US3552967A - Color developer composition - Google Patents

Abstract

A COLOR DEVELOPER COMPOSITION CONTAINING A COLOR DEVELOPING AGENT, A PRINCIPAL COUPLER AND, AD A REGULAROTRY COUPLER, AT LEAST ONE COMPOUND SELECTED FROM THE GROUP CONSISTING OF 1 - NAPHTHOL, 2,4 - DICHLORO 1 - NAPHTHOL, 2,4DIBROMO - 1 - NAPHTHOL, 2,4 - DICHLORO - 5 - (P - TOLUENESULFONAMIDE) - 1 - NAPTHOL AND 1,5 - DIHYDROXY - 2.6 - DIBROMONAPHTHALENE.

Description

United States Patent 3,552,967 COLOR DEVELOPER COMPOSITION Hikoharu Hara, Yoshio Yamamuro, and Motozumi Asakawa, Kanagawa, Japan, assignors to Fuji Shashin Film Kabushiki Kaisha, Kanagawa, Japan No Drawing. Filed Nov. 16, 1967, Ser. No. 683,490 Claims priority, application Japan, Nov. 16, 1966, il/75,358 Int. Cl. G03c 7/30 US. C]. 96-55 2 Claims ABSTRACT OF THE DISCLOSURE A color developer composition containing a color developing agent, a principal coupler and, as a regulatory coupler, at least one compound selected from the group consisting of 1 naphthol, 2,4 dichloro l naphthol, 2,4- dibromo 1 naphthol, 2,4 dichloro (p toluenesulfonamide) 1 naphthol and 1,5 dihydroxy 2,6 dibromonaphthalene.

BACKGROUND OF THE INVENTION (1) Field of the invention The present invention relates to a color developer composition containing difIusion-type couplers, and more particularly to a color developer composition containing a compound capable of increasing the color density of other layers without having bad effects on the color density of the layer to be developed therewith.

(2) Description of the prior art Generally, a multilayer photographic light-sensitive color material comprises a support, three different lightsensitive layers coated thereon, one after another, and subsidiary layers. For example, the photographic material is composed of a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a yellow filtering layer and a blue-sensitive silver halide emulsion layer superimposed on a support in order. In some cases, other emulsion layers, interlayers, and a protecting layer may be provided on the photographic material for other particular objects. Furthermore, in a photographic printing material, the yellow filtering layer may not be used or the order of the emulsion layers may be varied.

Usually, a coupler-containing color developer contains a developing agent and a coupler for cyan-, magenta-, or yellow-coloration.

However, in cases Where a color hue of a dye formed by coupling has various defects and the color density of the dye is insuificient, two or more couplers may be used with the aforesaid coupler for the purpose of overcoming the defects. For example, in case the principal coupler has defects of hue and color density in various required characteristics, another coupler (hereinafter this coupler is called a regulatory coupler) capable of increasing the hue of the layer developed therewith and the color density without injuring photographic characteristics and the characteristics of the principal coupler is used with the principal coupler.

We have done research into various couplers which are reacted with p-phenylenediamine or its derivative to pro duce similar dyes. Consequently, we have discovered the effective combination of principal coupler and a small amount of a regulatory coupler so that photographic properties, particularly coloring properties, of other layers can be increased without having any bad effect on the layer to be developed therewith.

3,552,967 Patented Jan. 5, 1971 SUMMARY OF THE INVENTION The present invention relates to a colar developer composition Which contains p-phenylenediamine or its derivative as a color developing agent, 1-hydroxy-N-[2-(o-propionamidephenyhethyl] 2 naphthoamide or 1 hydroxy- N [2 (o acetoamidephenyl)ethyl] 2 naphthoamide, as a principal coupler, and, as a regulatory coupler, at least one compound of the group l-naphthol, 2,4-dichloro- 1 naphthol, 2,4 dibromo 1 naphthol, 2,4 dichloro- S-(p toluenesulfonamide) l naphthol, and 1,5 dihydroxy-2,6-dibromonaphthalene.

For example, when a photographic material is treated with a developer containing as a coupler the compound having the following Formula A, only the color density of the cyan dye image together with an additive amount of the compound is increased, but the color densities of the magenta and the yellow dye images in other layers are not increased. However, when the photographic material is treated with a developer containing, as a principal color developing agent, coupler (A), and, as a regulatory coupler, coupler (B) represented by the following formula, in an amount of 10% by weight of the coupler (A), the color densities of not only the cyan dye images, but also the magenta and yellow dye images, in other layers, are increased.

In this case, the former is increased in relation to the amount of the coupler (A), and the latter is increased, but not in relation to the amount of the coupler (A).

NH0 0 CHZCH3 DETAILED DESCRIPTION OF THE INVENTION The present invention is explained more particularly by referring to examples, but the first object of the present invention is to improve photographic properties, particularly the coloring property in other layers, which is different from the object of using the above mixture, and further, a second object is to improve the photographic properties of its own layer.

Therefore, insofar as a serious obstacle, on the basis of using this solution, does not arise in its own color developing composition and in its photographic properties, the composite characteristics are promoted, even if some sacrifice is called for. In other words, even if an improvement is nullified in its own layer, the composite feature is promoted in the case that the primary effect, namely, the action of promoting the coloring properties in the other layers is remarkably improved.

In the case of developing a photographic color film in a coupler-containing developer, at least three dye-forming developments are required, as shown in the following examples. The order of the developments is (1) a cyan development for the lower most silver halide emulsion layer, (2) a yellow development for the upper most emulsion layer, and (3) a magenta development for the intermediate emulsion layer.

So, the developing composition of the present invention is limited to the cyan developing composition and yellow developing composition. But, an effect of the said developing solution by the present invention can not be expected for magenta developing.

The regulatory coupler to be used together with the principal coupler in this invention forms a dye of the type of said principal coupler by coupling with the oxidation product of the color developing agent, e.g., it forms a yellow dye in the case where the principal coupler forms a yellow dye. Also, the regulatory coupler may have at the coupling position a substituent capable of coupling by the liberation thereof.

Further, the regulatory coupler in this invention includes one capable of forming a colorless compound by coupling with the oxidation product of the color developing agent without liberating the substituent at the coupling position thereof as described in British Pat. No. 861,138.

Principal color developing agents in the color developer of the present invention comprise in general p-phenylenediamine derivatives, e.g., p-phenylenediarnine hydrochloride, N,N- diethyl-p-phenylenediamine sulfite, N,N-diethyl- 3-methy1-p-phenylenediamine hydrochloride, 4-amino-3- methyl-N-ethyl-methanesulfonamide ethyl aniline sulfate, 4-amino-3-methyl-N-ethyl-N-hydroxyethyl aniline sulfate, N-ethyl-N-hydroxyethyl-p-phenylenediamine sulfate, or the like.

An employable concentration of the regulatory coupler of the present invention depends variously upon color developability and hue of the principal coupler and generally is selected in the range of 0.05 to 1.0 grams/liter. But, the present invention is not limited by this disclosure.

Further, the effect of the present invention is not lost by the kind of gelatino silver halide emulsion, other additions to the emulsion besides the coupler, and the sensitizers or sensitizing processes of silver halide emulsion.

EXAMPLE I A color photographic film having multi-layers coated on a film support, in the order, (1) a gelatino-silver iodobromide emulsion having red sensitivity, (2) a gelatinosilver iodo-bromide emulsion having green sensitivity, (3) a yellow filter layer of silver colloid having absorbability of blue light, and (4) a gelatino-silver iodo-bromide emulsion having blue sensitivity, was exposed to an actinometer and was treated by the following procedures, in order:

Temperature,

Treating steps C. Time The first silver-forming development 24 5 min. Wash 24 2 min. Reversal exposure (Red light) 200 CMSJ Cyan dye-forming developmen 24 5 min.

as 24 2 min. Reversal exposure (Blue light). 2,000 CMS. Yellow dye-forming development 24 5 min.

ash 24 2 min. The second silver-forming development 24 2 min.

as 24 2 min. Reversal exposure (White light) 2,000 CMSJ Magenta dye-forming development 24 5 min. Wash 24 8 min. Silver bleach 24 2 min. Rinse 24 2 min. Eixing.-. 24 2 min. Wash. 24 2 min.

1 From the back surface of the film. 2 Candle meter second. 3 From the top surface of the film.

Compositions of the treating'solutions are specified below:

Amount The first and second silver-forming developers: (gms) N-methyl-p-aminophenol sulfate 2.0 Sodium sulfite anhydride 90.0 Hydroquinone 8.0 Sodium carbonate (mono-hydrate) 52.5 Potassium bromide 5.0

Potassium thiocyanate 1.0 Water to make 1,000 cc. Cyan dye-forming developer:

Sodium sulfite anhydride 5.0

2-amino-S-diethylaminotoluene hydrochloride 0.6 Sodium carbonate (mono-hydrate) 15.0

Potassium bromide 0.5 Potassium iodide (0.1% of aqueous solution, 5 cc. 1-hydroxy-N-[2-(o-propionamide phenyl) ethyl] -2-naphthoamide x Sodium hydroxide 2.0 MonobenZyl-p-aminophenol hydrochloride 0.2 Methyl alcohol, 4 cc. Water to make 1,000 cc. Yellow dye-forming developer:

Sodium sulfite anhydride 5.0 N,N-diethyl-p-phenylenediamine sulfite 2.5 Potassium bromide 1.0 Potassium iodide (0.1% of aqueous solution),

5 .0 cc. 1-w-benzoyl-4- (p-toluene sulfonamide acetanilide 1.2 Sodium hydroxide 2.5 Water to make 1,000 cc. Magenta dye-forming developer:

Sodium sulfite anhydride 5.0 2-amino-S-diethylaminotoluene hydrochloride 2.0 Potassium bromide 0.8 1-phenyl-3-(m-nitrobenzoylamino)-5- pyrazolone a 1 .4 Sodium hydroxide 2.0 n-Butylamine, 5.0 cc. Water to make 1,000 cc. Bleaching solution:

Potassium ferricyanide Potassium bromide 10 Borax 2 Boric acid 1 Water to make 1,000 cc. Fixing solution:

Sodium thiosulfate anhydride Sodium sulfite anhydride 10 Water to make 1,000 cc.

In external type color development, as shown above, regulatory couplers were added in the cyan dye-forming developer as follows:

Amount of addition Experiment N0.

Coupler or yellow layer, the effect of the present invention is So, gamma values and maximum densities of layers larger. were improved respectively.

Difierence Difference Difference Experiment Cyan from the Magenta from the Yellow from the N 0. density type density type density typo EXAMPLE II {Aaraognt I 0 8. l 1V0 The same film as in Example I was exposed by the Experiment NO Coupler (gm same process of Example I and treated with the color developers in which only the coupler of the cyan color 5 8 developer is changed as in the fol owing table: "m 1 3 0 1.5 {E 0. 27 4 .40 1.5 Amount 1F 0.30 of additive 5 "{Q 5 Experiment No. Coupler (g./l.) (1 0.36

Coupler B.The same as that in Example I. Coupler C.l-hydroxy-N-[2-(o-acetamidepheuyl)ethyll2-naphthoamide.

The results obtained here were similar to those in Example I and the color densities of yellow and magenta in Experiment Nos. 2 to 4, in comparison with that in Experiment No. 1, were increased. Those increased effects are arranged in a sequence of No. 4 (highest), No. 3, No. 2 and No. 1 (lowest).

EXAMPLE III Coupler C.The same as that in Example II.

Coupler D.1-naphtho1.

Coupler E .2,4 dibrom-1-naphthol.

Coupler F.1,5-dihydroxy-2,fi-dibromnaphthalene.

Coupler G.2,4-dichloro-5-(p-toluenesulfonaniide)-1-naphthol.

What is claimed is:

1. A color developer composition containing a color developing agent selected from the group consisting of p-phenylenediamine and its derivatives, a principal coupler selected from the group consisting of 1-hydroxy-N- [2- (o-propionamidephenyl ethyl] -2-naphthoamide, and l-hydroxy-N-[2-(o -acetoamidephenyl)ethyl] 2-naphthoamide and, as a regulatory coupler, at least one compound selected from the group consisting of l-naphthol, 2,4-dichloro-l-naphthol, 2,4-dib'rornol-naphthol, 2,4-dichloro-S-(p-toluenesulfonamide)-1-naphthol and 1,5-dihydroxy-2,6-dibromonaphthalene.

2. The color developer composition as claimed in claim 1 wherein said p-phenylenediamine derivative is selected from the group consisting of p-phenylenediarnine hydrochloride, N,N-diethyl-p-phenylenediamine sulfite, N,N- diethyl-3-methyl-p-phenylenediamine hydrochloride, 4- amino-3-rnethyl-N-ethyl-methanesulfonamide ethyl aniline sulfate, 4 amino 3 methyl-N-ethyl-N-hydroxyethyl aniline sulfate, and N-ethyl N-hydroxyethyl-p-phenylenediamine sulfate.

References Cited UNITED STATES PATENTS 2,197,311 4/1940 Merckx et al. 9655 2,772,161 11/1956 Loria et a1 96100X 2,921,851 1/19'60 Hoffstadt 9655 2,998,314 8/1961 Puschel 9655 3,165,407 1/ 196 5 McCarthy 96--55X 3,174,862 3/1965 Puschel 96-55X 3,369,895 2/1968 Loria et al. 9655 3,418,121 12/1968 Yoshida et al. 9655 3,458,315 7/1969 Loria 9655X 3,447,923 6/1969 Jaeken 9655 FOREIGN PATENTS 861.138 2/1961 Great Britain 9655 1,183,746 9/1957 France 9655 WILLIAM D. MARTIN, Primary Examiner H. J. GWINNELL, Assistant Examiner