US3793031A - Color photographic light-sensitive materials for diffusion transfer process - Google Patents

Abstract

A red-sensitive silver halide photographic emulsion for photographic light-sensitive material containing dye developing agent suitable for diffusion transfer process which comprises a combination of at least one sensitizing dye represented by the following general formula (I) and at least one sensitizing dye represented by the following general formula (II):

wherein Z and Z1, which may be the same or different, represent a nonmetallic atomic group necessary for completing a series of benzothiazole nucleus or a series of benzoselenazole nucleus; R and R1 represent each an alkyl group or a substituted alkyl group; at least one of said R and R1 being a hydroxyalkyl group, a carboxyl group-containing alkyl group, or a sulfo groupcontaining alkyl group; X represents an anion; and n is 1 or 2; and n being 1 when said dye forms an intramolecular salt and

WHEREIN Z2 and Z3, which may be the same or different, represent each a non-metallic atomic group necessary for completing a series of benzothiazole nucleus or a series of benzoselenazole nucleus; R2 and R3 have the same significance as R and R1 of the general formula (I); at least one of said R2 and R3 being a hydroxyalkyl group, a carboxyl group-containing alkyl group, or a sulfo group-containing alkyl group; X represents an anion; and m has the same significance as n of the general formula (I).

Description

United States Patent [191 Shiba et al.

[ 51 Feb. 19, 1974 COLOR PHOTOGRAPHIC LIGHT-SENSITIVE MATERIALS FOR DIFFUSION TRANSFER PROCESS [75] Inventors: Keisuke Shiba; Masanao Hinata;

Yasushi Oishi; Yoshiuobu Yoshida, all of Kanagawa, Japan [73] Assignee: Fuji Photo Film Co., Ltd.,

Ashigara-shi, Kanagawa, Japan 22 Filed: Dec. 30, 1971 211 App]. No.: 214,214

[30] Foreign Application Priority Data Dec. 30, Japan 45-123040 [52] US. Cl 96/99, 96/3, 96/29 D,

96/77, 96/124 [51] Int. Cl. G03c 1/40, G030 5/54, G030 7/00 [58] Field of Search..... 96/74, 124, 99, 3, 29 D, 77,

[56] References Cited UNITED STATES PATENTS 3,672,898 6/1972 Schwan et al 96/74 Primary Examiner-J. Travis Brown Assistant Examiner-Alfonso T. Su'ro Pico Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn, and Macpeak [5 7] ABSTRACT A red-sensitive silver halide photographic emulsion for photographic light-sensitive material containing dye developing agent suitable for diffusion transfer process which comprises a combination of at least one sensitizing dye represented by the following general formula (I) and at least one sensitizing dye represented by the following general formula (II):

wherein Z and Z which may be the same or different, represent each a non-metallic atomic group necessary for completing a series of benzothiazole nucleus or a series of benzoselenazole nucleus; R and R have the same significance as R and R of the general formula (l); at least one of said R and R being a hydroxyalkyl group, a carboxyl group-containing alkyl group, or a sulfo group-containing alkyl group; X represents an anion; and m has the same significance as n of the general formula (I).

7 Claims, 2 Drawing Figures (IN ODLJ' AWN COLOR PHOTOGRAPIIIC LIGHT-SENSITIVE MATERIALS FOR DIFFUSION TRANSFER PROCESS BACKGROUND OF THE INVENTION 1. Field of the Invention:

The present invention is directed to spectrally sensitized photographic light-sensitive materials used in a transfer process which contain dye developing agents the materials being suitable for use in a diffusion transfer process.

2. Description of the Prior Art:

A molecule containing a dye moiety and a moiety for developing silver halide is a necessary component of photographic elements used for forming dye images by a diffusion transfer process. Such a compound is ordinarily called a dye developing agent. It is known from US. Pat. No. 2,983,606; British Pat. No. 804,971; and French Pat. No. 1,313,767 that when a lightsensitive element containing a dye developing agent and a silver halide is light-exposed and treated with an alkali processing composition, the exposed areas of the light-sensitive element are developed and the dye developing agent in the exposed areas becomes substantially non-difiusable, while the dye developing agent in the unexposed areas is diffusable. When the lightsensitive element thus processed is brought into close contact with an image-receiving element, a transferred image of the dye can be obtained on the imagereceiving element, the transferred image thus formed being a positive image singe the density of the image is inversely proportional to the amount of exposure.

As is well known in this field, the dye developing agents such as the azo dye developing agents of the anthraquinone dye developing agents reduce the sensitivity of a silver halide photographic emulsion. In particular, this action is encountered with a spectrally sensitized silver halide emulsion although in this case the absorption of the dye developing agent may be neglected. This effect is encountered not only in the case of incorporating the dye developing agent directly into the spectrally sensitized silver halide emulsion layer, more especially a red-sensitized layer, but also in the case where the dye developing agent is in a layer brought into contact with the red-sensitive silver halide emulsion layer. This is believed to be caused by a part of the dye developing agent in the layer diffusing into the redsensitive emulsion layer.

SUMMARY OF THE INVENTION One object of this invention is to provide a redsensitive emulsion layer having a high red sensitivity in the presence ofa dye developing agent in a silver halide photographic light-sensitive material suitable for diffusion transfer process use using a dye developing agent.

The object of this invention can be achieved by redsensitizing a silver halide emulsion with a combination of at least one sensitizing dye represented by the following general formula (I) and at least one sensitizing dye represented by the general formula (II):

wherein Z and 2,, which may be the same or different, represent a nonmetallic atomic group necessary for completing a series of benzothiazole nucleus or a series of benzoselenazole nucleus; R and R represent an alkyl group such as a methyl group, an ethyl group, and a n-propyl group; a substituted alkyl group such as acetoxyalkyl group (e.g., a B-acetoxyethyl group, a y-ace toxypropyl group), a hydroxyalkyl group (e.g. a B-hydroxyethyl group, a S-hydroxybutyl group, etc.), a car boxyl groupcontaining alkyl group (e.g., a cabroxymethyl group, a fi-carboxyethyl group, a y-carboxypropyl group, a 8-carboxybutyl group, and a 2-(2-carboethoxy)-ethyl group), a sulfo groupcontaining alkyl group (e.g., a B-sulfoethyl group, a y-sulfopropyl group, a y-sulfobutyl group, a fi-sulfobutyl group, a 2-hydroxy-l-sulfopropyl group, a 2-(3-sulfopropoxy)ethyl group, a 2-acetoxy-l-sulfopropyl group, a 3-methoxy-2-(3-sulfopropoxy)propyl group, a 2-[2-(3-sulfopropoxy)ethoxy1ethyl group and a 2- hydroxy-3-(3'-sulfopropoxy)propyl group; at least one of said R and R being selected from a hydroxyalkyl group, a carboxyl group-containing alkyl group or a sulfo-group-containing alkyl group; X represents an anion; and n is l or 2; n being 1 when the compound forms an intramolecular salt.

wherein Z and Z which may be the same or different, represent each a non-metallic atomic group necessary for completing a series of benzothiazole nucleus or a series of benzoselenazole series; R and R have the same significance as R and R at least one of R or R being a hydroxyalkyl group, a carboxyl group containing alkyl group, or a sulfo group-containing alkyl group; X represents an anion such as halide ion, thiocyanate ion, benzene sulfonate ion, p-tolune sulfonate ion, methyl sulfate ion and ethyl sulfate ion, and m is 1 or 2, n being 1 when the compound forms an intramolecular salt betain-like structure.

BRIEF DESCRIPTION OF THE DRAWINGS:

FIGS. 1 and 2 represent elements in accordance with the present invention.

DETAILED DESCRIPTION OF THE INVENTION:

methoxybenzthiazole, 5-bromobenzothiazole, 5,6-dimethylbenzothiazole, S-cyanobenzothiazole, 5- phenylbenzothiazole, 5-hydroxy-6- methyibenzothiazole, 5-hydroxy-6- methylbenzothiazole, S-hydroxybenzothiazole, 5- ethoxy--methylbenzothiazole, Scarboxybenzothiazole, benzoselenazole, S-methylbenzothiazole, 5- chlorobenzoselenazole, 5-methoxybenzoselenazole, S-phenylbenzoselenazole, 5,6- dimethylbenzoselenazole, 5- hydroxybenzoselenazole rings.

and

The sensitizing dyes used in this invention are known dyes. The dyes represented by general formulae (1) and (11) shown above are described for instance, in US. Pat. No. 2,503,776; German Pat. No. 1,929,037 and German Pat.

No. 1,811,542; French Pat. No.

1,573,694; and British Pat. No. 1,128,418. The sensitizing dyes can readily be synthesized by one skilled in the art by referring to the above patents.

Concrete examples of the sensitizing dyes represented by general formula (I) used in this invention are shown below by way of illustration.

H'C 02H: CHt CH=JJCH= C1 C1 4 \g N/ (Hfla H2)a8 0 QB 02H: -CH==(|JCH N N (JEHQJSOF (HzhSOaH 02H; -CH=o-CH= B (IJHICHZOH JHzCHgOH 0 $13M. 7 Se .7 7 iv .1 WWW C1 1 3/ 2 5 JzHa Hz): S F

02H; CH=(CH= N/ I v 7 2):| n'- (HihSOIH 1-l5 Se S0 CzHa =CH(IJ=CH N 13 I h oaH HDaS a 1-16 S Se 01H! 40 =CH-(5-CH 2 3 (CH2): S Or Concrete examples of the sensitizing dyes used in this invention represented by the general formula (II) are shown below by way of illustration.

M in" d.- 17m.

II-l S S mo E on,

-CH=C-CH= HaC CH3 N N [W 2)a s' ((iIHUaSOaH (3H1 I -CH=C-CH= I F30 y CF:

v (Crimson (cams 0,11

11-3 Se S ([7113 *CH=C-CH= I C1 Cl N N flfias r ((iJHzOaS 01H The dye developing agents used in this invention are known. In a diffusion transfer process such a compound acts as a developing agent for silver halide and as a dye. The dye developing agent does not substantially'difiuse into a colloid layer such as a hydrophilic organic colloid layer used for photographic emulsions at a neutral hydrogen concentration, but it can diffuse in such an emulsion layer in the presence of an alkali processing composition. Dye developing agents used in the present invention are described in the specifications of, e.g., Australian Pat. No. 220,279; German Pat. No. 1,036,640; British Pat. Nos. 804,971; 804,973; 804,974; and 804,975; Belgian Pat. No. 554,935; French Pat. Nos. 1,168,292; and 1,313,76; Canadian Pat. Nos. 577,021 and 579,038; and US. Pat. Nos.

3,236;873; and 3,252,990.

ln general, a dye developing agent contains in one molecule a dye moiety and at least one silver halide developing group. The term silver halide developing group means a group suitable for developing an exposed silver halide. A preferred silver halide developing group is the hydroquinonyl group, but the group may be an o-hydroxyphenyl group, an 0- or p-aminosubstituted hydroxyphenyl group, etc. A developing group generally contains a benzenoid group, i.e., an aromatic developing group forming a quinoid or a quinone material when it is oxidized. The typically used dye moiety of the most common dye developing agents is an azo dye moiety or an anthraquinone dye moiety. In this specification a dye developing agent having an azo dye moiety is called an azo dye developing agent and a dye developing agent having an anthraquinone dye moiety is called an anthraquinone dye developing agent.

By using the dye-image forming components such as the dye developing agents described above, monochromatic images or multi-chromatic images can be formed according to various techniques known in the diffusion transfer process art.

In accordance with one process of obtaining color transfer images utilizing dye developing agents, at least two light-sensitive emulsion layers selectively sensitized are formed on a support and the light-sensitive material is simultaneously processed with an image-receiving layer in a closely contacted state.

FIG. 1 of the accompanying drawing shows an embodiment for forming a monochromatic transfer image. A light-sensitive element is composed of a support A, a layer B containing a color image-forming component and a silver halide emulsion layer C. A rupturable cell F containing alkaline processing composition is placed on the light-sensitive element so that the alkali processing composition is isolated from the light-sensitive element. An image receiving element is composed of a support E and an image-receiving layer D. After subjecting the light-sensitive element to light exposure, the image-receiving element is contacted with the lightsensitive layer with the inserted cell F between them and then the cell F is ruptured by a suitable pressure, for example by passing the laminated elements through a pair of grooved rolls (not shown), whereby the liquid processing composition in the cell F thus ruptured is spread in a layer between the two laminated elements. The processing composition is diffused into the silver halide emulsion layer C to develop the latent image formed in said layer. A color image forming component contained in the layer B is transferred from the unexposed areas of the layer B into the image-receiving layer D of the image-receiving element to reproduce thereon the positive color image in the light exposure. Then, after at least a part of the color image forming component has been transferred to the image-receiving element, the latter is separated from the light-sensitive element.

The silver halide emulsion layer explained above is composed of, for example, a blue-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer, formed on a support, and the emulsion layers contain a magenta dye developing agent and a cyan dye developing agent, respectively. The dye developing agent may be incorporated in the silver halide emulsion layers as in the form of grains or may be incorporated in a layer adjacent to the silver halide emulsion layer. The silver halide emulsion layer containing the dye developing agent or the combination of a silver halide emulsion layer and an adjacent layer containing the dye developing agent is isolated from other silver halide emulsion layers containing other dye developing agents or other combinations of a silver halide emulsion layer and other dye developing agent-containing adjacent layers by a suitable intermediate layer (e.g., a gelatin or polyvinyl alcohol layer).

A natural color photographic light-sensitive material of another type is composed of a support having a redsensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a blue-sensitive silver halide emulsion layer. The emulsion layers contain a cyan dye developing agent, a magenta dye developing agent, and a yellow dye developing agent, respectively. The mode of incorporating the dye developing agents in the color photographic material is the same as stated above.

In yet another element useful for obtaining a multicolor image, plural image-receiving elements or sheets suitable for being processed by more than one liquid processing composition and suitable dye developing agents are contained in the light-sensitive elements. A system of this type is described in, for example, U.S. Pat. No. 2,647,049.

In still another element useful for obtaining a multi color image, a light-sensitive silver halide emulsion layer comprises at least two kinds of fine light-sensitive grains each selectively sensitized and arranged in the form of a light-sensitive screen. Concretely speaking, each of the light-sensitive grains is composed of a silver halide emulsion containing a proper dye developing agent. For example, in the light-sensitive screen, the fine grains of a blue-sensitized emulsion and the fine grains of red-sensitized emulsion are alternately arranged in a screen pattern and contain a magenta dye developing agent and a cyan dye developing agent, respectively. A light-sensitive screem suitable for color photography by a subtractive color process has a screen pattern of fine grains of red-sensitive emulsion, fine grains of a green-sensitive emulsion, and fine grains of a blue-sensitive emulsion, each which contains a cyan image-forming dye developing agent, a magenta image-forming dye developing agent, and a yellow image-forming dye developing agent, respectively. A transfer element of this type is described in U.S. Pat. No. 2,968,554 and U.S. Pat. No. 2,983,606.

In the red-sensitive emulsion used in this invention, a cyan-forming dye developing agent, (e.g., anthraquinone dye developing agent hereinbefore defined), a magenta-forming dye developing agent (e.g., azo dye developing agent hereinbefore defined), and a yellowforrning dye developing agent (refer to the above- I mentioned U.S. patents) are used, but other color dye developing agents such as a black dye developing agent as well as mixtures of the above-mentioned dye developing agents may also be used.

The dye developing agent used in this invention is incorporated into a silver halide photographic emulsion or into an emulsion layer adjacent the silver halide emulsion layer. Such a layer containing the dye developing agent may be formed of about 0.5-8 percent by weight of the dye developing agent dispersed in a colloidal binder such as gelatin, or gelatin derivatives such as gelatin phthalate, or dissolved in a polymer binder such as acetate hydrogen phthalate cellulose.

The alkali processing composition used in this invention consists of an aqueous solution containing at least one alkaline compound showing a pH range more than 10, preferably about 14 of pH when added to. the aqueous solution such as diethyl amine, sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium carbonate. In addition triethylamine may be added to said aqueous solution. If it is desired to apply the alkali processing composition as a uniform layer to the emulsion layer of the light-sensitive element by spreading the processing composition thereon, the abovementioned alkali processing composition may contain a film-forming viscosity improver which when the composition is spread over the emulsion layer and dried, provides a comparatively hard and comparatively stable film. The preferred film-forming materials used as the viscosity improver are high molecular weight polymers such as a water-soluble polymer ether inactive to the alkali solution, e.g., hydroxyethyl cellulose or carboxymethyl cellulose sodium. Other film-conning materials of which the viscosity increasing faculty is not substantially influenced by contact with an aqueous solution for long periods of time can also be used.

Furthermore, an alkali processing composition containing a mordant can be used in this invention; for example, a composition as is disclosed in Japanese Pat. No. 6449/1963.

Suitable examples of the alkali processing compositions are shown in the examples of the present invention.

It is also sometimes desirable under some conditions to apply the alkali processing composition to the lightsensitive element before exposure in accordance with the technique described in the specification of US. Pat. No. 3,087,816.

The alkali processing composition used in this invention may further contain a developing aid, i.e., a developing promoter such as p-methylaminophenol, 2,4- diaminophenol, p-benzylaminophenol, hydroquinone, toluhydroquinone; phenylhydroquinone, and 4'-methylphenylhydroquinone. Also, as described in specification of US. Pat. No. 3,039,869, a combination of developing promoters such as a 3-pyrazolidone developer and a benzenoid developer may be used. Examples of combinations of the developing promoters include combinations of 1-phenyl-3-pyrazolidone and pbenzylaminophenyl, and combinations of 1-phenyl-3- '25 pyrazolidone and 2,5-bis-ethylamino hydroquinone. Such a developing promoter is usually incorporated in -the alkali processing composition, but at least one member of the combination may be preliminarily incorporated in a silver halide emulsion layer or a layer adjacent thereto containing the dye developing agent. In the dye developing agent-developer promoterexposed silver halide system, an oxidation-reduction reaction is repeatedly conducted and the developing promoter acts as catalyst in the reaction.

The azo developing agents used in this invention are known compounds and are described in, for example, US. Pat. No. 3,134,672. As concrete examples of the azo developing agents used in this invention, the following compounds are illustrated:

. 1-phenyl-3-n-carbobutoxy-4-[p-(2 ,5 dihydroxyphenethyl)-phenylazo]5-pyrazolone.

2. l-phenyl-3-(N-2 '-ethylhexylc'arbamido )-4- [p- (2 ,5 -dihydroxyphenethyl )-pehnylazol--pyrazolone.

3. l-(p-N,N-diethylsulfonemidophenyl )-3-N-nbutylcarbamido-4-[p-( 2 ,5 '-dihydroxyphenethyl phenylazol-S-pyrazolone.

4. 1-phenyl-3-N-n-hexy1carbamido-4-[ p-( 2 ,5 dihydroxyphen ylpropyl )-phenylazo ]-5 -pyrazolone.

5. 1-Phenyl-3-trifluoromethyl-4-[ p( 2 ,5 dihydroxyphenylisobutyl)phenylazo]-5-pyrazolone.

.6. l-Phenyl-3-N-,B-hydroxyethylcarbamido-4-]p- (2 ,5 '-dihydroxyphenethyl )-phenylazo]-5-pyrazolone.

7. l-Pheny1-3-N-n-hexylcarbamido-4-[p-( 2 ,5 dihydrozy-4'-methyl-phenethyl)-phenylazol]-5- pyrazolone.

8. l-Phenyl-3-N-n-hexylcarbamido-4-[p-( 2 ,5 dihydroxy-phenethyl )-phe nylazo]-5-pyrazolone.

9. l-Phenyl-3-N-n-heptylcarbamido-4-[p-( 2 ,5 dihydroxyphenethyl)-phenylazo]-5-pyrazolone.

l0. l-Phenyl-3-N-n-hexylcarbamido-4-[p-( 2 ,5 dihydroxy-4-chlorphenethyl-phenylazo]-5- pyrazolone.

l 1. l-phenyl-3 -trifluoromethyl-4-[p-( 2 ,5 dihydroxyphenethyl)-phenylazo] -5-pyrazolone.

dihyd roxyphenethyl )-phenylazo ]-5 -pyrazolone.

hydroxyethoxy 1 naphthol. 60 3 6 13. 1-Phenyl-3-N-cyclohexylcarbamido-4-[p-(2',5'- dihydroxyphenethyl)-phenylazo]-5-pyrazolone.

14. 1-Phenyl-3-N-n-butyl-carbamido-4-[p-( 2 ,5 dihydroxyphenethyl)-phenylazo]-5-pyrazolone having 5 the following formula:

methylphenylazo] -4-methoxyl -naphthol.

19. 2-[p-(2,5'-dihydroxyphenethyl)-phenylazo]-4- isobutoxyl -naphthol.

20. 2-[p-(2',5-dihydroxyphenethyl)-phenylazo]-4- N-methyl-N-phenylsu1foneamidol -naphthol.

21. 2-[p-(2,5 '-dihydroxyphenethyl)-phenylazo]-4- methylsulfone- 1 -naphthol.

22. 2[m-(2',5-dihydroxyphenethyl)-phenylazo]-4- n-propoxyl -naphthol.

23. 2-[p-(2',5'-dihydroxyphenethyl)-phenylazo]-4- ethoxyethoxy-cthoxyl -naphthol.

24. 2-[p-(2',5-dihydroxyphenethyl)-phenylazo]-4- methylsulfide-l-naphthol.

25. 2-[p-(2',5'-dihydroxyphenethyl)-phenylazo]-4- B-chloroethoxyl-naphthol.

26. 2-[p-(2,5 '-dihydroxyphenethyl-a naphthylazo]- 40 4-methoxyl -naphthol.

2-[p-( 2 ,5 '-dihydroxyphenylisobutyl phenylazo]-4-methoxyl -naphthol.

28. 2-[p-( 2',5 '-dihydroxyphenylpropyl)-phenylazo]-4-isopropoxy- 1 -naphthol.

5 phenylazo1-4-methoxyl-1-naphthol.

34. 2-]p-( 2 ,5 -dihydroxy-4'-methylphenethyl phenylazo]-4-n-propoxyl -naphthol.

35. 2-[p-2',5-dihydroxyphenethyl)-phenylazo]-4-B- 2-[p-(2 ,5 dihydroxy-3 ,4 6 '-trimethylphenethyl)-phenylazo]-4-methoxy-1- naphthol.

37. 2-[p-(2,5 '-dihydroxy-3 '-methylphenethyl)- phenylazo ]-4-n-propoxy- 1 -napthol.

38. 2-[ p-( 3 ,4 '-dihydroxyphenethyl )-phenylazo]-4- n-porpoxy- 1 -naphthol.

39. 2-[p-2 ,5 -dihydroxyphenethyl )-o- 106. 1 ,5 -bis-hydroquinonylmethylaminoanthraquinone.

107. l,5-bis-[B-( 3,4'-dihydroxyphenyl)]- ethylamino-anthraquinone.

108. l,5-bis-( B-hydroquinonylethylamino)- anthraquinone.

109. l,5-bis-(a-methyl-B-hydroquinonyl- 1 l8. 4-(2,5'-dihydroxyanilino)-8-chloroanthraquinone.

1 l9. l-[p-(B-hydroquinonylethyl)-phenylamino]- anthraquinone.

120. l-[B-( 3',4'-dihydroxyphenyl)-ethylamino]- anthraquinone.

121 l-homogentisamido-5-amino-4,8-dihydroxyanthraquinone.

It is known that the sensitizing dyes used in this invention are useful for spectral sensitization of usual silver halide emulsions. Also, sensitizing dyes useful in the case of using an anthraquinone dye developing agent are disclosed in .lapenese Pat. No. 392/1965. The sensitizing dyes described in the above Japanese patent have a carboxyalkyl group or a sulfoalkyl group (the alkylene chain used in a n-alkylene chain) and when the anthraquinone dye developing agent is used, the sensitizing dye of this Japanese patent shows a higher sensitizing property than a sensitizing dye having an alkyl group, but a sufficient sensitivity is not obtained without using a large proportion of the sensitizing dye per silver halide (this may be caused by a desensitizing action based on the presence of the dye developing agent). However, in the case of producing multi-layer color photographic material using a large amount of sensitizing dye, there occurs the fault that the sensitizing dye in the red-sensitive emulsion layer of the color photographic material diffuses into other silver halide light-sensitive layers such as a blue-sensitive lightsensitive emulsion layer, or a green-sensitive lightsensistive emulsion layer to spectrally sensitize the layer. Particularly, an alkyl group-containing sensitizing dye having a carboxyl group or a sulfo group diffuses readily and tends to spectrally sensitize other silver halide emulsion layers.

On the other hand, it has been astonishingly discovered that by using the combination of the sensitizing dyes according to the present invention, a red-sensitive emulsion layer having a high sensitivity is obtained and the sensitization of other emulsion layers is remarkably decreased.

It is known from Japanese Pat. No. 4933/1968 and German Pat. No. 1,929,037 that the combination of the sensitizing dyes used in the present invention gives good results in a system containing a color coupler dispersion, but the present inventors have found that when the combination of the sensitizing dyes is used in a system containing a dye developing agent in accordance with the present invention, the effect of the combination of the sensitizing dyes is unexpectedly higher than the case of using it in the coupler dispersion system.

In case of using a combination of sensitizing dyes and dye developing agents, the sensitivity of a red-sensitive emulsion is usually greatly reduced by coaction of the sensitizing dyes and the dye developing agents (the theoretical reason of such phenomena is not yet known, but such a reduction in sensitivity may be due to a resensitization action caused by the dye developing agent), but by using the combination of the specific sensitizing dyes of this invention, the above-mentioned coaction can be reduced and a photographic emulsion having a high red-sensitivity is obtained.

The using ratio of the sensitizing dye represented by the general formula (I) mentioned above to the sensitizing dye represented by the general formula (II) is not restricted, but is preferably from 9:1 to 1:9. The ratio may be varied according to the purposes of using the combination.

The sensitizing dyes of this invention may be added to a photographic emulsion by any known method in the field of manufacturing photographic emulsions. Or dinarily, the sensitizing dyes may be incorporated in the photographic emulsion as a solution thereof in a solvent such as water, methanol, ethanol or methyl cellusolve. In this case, ultrasonic waves may be applied to the system to improve the resolution of the sensitizing dye in the solvent. The amount of sensitizing dye used may be varied according to the properties of silver halide emulsion and the desired results. In general, the optimum amount of the sensitizing dyes to obtain better sensitivity is 0.005 to 0.3 g. per gram molecule of silver halide.

For the silver halide emulsion used in this invention, a silver halide such as silver chloride, silver bromide, silver iodobromide, silver chlorobromide, and silver chloroiodo-bromide may be used, but the use of silver iodobromide is particularly effective.

In the present invention an ordinary gelatino silver halide emulsion is usually used but a part of the whole of the gelatin may be replaced by a resinous material or a cellulose derivative having no bad physical or photographic (e.g., sensitivity, fog, etc.) influence on lightsensitive material. 7

The photographic emulsion used in this invention may contain ordinary additives such as chemical densitizers, anti-foggants, stabilizers, hardening agents, wetting agents, plasticizers, development promotors, air fog preventing agents, etc., and is applied to a normal support such as a glass sheet, a cellulose derivative film, a synthetic resin film, a synthetic paper, a barytacoated paper, and a polyolefin-coated paper. Such additives and supports are standard and well known in this art.

The image-receiving element used in this invention comprises a support and an image-receiving layer having alkali permeability which is capable of dyeing the dye developing agent in an alkaline solution. That is to say, the image-receiving element comprises a support having coated thereon at least one image-receiving layer which is alkali permeable and can be dyed. The image-receiving layer contains a chemical suitable for mordanting or has the ability to fix the dye developing agent which has not been oxidized. Materials useful as the image-receiving layer and the construction of the image-receiving layer are described in Japanese Pat. Nos. 8274/1963, 8449/1963 and 29,756/1961 and US. Pat. Nos. 3,003,872; 3,043,689; 3,065,074; 3,148,061; 3,239,337; 3,353,056 and 3,362,819.

In some cases this dyeable layer comprises an alkali processing composition suitable to remain on the support separating the light-sensitive material.

The support for the image-receiving element is preferably a synthetic paper, a baryta-coated paper, and a polyolefin-coated paper but other supports such as a glass sheet, a cellulose derivative film, and a synthetic resin film may be used.

The following examples are intended to illustrate the present invention but not to limit it in any way.

EXAMPLE 1 5 g of a cyan dye developing agent, 5,8-dihydroxy- 1,4-bis[B-hydroquinonyl-a-methyl)ethylamino]anthraquinone was dissolved in a mixture of cc of N-nbutylacetanilide and cc of methanol and the solution obtained was dispersed by emulsification in 50 cc of a iuireentaqiieus gelatinsolu t ion containirimcof a 50 percent aqueous solution of sodium dodecylbenzene-sulfonate. After further adding to the emulsion 2cc of a 2 percent aqueous solution of 2-hydroxy-4,6- dichloro-S-triazine, water was added to the mixture to make the total volume 100cc. The mixture was coated tion containing lcc of a 5 percent aqueoussolution of sodium n-dodecylbenzenesulfonate to provide an emulsion. A silver iodobromide emulsion containing 5.3g of gelatin and 3.6 X 10 mols of silver per 100g of the emulsion and having added thereto 20g of the emulsion prepared above and a sensitizing dye, or a combination of sensitizing dyes as shown below, was coated onto the emulsion layer formed above to a dry thickness of 2.5 microns.

Thereafter, 100 cc of a 3 percent aqueous gelatin solution containing 1 cc of a 2 percent aqueous solution of 2-hydroxy-4,6-dichloro-S-triazine was coated onto the silver halide emulsion layer to a dry thickness of 0.8 microns.

The light-sensitive film thus obtained was exposed behind an optical wedge giving a continuously varying density, treated with an alkali processing agent having the composition below shown, and brought into contact with an image-receiving sheet having the construction shown below. Upon separating the image-receiving sheet from the light-sensitive film after two minutes, a positive dye transfer image of the dye developing agent having a lower density at the areas of high exposure and a higher density at the areas of low exposure was obtained on the image-receiving sheet. Composition of alkali processing agent:

mercaptotetrazole was coated on a baryta-coated paper to a dry thickness of 10 microns, the ratio by weight of said mordant to the mercapto compound being 18: 1. The reflection density of the dye image obtained on the image-receiving sheet was measured by means of a sensitometer and the exposure amount when the reflection density was 1.0 was checked, the results of whichare shown in Table 1 and Table 2.

The concentration of the sblution of the sensitizing dye was 1 X 10- mol/liter. The sensitivity is the relative value of the reciprocal of tlie'e'xposure amount necessary for giving D= 1.0.

** The results obtained by subjecting a sample prepared by coating a red-sensitive emulsion onto a tn'acetyl cellulose film and subjecting the same to black and white processing of the following formula. A red filter, Fuji Filter No. 7, was used.

on a triacetyl cellulose film to a dry thickness of 5 microns.

2.0g of 4-methylphenyl hydroquinone was dissolved in a mixture of 2cc of N-n-butyl-acetanilide and 4cc of ,ethyl acetate and the solution was dispersed by emulsification in 20cc of a 10 percent aqueous gelatin solu- Formula:

Metol 2g Anhydrous sodium sulfitc g Hydroquinone 5g Borax (H O) W er t s 1 1t (20C, 15 minutes) Table 2 Test No. Sensitizing dye Sensitivity (ml/100 g-emulsion) 145(2) 707 11 145(4) 100 12 145(8) 95.5 13 114(2) 72.5 14 1|-4(4) 77.5 15 11-4 77.5 16 |l5(2) I1-4(2) 219 17 ll5(4)11-4(2) 234 18 145(8) 114(4) 224 19 142(2) 79.4 20 1-12(4) 100 21 l-l2(8) 95.5 22 11-3(2) 89.1 23 1l-3(4) 103 24 11-31(8) 103 25 l-l2(2) 11-13(2) 240 26 1-12(4)11-l3(2) 257 27 142(4) 11-13(4) 252 (Note): Text numbers 10-15 and 19-24 are for comparison. The sensitivity was determined ax in Table l.

1 EXAMPLE 2 2 g ofa yellow dye developing agent, l-phenyl-3-N-nhexyl-carboxyamide-4-[p-( 2 ',5 '-dihydroxyphentyl phenylazo]-5-pyrazolone was dissolved in a mixture of 2cc of tricresyl phosphate and Sec of cyclohexanone with heating. The solution obtained was dispersed by emulsification in 50cc, of a 10 percent aqueous gelatin solution containing 2cc of a 5 percent aqueous solution of sodium n-dodecylbenzenesulfonate. After adding to the emulsion lcc of a 2 percent aqueous solution of 2- hydroxy-4,6'dichl0ro-S-triazine, water was added to the mixture to make the total volume 100cc. The emulsion thus prepared was coated on a triacetyl cellulose film to a dry thickness of 4 microns. A red-sensitive silver iodobromide emulsion containing 4.8g of gelatin and 3.5 X 10* mols of silver per 100g of the emulsion and having added thereto a sensitizing dye, or a combination of sensitizing dyes, shown in Table 3 was coated on the emulsion layer formed above to a dry thickness of 2 microns.

lg of 4-methylphenyl hydroquinone was dissolved in a mixture of 2cc of N,N-diethyllaurylamide and 4cc of ethyl acetate, and the solution was dispersed by emulsification in 20cc of a 10 percent aqueous gelatin solution containing lcc of a 5 percent aqueous solution of sodium n-dodecylbenzenesulfonate. After adding 2cc of a 2 percent aqueous solution of mucochloric acid, water was added to the emulsion to make the total volume 50cc. The emulsion thus prepared was coated on the silver halide emulsion layer prepared above to a dry thickness of 0.8 microns.

By processing the light-sensitive film as in Example 1, a transfer image of the dye developing agent was obtained on the image-receiving sheet. The exposure amount when the reflection density was 1.0 was measured, the results of which are shown in the following table.

(Note): Test numbers 28-33 are for comparison. The sensitivity was determined as in Table 1.

EXAMPLE 3.

3g of a magenta dye developing agent, 4-isopropoxy- 2-[p-(B-hydroquinonylethyl )phenylazo l -naphthol, was dissolved in a mixture of 6 cc of N,N-diethyl Iauryl amide and 10cc of ethyl acetate with heating and the solution was dispersed by emulsification in 50cc of a 10 percent aqueous gelatin solution containing 2cc of a 5 percent aqueous solution of sodium n-dodecylbenzene sulfonate. 200 of a 2 percent aqueous mucochloric acid solution was added to the emulsion and then water was added thereto to make the total volume 10000. The emulsion thus obtained was coated on a triacetyl film to a dry thickness of 5 microns.

A red-sensitive silver iodobromide emulsion containing 5.3g of gelatin and 3.7 X 10' mols of silver per g of emulsion having added thereto a sensitizing dye, or a combination of sensitizing dyes, shown in Table 4 was coated on the emulsion layer to a dry thickness of 2 microns.

1.3g of phenyl hydroquinone was dissolved in a mixture of 2cc. of N,N-diethyl lauryl amide and 4cc of ethyl acetate and the solution was dispersed by emulsification in 20cc of a 10 percent aqueous gelatin solution containing ice of a 5 percent aqueous solution of sodium n-dodecylbenzenesulfonate. After further adding 2cc ofa 2 percent mucochloric acid solution, water was added to the emulsion to make the total volume 50cc. The emulsion thus prepared was coated on the silver halide emulsion layer described above to a dry thickness of 0.8 microns.

By processing the light-sensitive film as in Example 1, a transfer image of the dye developing agent was obtained on the image-receiving sheet. The exposure amount when the reflection density was 1.0 was measured and the results are shown in Table 4.

Table 4 Test No. Sensitizing Dye Sensitivity Red Sensitivity of Only (ml/100g emulsion) Red-Sensitive Layer" Coupler No Coupler Added 37 l-4(2) 97.8 81.2 77.5 38 14(4) 100 100 100 39 l-4(8) 91.2 97.8 100 40 ll-6(2) 95.5 87.0 77.5 41 1l-6(4) 110 103 42 11-61(8) 105 105 105 43 1- (2) 11-6(2) 426 214 204 44 1-4(4)11-6(2) 436 224 219 45 1 4(4) 116(2) 417 219 219 (Note): Text numbers 37-42 are for comparison.

The sensitivity was determined as in Table 1. V g I n The results obtained by subjecting a sample prepared by coating aTed-sensitivemulsion on a triacetyl cellulose film to black and white development. A red filter, Fuji Filter No. 7, was

used.

In the above table, the use of no coupler in the case of the red-sensitive layer used the same red-sensitive emulsion in the example. In the case of using the coupler, an emulsified dispersion was prepared using 13g of l-(2,6-dichloro-4-methoxy)-3 [3ax-(2",4"-di tertiary-amylphenoxy)butylamido)-phenylureido]-5- pyrazolone in place of the magenta dye developing agent by the same procedure used to prepare the magenta dye developing agent-containing emulsion, and a red-sensitive silver halide emulsion containing 20g/1- g of the dispersion thus prepared was used.

EXAMPLE 4.

A multilayer color photographic film was prepared by coating the layers shown below successively onto a triacetyl cellulose film, shown in FIG. 2 by numeral 10. In FIG. 2 the layer structure of the color photographic film prepared as above is shown schematically.

1. Cyan dye developing agent layer (numeral 9 of FIG. 2):

10g of 1,4-bis(a-methyl-B-hydroquinonylethylamino)-anthraquinone was completely dissolved in a mixture of 1000 of N,N-diethyl laurylamide and 20cc of ethyl acetate by heating for 20 minutes at 60 C. The solution was dispersed by emulsification in 100cc of 10 percent aqueous gelatin solution containing Scc of a percent aqueous solution of sodium n-dodecylbenzenesulfonate. 4cc of a 2 percent aqueous solution of 2-hydroxy-4,6-dichloro-S-triazine was added to the emulsion, water was added to the emulsion to make the total volume 200cc, and the resultant mixture was coated on the triacetyl cellulose film to a' dry thickness of 6.0 microns.

2. Red-sensitive emulsion layer (8 in FIG. 2):

A red-sensitive silver iodobromide emulsion containing 5.8g of gelatin and 3.8 X mols of silver per 100g of the emulsion was coated on the emulsion layer 9 to a dry thickness of 5.2 microns.

3. Intermediate layer (7 in FIG. 2):

lg of phenyl hydroquinone was dissolved in a mixture of Ice of N,N-diethyl laurylamide and 4cc of cyclohexane and the solution was dispersed by emulsification in 30cc of a 10 percent aqueous gelatin solution containing 200 of a 5 percent aqueous sodium n-dodecylbenzene-sulfonate. 100cc of a 5 percent aqueous gelatin solution containing 30g of the emulsion was coated on the red-sensitive emulsion layer 8 to a dry thickness of 3.2 microns.

4. Magenta dye developing agent laye r(6 in FIG. 2):

7g of 4-ethoxy-2-[p-(B-hydroxyethyl )-phenylazol naphthol was dissolved in a mixture of 7cc of N,N- diethyl lauryl amide and 14cc of ethyl acetate and the solution was dispersed by emulsification in 100cc of a 10 percent aqueous gelatin solution containing 7cc of a 5 percent aqueous solution of sodium n-dodecylbenzenesulfonate. After further adding 4cc of a 2 percent aqueous solution by hydroxy-4,6-dichloro-S-triazine and also adding water to make the total volume 200cc, the resultant mixture was coated on the intermediate layer 7 to a dry thickness of 4.0 microns.

5. Green-sensitive emulsion layer (5 in FIG. 2):

A green-sensitive emulsion prepared by adding a sensitizing dye, or a combination of sensitizing dyes, as shown in Table 5 to a silver iodobromide emulsion containing 6.3g of gelatin and 3.5 X 10 mols per 100g of' 6. Intermediate layer (4 in FIG. 2):

The coating composition as in (3) was coated on the green-sensitive layer 5 to a dry thickness of 2.8 microns.

7. Yellow dye developing agent layer (3 in FIG. 2):

5g of 1-phenyl-3-N-n-butyl-carboxyamido-4-[p- (2,5 '-dihydroxyphenethyl)-phenylazo ]-5-pyrazolone was dissolved in a mixture of Sec of N,N-diethyl laurylamide and 14cc of ethyl acetate and the solution was dispersed by emulsification in cc of a 10 percent aqueous gelatin solution containing 500 of a 5 percent aqueous solution of sodium dodecylbenzene sulfonate. After adding 400 of a 2 percent aqueous solution of 2-hydroxy-4,6-dichloro-S-triazine and adding water to make the total volume 200cc the resultant mixture was coated on the intermediate layer 4 to a dry thickness of 3.4 microns.

8. Blue-sensitive emulsion layer (2 in FIG. 2):

A blue-sensitive silver iodobromide emulsion containing 5.3g of gelatin and 3.6 X 10 mols of silver per 100g of the emulsion was coated on layer 3 to a dry thickness of 2.5 microns.

9. Protective layer (1 in FIG. 2):

3g of phenyl hydroquinone was dissolved in a mixture of 3cc of N,N-diethyl laurylamide and 10cc of cyclohexane and the solution was dispersed by emulsification in 30cc of a 10 percent aqueous gelatine solution containing 2cc of a 5 percent aqueous solution of sodium n-dodecylbenzenesulfonate. 100cc of a 5 percent aqueous gelatin solution containing 30g of the emulsion prepared above was coated on the blue-sensitive emulsion layer 2 to a dry thickness of 1.5 microns.

The color photographic film thus prepared was first uniformly exposed to blue light and green light and then exposed to red light behind an optical wedge giving a continuously varying density. When the color photographic film thus exposed was treated with the alkali processing composition as in Example 1, brought intocontact for 2 minutes with the image-receiving sheet having the same structure as in Example 1, and the image-receiving sheet was separated therefrom,'a positive transfer image of the cyan dye developing agent having a dye density inversely proportional to the exposure amount was obtained on the image-receiving sheet. The density of the image-receiving sheet was measured by means of a densitometer and the exposure amount at a density of 1.0 was checked, the results of which are shown in the following table.

(Note): Test numbers 46-49 are for comparison The sensitivity was determined as in Table 1.

As is clear from Tables l-5 above, the light sensitive material containing the combination of sensitizing dyes according to the present invention has an excellent photographic effect as compared to known lightsenstive materials.

'carboxyalkyl group wherein a carboxyl group is attached to the alkyl sensitizing dye represented by the following general formula (I) and at least one sensitizing dye represented by the following general formula (ll):

wherein Z and Z,, which may be the same or different, represent each a non-metallic atomic group necessary for completing a series of benzothiazole nucleus or a series of benzoselenazole nucleus; R and R, represent each an alkyl group or a substituted alkyl-group; at least one of said R and R being a hydroxyalkyl group, a carboxyl group-containing alkyl group, or a sulfo group containing alkyl group; X represents an anion; and n is 1 or 2; said n being 1 when said dye forms an intramolecular saltand A I wherein Z and Z which may be the same or difi'erent; represent each a non-metallic atomic group necessary for completing a series of benzothiazole nucleus or a series of benzoselenazole nucleus; R and R have the, same significance as R and R of e general formula (I); at least one of said R and R being a hydroxyalkyl group, a carboxyl group-containing alkyl group, or a sulfo group-containing alkyl group; X represents an anion; and m has the same significance as n of the general formula (I).

2. A photographic emulsion as claimed in claim 1 wherein the substituted alkyl group is an acetoxy alkyl group, a hydroxyl alkyl group, a carboxy groupcontaining alkyl group, or a sulfo group-containing alkyl group.

3. A photographic emulsion as claimed in claim 1.

wherein the carboxy group-containing alkyl group is a group or a carboxy-substituted alkyl moiety through at least one alkoxy group, and wherein the sulfo group-containing alkyl group is a sulfoalkyl group, a hydroxy(sulfo) alkyl group, an acetoxy(sulfo) alkyl group, an alkoxy(sulfo) alkyl group, or a sulfo-.

substituted alkyl group wherein a sulfo group is attached to the alkyl moiety through at least one alkoxy group.

4. A photographic emulsion as claimed in claim 1 wherein the dye-combination is a member selected fr m h m ina iqaqL a.

5. A photographic emulsion as claimed in claim 1 wherein the dye developing agent is an azo dye developing agent or an anthraquinone dye developing agent,

said azo dye developing agent being a member selected from the group consisting of:

, l-phenyl-3-N-B-hydroxyethylcarbamido-4-[p-(2',

5 '-dihydroxyphenethyl )-phenylazo]-5-pyrazolone,

7. l-phenyl-3-N-n-hexylcarbamido-4-[p-(2, 5 -dihyd roxy-4 '-methyl-phenethyl )-phenylazo]-5 pyrazolone,

8. l-phenyl-3-N-n-hexylcarbamido-4-[ p-( 2 dihydroxyphenethyl )-phenylazo]-5-pyrazolone 9. l-phenyl-3-N-n-heptylcarbamido-4-[ p-( 2 5 -dihydroxyphenethyl )-phenylazo]-5-pyrazolone,

l0. l-phenyl-3-N-n-hcxylcarbamido-4-[p-(2, 5 fi ihu l zyiflqea wwitteaxlaflipyrazolone, ll. l-phenyl-3-trifluoromethyl-4-[p-(2,

dihydroxyphenethyl )-phenylazo 1-5 -pyrazolone, l2. l-phenyl-3-phenyl-4-[p-(2, 5 -dihydroxyphenethyl )-phenylazo]-5 -pyrazolone,

l3. l-phenyl-3-N-cyclohexylcarbamido-4-[ p-( 2 5 '-dihydroxyphenethyl )-phenylazo]-5-pyrazolone,

l4. l-phenyl-3-N-n-butyl-carbamido-4-[p-(2', 5 -dihydroxyphenethyl)-phenylazo]-5-pyrazolonc having the following formula:

Claims (124)

1. 2. A photographic emulsion as claimed in claim 1 wherein the substituted alkyl group is an acetoxy alkyl group, a hydroxyl alkyl group, a carboxy group-containing alkyl group, or a sulfo group-containing alkyl group.
2. 2. 1-phenyl-3-(N-2''-ethylhexylcarbamido)-4-( p-(2'', 5''-dihydroxyphenethyl)-phenylazo) 5-pyrazolone,
3. 3. 1-(p-N,N-diethylsulfoneamidophenyl)-3-N-n-butylcarbamido-4-)p-2'', 5''-dihydroxyphenethyl)-phenylazo)5-pyrazolone,
4. 3. A photographic emulsion as claimed in claim 1 wherein the carboxy group-containing alkyl group is a carboxyalkyl group or a carboxy-substituted alkyl group wherein a carboxyl group is attached to the alkyl moiety through at least one alkoxy group, and wherein the sulfo group-containing alkyl group is a sulfoalkyl group, a hydroxy(sulfo) alkyl group, an acetoxy(sulfo) alkyl group, an alkoxy(sulfo) alkyl group, or a sulfo-substituted alkyl group wherein a sulfo group is attached to the alkyl moiety through at least one alkoxy group.
5. 4. A photographic emulsion as claimed in claim 1 wherein the dye-combination is a member selected from the combination of
6. 4. 1-phenyl-3-N-n-hexylcarbamido-4-(p-2'', 5''-dihydroxyphenylpropyl)-phenylazo) -5-pyrazolone, 5 1-phenyl-3-trifluoromethyl-4-(p-(2''5''-dihydroxyphenylisobutyl)-phenylazo) -5-pyrazolone, 6 1-phenyl-3-N- Beta -hydroxyethylcarbamido-4-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo) -5-pyrazolone,
7. 5. A photographic emulsion as claimed in claim 1 wherein the dye developing agent is an azo dye developing agent or an anthraquinone dye developing agent, said azo dye developing agent being a member selected from the group consisting of:
8. 6. A photographic emulsion is claimed in claim 1 wherein the silver halide developing group of the dye developing agent is a hydroquinonyl group, o-hydroxy phenyl group or o- or p-amino-substituted hydroxyphenyl group.
9. 7. 1-phenyl-3-N-n-hexylcarbamido-4-(p-(2'', 5''-dihydroxy-4''-methyl-phenethyl)-phenylazo) -5-pyrazolone,
10. 7. A photographic emulsion as claimed in claim 1 wherein the dye developing agent is 4-isopropoxy-2-(p-( Beta -hydroquinonylethyl) phenylazo)-1-naphthol, 1-phenyl-3-N-n-hexylcarboxyamido-4-(p-(2'', 5''-dihydroxy phenethyl)phenylazo)-5-pyrazolon, or 5,8-dihydroxy-1,4-bis-(( Beta -hydroquinonyl-Alpha -methyl)-ethylamino)-anthraquinone.
11. 8. 1-phenyl-3-N-n-hexylcarbamido-4-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo) -5-pyrazolone,
12. 9. 1-phenyl-3-N-n-heptylcarbamido-4-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo) -5-pyrazolone,
13. 10. 1-phenyl-3-N-n-hexylcarbamido-4-(p-(2'', 5''-dihydroxy-4'' -chlorophenethyl)-phenylazo)-5-pyrazolone,
14. 11. 1-phenyl-3-trifluoromethyl-4-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo) -5-pyrazolone,
15. 12. 1-phenyl-3-phenyl-4-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-5-pyrazolone,
16. 13. 1-phenyl-3-N-cyclohexylcarbamido-4-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo) -5-pyrazolone,
17. 14. 1-phenyl-3-N-n-butyl-carbamido-4-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo) -5-pyrazolone having the following formula:
18. 15. 1-phenyl-3-carbethoxy-4-)p-(2'', 5''-dihydroxyphenethyl)-phenylazo) -5-pyrazolone,
19. 16. 1-phenyl-3-methyl-4-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-5-pyrazolone,
20. 17. 1-phenyl-3-amino-4-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo) -5-pyrazolone,
21. 18. 2-(p-(2'', 5''-dihydroxyphenethyl)-5-methylphenylazo)-4-methoxy-1-naphthol,
22. 19. 2-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-4-isobutoxy-1-naphthol,
23. 20. 2-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-4-N-methyl-N-phenylsulfoneamido-1 -naphthol,
24. 21. 2-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-4-methylsulfone-1-naphthol,
25. 22. 2-(m-(2'', 5''-dihydroxyphenethyl)-phenylazo)-4-n-propoxy-1-naphthol,
26. 23. 2-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-4-ethoxyethoxyethoxy-1-naphthol,
27. 24. 2-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-4-methylsulfide-1-naphthol,
28. 25. 2-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-4- Beta -chloroethoxy-1-naphthol,
29. 26. 2-(p''-(2'', 5''-dihydroxyphenethyl)- zeta -naphthylazo)-4-methoxy-1-naphthol,
30. 27. 2-(p-(2'', 5''-dihydroxyphenylisobutyl)-phenylazo)-4-methoxy-1-naphthol,
31. 28. 2-(p-(2'', 5''-dihydroxyphenylpropyl)-phenylazo)-4-isopropoxy-1-naphthol,
32. 29. 2-(p-(2'', 5''-dihydroxyphenylpropyl)-phenylazo)-4-n-propoxy-1-naphthol,
33. 30. 2-(p-(2'', 5''-dihydroxy-4''-methylphenethyl)-phenylazo)-4-N,N-diethylsulfoneamido-1 -naphthol,
34. 31. 2-(p-(2'', 5''-dihydroxy-3'', 4''-dimethylphenethyl)-phenylazo)-4-methoxy-1-naphthol,
35. 32. 2-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-4-acetyl-1-naphthol,
36. 33. 2-(p-(2'', 5''-dihydroxy-4''-methylphenethyl)-phenylazo)-4-methoxyl-1-naphthol,
37. 34. 2-(p-(2'', 5''-dihydroxy-4''-methylphenethyl)-phenylazo)-4-n-propoxy-1-naphthol,
38. 35. 2-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-4- Beta -hydroxyethoxy-1-naphthol,
39. 36. 2-(p-(2'', 5''-dihydroxy-3'', 4'', 6''-trimethylphenethyl)-phenylazo-4-methoxy-1-naphthol,
40. 37. 2-(p-(2'', 5''-dihydroxy-3''-methylphenethyl)-phenylazo)-4-n-propoxy-1-naphthol,
41. 38. 2-(p-3'', 4''-dihydroxyphenethyl)-phenylazo)-4-n-propoxy-1-naphthol,
42. 39. 2-(p-2'', 5''-dihydroxyphenethyl)-o-methoxyphenylazo)-4-N,N-dimethylsulfoneamido-1 -naphthol,
43. 40. 2-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-4-hexyloxy-1-naphthol,
44. 41. 2-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-4-cyclohexy-1-naphthol,
45. 42. 2-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-4-isopropoxy-1-naphthol,
46. 43. 2-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-4-n-propoxy-1-naphthol,
47. 44. 2-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-4-ethoxy-1-naphthol,
48. 45. 2(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-4-methoxy-1-naphthol,
49. 46. 2-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-4-acetamido-1-naphthol,
50. 47. 2-(p-(2'', 5''-dihydroxyphenethyl)phenylazo-4-amino-1-naphthol,
51. 48. 2-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)4sulfo-1-naphthol,
52. 49. 5-amino-8-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-1-naphthol,
53. 50. 5- Beta -hydroxyethylamino- 8-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo) -naphthol,
54. 51. 4-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-5-acetamido-1-naphthol,
55. 52. 1-(p-(2'', 5''-dihydroxyphenethyl)-o-methoxy-phenylazo)-8-acetamido-2-naphthol,
56. 53. 1-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)2-naphthol,
57. 54. 4-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-1-N-ethylaminonaphthol,
58. 55. 4-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-1-naphthylamine,
59. 56. 4-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-5-hydroxyacenaphthene,
60. 57. 8-amino-5-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-quinoline,
61. 58. 2, 5-dimethoxy-4-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-aniline,
62. 59. 2-formyl-4-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo) -phenol, and
63. 60. 4-(p-(2'', 5''-dihydroxyphenethyl)-phenylazo)-3-phenyl-isoxazolone-5, and said anthraquinone dye developing agent being a member selected from the group consisting of:
64. 61. 1,4-bis(p-(N-(hydroquinonylcarbamylmethyl)-amino) -phenylamino anthraquinone,
65. 62. 1,4-bis-hydroquinonylcarbamylmethylamino-anthraquinone,
66. 63. 1,4-bis-( Beta -methyl- Beta -hydroquinonylethylamino)-anthraquinone,
67. 64. 1,4-bis( Alpha -methyl- Beta -hydroquinonylethylamino)-5, 8-dihydroxy-anthraquinone,
68. 65. 1,4-bis( Alpha -methyl- Beta -hydroquinonylpropylamino)-5, 8-dihydroxy-anthraquinone,
69. 66. 1,4-bis-( Alpha -methyl- Beta -hydroquinonylpropylamino)-anthraquinone,
70. 67. 1,4-bis-hydroquinonylmethylamino-anthraquinone,
71. 68. 1,4-bis-( Alpha -methyl- Beta -hydroquinonylethylamino)-6, 7-dichloroanthraquinone,
72. 69. 1,4-bis-( Alpha -methyl-2'', 5''-dihydroxybenzylamino)-anthraquinone
73. 70. 1,4-bis-( Alpha -methyl- Beta -hydroquinonyethylamino)-5,8-bis-benzene-sulfoneamidoanthraquinone,
74. 71. 1,4-bis-( Alpha -methyl- Beta -hydroquinonylethylamino)-5-hydroxy-8-amino-anthraquinone,
75. 72. 1,4-bis-( Alpha -hydroquinonyl-ethylamino)-anthraquinone,
76. 73. 1,4-bis-( Beta -(3'', 4''-Dihydroxyphenyl)-ethylamino)-5,8-dihydroxy-phenyl)-ethylamino -dihydroxyanthraquinone,
77. 74. 1,4-bis-( Beta -(3'', 5''-dihydroxyphenyl)-ethylamino)-anthraquinone,
78. 75. 1,4-bis-( Alpha -ethyl- Beta -hydroquinonylethylamino)-anthraquinone,
79. 76. 1,4-bis-(2'', 5''-dihydroxyanilino)-anthraquinone,
80. 77. 1,4-bis- Alpha -(homogentisamido)-ethylamino-anthraquinone,
81. 78. 1,4-bis-homogentisamido-anthraquinone,
82. 79. 1,4-bis-(2'', 5''-dihydroxyanilino)-anthraquinone,
83. 80. 1,4-bis-( Beta -(2'', 5''-dihydroxyphenyl)-propylamino)-anthraquinone,
84. 81. 1,4-bis-(1'', 5''-bis-(2'''', 5''''-dihydroxyphenyl)-3''-pentyl)-aminoanthraquinone,
85. 82. N-monobenzoyl-1,4-bis( Beta -(3'',4''-dihydroxyphenyl)-ethylamino)-anthraquinone,
86. 83. N-monobenzoyl-1,4-bis( Beta (2'', 5''-dihydroxyphenyl)-ethylamino) -anthraquinone,
87. 84. 1,4-diamino-N- Beta -(2'', 5''-dihydroxyphenyl- Alpha -methyl-ethyl)-2,3-anthraquinone-dicarboxyamide,
88. 85. 1-amino-4-hydroxy-N- Beta -(2'', 5''-dihydroxyphenyl- Beta -methylethyl)-2,3-anthraquinone-dicarboxyimide,
89. 86. 1-hydroxy-4-(1'', 5''-bis-(25''''-dihydroxyphenyl)-3''''-pentyl) -amino-anthraquinone,
90. 87. 1amino-4-anilino-2-hydroquinonylsulfamyl anthraquinone,
91. 88. 1-aminoethylamino-4-hydroquinonylcarbamylmethylaminoethylamino -anthraquinone,
92. 89. 1-sodium-amino-4-(p-(N-hydroquinonylcarbamylmethylamino)-phenylamino)-2 -anthraquinonesulfonate,
93. 90. 1-( Alpha -hydroxymethyl-propylamino)-4-( Alpha -methyl-Beta -hydroquinonyl-ethylamino)-anthraquinone,
94. 91. 1-( Alpha -hydrozymethyl-propylamino)-4-( Alpha -methyl-Beta -hydroquinonyl-methylamino)-5,8-dihydroxyanthraquinone,
95. 92. 1-hydroxy-4-(2'', 5''-dihydroxyanilino)-anthraquinone,
96. 93. 1-hydroxy-4-( Alpha -methyl-hydroquinonylethylamino)-anthraquinone,
97. 94. 1-( Alpha -methyl- Beta -hydroquinonylethylamIno)-4-( Alpha -ethyl- Beta -hydroquinonylethylamino)-anthraquinone,
98. 95. 1-( Alpha -methyl- Beta -hydroquinonylethylamino)-4-( Alpha -ethyl- Beta -hydroquinonyl-ethylamino)-5,8-dihydroxyanthraquinone,
99. 96. 1-( Alpha -hydroxymethyl-propylamino)-4- Alpha -methyl-Beta -hydroquinonyl-ethylamino)-5-hydroxyanthraquinone,
100. 97. 1-( Alpha -hydroxymethylpropylamino)-4-( Beta -(4''-methyl-2'', 5''-dihydroxyphenyl)- Alpha -methyl-ethylaminoe))-anthraquinone,
101. 98. 1-ethylamino-4-( Beta -(3'', 4''-dihydroxyphenyl)-ethylamino) -anthraquinone,
102. 99. 1-chloro-4-( Beta -hydroquinonylethylamino)-anthraquinone,
103. 100. 1-hydroxy-4-( Beta -(3'', 4''-dihydroxyphenyl)-ethylamino) -anthraquinone,
104. 101. 1-( Beta -hydroxyethylamino)-4-( Beta -hydroquinonylethylamino)-anthraquinone,
105. 102. 1-( Beta -hydroxyethylamino)-4-( Alpha -methyl- Beta -hydroquinonylethylamino)-5,8-dihydroxyanthraquinone,
106. 103. 1-methylamino-4-( Beta -hydroquinonylethylamino)-anthraquinone,
107. 104. 1- Beta -hydroxyethylamino-4-( Alpha -methyl- Beta -hydroquinonyl-ethylamino)-anthraquinone,
108. 105. 1- Beta -aminoethylamino-4- Beta -(homogentisamido)-ethylaminoanthraquinone,
109. 106. 1,5-bis-hydroquinonylmethylamino-anthraquinone,
110. 107. 1,5-bis-( Beta -(3'', 4''-dihydroxyphenyl)-ethylamino)-anthraquinone,
111. 108. 1,5-bis-( Beta ''-hydroquinonylethylamino)-anthraquinone,
112. 109. 1,5-bis-( Alpha -methyl- Beta -hydroquinonyl-ethylamino)-anthraquinone,
113. 110. 1,5-bis-homogentisamido-4,8-dihydroxy-anthraquinone,
114. 111. 1,5-bis-homogentisamido-anthraquinone,
115. 112. 1,5-bis(N-methyl-homogentisamido)-5,8-dimethylamino-anthraquinone,
116. 113. 1-chloro-5-( Beta -hydroquinonylethylamino)-anthraquinone,
117. 114. 1-( Beta -(3'', 4''-dihydroxyphenyl)-ethylamino)-anthraquinoen,
118. 115. 1,8-bis-( Beta -(3'', 4''-dihydroxyphenyl)-ethylamino)-anthraquinone,
119. 116. 1,8-bis-( Beta -hydroquinonylethylamino)-anthraquinone,
120. 117. 4,8-bis-(2'', 5''-dihydroxyanilino)-anthraquinone,
121. 118. 4-(2'', 5''-dihydroxyanilino)-8-chloro-anthraquinone,
122. 119. 1-(p-( Beta -hydroquinonylethyl)-phenylamino)-anthraquinone,
123. 120. 1-( Beta -(3'', 4''-dihydroxyphenyl)-ethylamino)-anthraquinone,
124. 121. 1-homogentisamido-5-amino-4,8-dihydroxyanthraquinone.

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