then processed for 15 minutes using a dye bleaching bath having the following composition:

Thiourea g 60 Potassium bromide g 30 Concentrated hydrochloric acid m 30 2-arnino-3-hydroxyphenazine g 0201 Water added to make the total volume to 1 liter.

The film was washed with water and then treated using a silver bleaching bath having the following composition:

Crystalline copper sulfate g 100 Concentrated hydrochloric acid ml 100 Water added to make the total volume to 1 liter.

The film was washed with Water, fixed again using the fixing bath having the composition shown above, washed further with Water, and dried.

Using the above-described treatments, a completely bleached cyan image was formed at the highlight portion. The image produced was suitable as the cyan component image of a multi-color type light-sensitive material for the silver dye bleaching method.

EXAMPLE 2 wherein X is selected from the group consisting of a The same procedure as used in Example 1 was followed gggiz igg i 3132 fifggg giggi g f ga 23g :3 2:1 a 21ri ir i gi fvi h t faiii d fiz h igig l gggl? pound capable of reacting with the most readily reactive the image was completely blea'ched and the image was 5 chlorine atom of cyanuric chloride selected from the group suitable as the cyan component image of a multi-color consisting of a hydrpxyl group an g type light-sensitive material using a silver dye bleaching aryloxy an a S flute ammo method. group wherein the substrtuent is an aryl group, a mtrogencontaining saturated cychc ring group having 6 members, EXAMPLE 3 10 a sulfoamino group, a thioalkyl group, and the sodium The same procedure as used in Example 1 was followed and ammomum Salts thereofusing the cyan dye having the structural Formula 3 and The 00101 PhOtOgraphic light-Sensitive material a cyan image was obtained. The highlight portion of the cording to claim 1, wherein said cyan dye has the followcolor image was completely bleached and was suitable as ing formula N L 11 00m 011 NH \N a I i N=N N=N H 0,,s son: sons the cyan component image of a multi-color type light- 3. The color photographic light-sensitive material acsensitive material using a silver dye bleaching method. cording to claim 1, wherein said cyan dye has the following formula What is claimed is: 4. The color photographic light-sensitive material 1. A color photographic silver halide light-sensitive according to claim 1, wherein said cyan dye has the material for the silver dye bleaching method comprising following formula N-i Q-OOHN on non, OH IgIH N N=N-Q-N: In H0 3 305E CH3 Hogs son:

a support having thereon a photographic emulsion layer containing a member selected from the group consisting of a cyan dye having the following general formula:

N: -N=N Y H038 S0311 OOH; H0 SOaH 5. The color photographic light-sensitive material according to claim 1, wherein said cyan dye has the following formula ore-om N=N N=N a 110 s S0311 cm H035 SOaH om-o 10 6. The color photographic light-sensitive material according to claim 1, wherein said cyan dye has the following formula Q N 00111 on 00113 on ITIH- N [N=NN=N NH- HO3S- SOaH (IJCH3 H033 S03H 7. The color photographic light-sensitive material according to claim 1, wherein said cyan dye has the following formula 31 N OCHN OH 00113 0H NH- \N N=N N=N-- O 0 2H 5 H038 SOQH (3cm H038 S0311 References Cited UNITED STATES PATENTS 3,178,291 4/1965 Mory et a1. 96-99 3,211,554 10/1965 Dreyfuss 96-99 J. TRAVIS BROWN, Primary Examiner IU.S. Cl. X.R.