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Publication numberUS3520690 A
Publication typeGrant
Publication dateJul 14, 1970
Filing dateJun 24, 1966
Priority dateJun 25, 1965
Also published asDE1547847A1
Publication numberUS 3520690 A, US 3520690A, US-A-3520690, US3520690 A, US3520690A
InventorsIwano Haruhiko, Nagae Tadashi
Original AssigneeFuji Photo Film Co Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Process for controlling dye gradation in color photographic element
US 3520690 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent 01 ice 3,520,690 Patented July 14, 1970 ABSTRACT OF THE DISCLOSURE A process for controlling the gradation of dye images in color photographic processing employing a developer containing p-phenylencdiamine or a derivative thereof, which comprises processing with a developer additionally incorporating at least one member selected from the group consisting of compounds represented by the general formulas COOM wherein X represents a member selected from the group consisting of H, OH, and NH and M represents a member selected from the group consisting of H, Na, K, NH other mono-valent positive atoms and mono-valent atomic groups.

and

The present invention relates to a process for processing colorv photographic elements and more particularly to an improved processing method in color photography for controlling the gradation of dye images and the graininess thereof.

A conventionally employed process for processing the usual silver halide, color photographic elements, after exposure, for obtaining color images includes the step of processing the exposed color photographic element in an alkaline solution. The solution contains a primary aromatic amine type color developer in the presence of a coupler and forms a color image by the reaction of the coupler and the thus formed oxidation product of the color developer.

However, on comparison with a black and white photographic image obtained by applying the usual black and white development process, the density of the color photographic image obtained by the abovementioned color development is generally extremely high, by the high extinction coefiicient of the dye, and the gradation thereof is generally hard. Accordingly the phenomenon of hardening in gradation of the color image, incidental to color development for color photographic elements, must be settled.

The simplest method for overcoming such a difficulty is to reduce the quantity of silver halide in the emulsion layer of the color photographic element to control the gradation to a normal state. Therefore, the content to silver halide in a color photographic element is usually markedly less than that which is practical and general in a black and white photographic element. However, it is not preferable to reduce the quantity of silver halide, since there are substantial drawbacks, namely, graininess becomes coarser and resolving power becomes lower.

In order to overcome such drawbacks, the grain size of the silver halide may be fined. However, the fining of the silver halide particle is inevitably accompanied by a reduction in sensitivity, which makes the employment of such a process dilficult except for a specific purpose.

Therefore, for obtaining a color image in which the graininess and resolving power are generally good and the graduation is not too hard, a process is desired wherein the gradation of the color image is softened without reducing the quantity of silver halide.

For satisfying this purpose, a process has already been provided in which the processing is conducted while incorporating a compound having a gradation controlling action, as will be shown below, in the color developer or in the light-sensitive emulsion layer.

As examples of compounds to be incorporated in the color developer, there are described a series of compounds, such as 1-arnino-8-naphthol-3,6-disulfonic acid in US. Pat. 2,689,793. However, these compounds have the drawback that the rate of reaction thereof with the oxidation product of the developer is fast and the control range of gradation is narrow.

Further, compounds, such as 2,6-dihydroxy isonicotinic acid, described in US. Pat. 2,741,832, are less troubled by the foregoing drawback and have excellent gradation controlling ability, but they are not yet available in sufiicient quantity.

As examples of compounds to be added to the color developer or the light-sensitive emulsion layer, there are described {3 naphthols in German Pats. 1,123,558 and 1,099,350, but they are also not available in sufiicient quantity.

Furthermore, there is reported in German Pat. 1,155,- 675 that compounds having a substituted-type active methylene are effective for such a purpose.

A main object of this invention is to provide a novel gradation controlling compound having better properties than known gradation controlling compounds.

The inventors have found that the compounds shown by the following general structural formulas have not only very excellent effects in the control of gradation, the improvement of graininess and the increase of resolving power, but also are capable of enlarging effectively the range of gradation control, which contribute to the improvement of the qualities of photographic dye images more effectively than conventional gradation controlling compounds.

The compounds used in this invention are represented by the following general formulas:

COOM

H. OH

I fi coon 3 wherein X represents H, OH or NH and M represents H, Na, K, NH 01' other mono-valent positive atom or atomic group.

Typical examples of the compounds shown by the Formula I are as follows:

(1) Salicylic acid (2.) Sodium 4-aminosalicylate COONa (3) 4-oxysalicyclic acid COOH Typical examples of the compounds shown by the Formula II are as follows:

(4) l-hydroxy-Z-naphthoic acid (5) Sodium l-hydroxy-6-amino-2-naphthoate GOONa The optimum amount in which the compound should be used as an additive is influenced by the kind and the concentration of the coupler to be employed, the kind of developing agent, the pH of the processing solution, and the extent of gradation to be controlled, but, in general, the amount of 0.1-3 g. of the compound per one liter of color developer is applicable.

An amount of the compound less than the above range gives only a poor effect and an amount more than this range tends to reduce the color density too much. For obtaining the usual gradation an amount of 0.8-1.2 g./ liter is preferable.

The compound of this invention may be applicable for processing a color photographic film or a color photographic printing paper of the type wherein a coupler is incorporated in the emulsion layer of the color photographic element, as well as a color photographic film of the type in which a coupler is incorporated in a processing solution.

The invention will be explained more practically by the following examples, but it should be understood that the invention is not limited to them by any means.

EXAMPLE 1 To a film support of cellulose acetate were applied a red-sensitive gelatino silver bromo-iodide emulsion, a green-sensitive gelatino bromo-iodide emulsion, a yellow filter layer composed of colloidal silver capable of absorbing blue light, and a blue-sensitive gelatino silver bromoiodide emulsion, successively, in this order to provide a multi-layer color photographic film, which was exposed by means of a sensitometer and subjected to the following processings:

First and second developers: I I N-Methy1-p-aminophen0l /2 sulfate-2.0 g.

Sodium sulfite90.0 g. Hydroquinone8.0 g. Sodium carbonate (mono-hydrate)52.5 g. Potassium bromide5 .0 g. Potassium thiocyanatel.0 g. Water to make 1 liter.

Cyan color developer:

Sodium sulfite5.0 g. 4-amino-3-methyl-N,N-diethylaniline hydrochloride0.6 g.

Potassium bromide-0.25 g. Sodium carbonate (monohydrate)-15.0 g. Potassium iodide (0.1% aq. soln.)--2 ml. 1.5-dihydroxy-2,6-dibromonaphthalene1.2 g. Sodium hydroxide2.0 g. Water to make 1 liter.

Yellow color developer:

Sodium sulfiteS.0 g. Y

4-amino-N,N-diethylaniline hydrochloride-25 g.

Potassium bromide-4.0 g.

Potassium iodide (0.1% aq. soln.)-5 ml.-

1-benzoy1-4-(p-toluenesulfoamido) acetanilide1.2 g.

Sodium hydroxide-2.0 g.

Water to make 1 liter.

Magenta color developer:

Sodium sulfite5.0 g.

4-amino-3-methyl-N,N-diethylaniline hydrochloride-2.0 g.

Potassium bromide-O.2 g. I I

l-phenyl-3-(m-nitrobenzoylamino)-5- pyrazolone-1.4 g.

Sodium hydroxide2.5 g.

n-Butylamine5 ml.

Water to make 1 liter.

Bleaching solution:

Potassium ferricyanide-AOO g. Potassium bromide-l0 g. Borax-2 g. r Boric oxide-l g. 1 J Water to make 1 liter. 1

Fixing solution:

Sodium thiosulfate g. Sodium sulfite-lO g. Water to make 1 liter.

The above-mentioned standard processin gs were conducted while adding the compounds of this invention to 1 the magenta color developer as shown in the following,

table in accordance with the process of this invention and the results are shown in the same table.

TABLE 1 Relative Magenta sensitivity Addition develop- Increase of magenta Compounds added in amount ing time Gradain coupling magenta color developer (g./l.) (min.) tion latitude layer None 5 1. 76 0. 84 Compound (1) 0. 7 7 l. 55 +0. 15 1. 09 Compound (2) 0.8 7 1. 60 +0. 08 0. 99 Compound (3) 1. 0 7 1. 64 +0. 11 1. 04 Compound (4) 0. 6 7 1. 63 +0. 12 1. Citrazic acid 0. 4. 7 1. 65 +0. 0. 99

In the table, the gradation is shown by the average gradient of the line passing through the points on the characteristic curve corresponding to density 0.4 and density 2.0 and the increase in latitude is shown by the increase in relative value of the difference between the exponential exposure amounts corresponding to density 0.3 and density 2.5 to the value of the standard development. Further, the addition amount is the optimum amount.

As shown in Table 1, the gradation controlling effect by the addition of the compounds in this invention is far better than that of the known additive citrazic acid.

More conveniently, by the addition of the compounds of this invention, the sensitivity of the magenta coupling layer is increased, the formation of undesirable coupling which results in color contamination is prevented and excellent color reproduction can be obtained.

EXAMPLE 2 The multi-color photographic film, as in Example 1, was processed after exposure as in Example 1, but in this case the composition of the magenta developer was varied as follows:

Formula A Formula B Composition A further added with 1 g./liter of sodium 4-amino-salicyalate. The results are shown in the following table.

TAB LE 2 Relative sensitivity of magenta Formula of magenta Processing Increase in coupling developer time (min) Gradation latitude layer Formula A 5 1. 83 0 0.85 Formula B 7 l. 65 +0.20 1. 00

As shown in the above table, by the addition of sodium 4-amino-salicyate, the gradation of the magenta color image can be softened, the latitude can be enlarged and high sensitivity is obtained.

EXAMPLE 3 A gelatino silver bromo-iodide emulsion containing a cyan coupler was applied to a film of cellulose acetate Color development6 min. at 24 C.

Wash-30 sec. First fixation-4 min. Wash-5 min.

Silver-bleach4 min. Rinse5 min.

Second fixation-4 min. Wash5 min.

The bath formula in the above processings were as follows:

Color developer:

Benzyl alcohol-31 ml.

Sodium sulfite-2 g.

3-methyl-4-amino-N,ethyl N,methanesulfonamidoethylaniline sulfate-1.5 g.

Sodium carbonate (mono-hydra-te)60 g.

Potassium bromide-l g.

Sodium hydroxide (10% )1 ml.

Water to make 1 liter.

Formula (A) having added to it 1 g./liter of sodium 4-oxysalicylate.

Formula (A) having added to it 0.8 g./liter of sodium 4-aminosalicylate.

Formula (A) having added to it 1 g./liter of l-hydroxy-2-naphthoic acid.

Formula (A) having added to it 0.8 g./ liter of sodium l-hydroxy-6-amino-2-naphthoate.

After processing, the cyan color density of the thus processed film was measured by means of a semidiifuse type densitometer, the results of which are shown in Table 3, wherein the gamma value is shown by the curve.

8 Formula (C) Formula A having added to it 1 g./liter of l-hydroxynaphthoic acid.

TABLE 3 F l I P 1 mm Rflatlvefsensl- Bleaching solutioni t t n 0 0 1 1 tielei gi recess 5111111.? coi ipl i n g 1i? Gamma'value Potassium fen Wanda-100 Sodium acetate-40 g. 8 g: ,2 51 gg Glacial acetic acid--2Q ml. 2. 06 0. 85 Potassium bromide-30 g. B 3:82 333.- Water to make 1 liter.

3 Fixing solution: I As shown from Table 3, by the addition ofjjthe com-'f Sodium thiosulfate. :150 g. pounds used in this invention, the gamma value can-be Sodium acetate-70g. considerably reduced, and the latitude can be enlarged Sodium sulfite10 g. as well. m .Potassium alurn-2 0 g.

EXAMPLE 4 Water to make; .liter. a v I r I To a film of cellulose acetate were appliedared se I I: a result 'of ineasurement after processing it was tive silver bromo-iodide emulsion containing-.21 cyan couobserved that the gradation was improved, the latitude pler, a green-sensitive silver bromo-iodide emulsion .co nenlarged and the colorcontamination was reduced taining a magenta-coupler, a yellow filter layercontaining as. shown in the ,tollowing table.

Gradation Increase in Relative sens. Processln Formula time (min. (1) (2) (3) A 0 1.75 1.80 1.85 'i ..0 0 0 1.20 v.112 1.15 B 7 1.70 1. s5 1. 75 +0.08 +0.15 +0.11 1.35 1. 2.1 1.21 c 8 1.68 1. 60'.= 1. 70' +0.16 1.30 I 1. 30 1. 21

(1) Cyan; (2) Magenta and (3) yellow. 7

First developer: same as the first developer in,Example 1 Stopping solution: I Sodium acetateg, Acetic acid-3 ml. Water to make 1 liter.

Hardening solution:

Potassium alum-30 g. Water to make 1 liter. Color developer: Formula (A) Benzyl alcohol-5 ml. I

Sodium sulfite5 g. Sodium hydroxide (10% )-5 ml. Sodium phosphate-30 g. 3-methyl-4-amino-N,ethyl-N,methane-sulfoamidoethylaniline sulfate10 g. Potassium bromide1 g.= V .Ethylene diamine--5 'ml. Water to makel liter.

' 4 Formula (B) added to it 1".5 .g Q/liter '01; sodium Formula vA having salicylate.

" What is claimed is:

1. In a process for processing'color photographic elements employing a color developer containing a member selected from the group consisting of p-phenylenediamine and a derivative thereof, the improvement which comprises controlling the gradation of dye images obtained therein by processing with a developer additionally incorporating at least one member selected from the group consisting of compounds having the formula wherein X is a member selected from the group consisting of H, OH and NH and M is a member selected from the group consisting of H, Na, K, NH other monovalent positive atoms and mono-valent atomic groups.

2. The process as claimed in claim 1 wherein the proportion of said compound is from about 0.1 to 3 g. per 1"literfof the color developer. I

3. The process as claimed in claim 1"wherei'n the proportion of said compound is from about 0.8 to' 1.28"g. per 1 liter of the color developer.

4. The process as claimed in claim 1 wherein-said color developer further contains a soluble color coupler. "5. The process as claimed in claim 1 wherein said com- COOM pound is lhydroxy 2-naphthoieacid. v 6.-The= process as claimed in claim 1 wherein said compoundis sodium I-hydroxy-6-amino 2-naphthoate.

References Cited y UN TE A E P E 2,156,626, 5/1939 Ham1 96566.4 2,444,803. 7/1948 Bean 96-663 2,728,660 12/1955 Salminenet a1. .96

J. TRAVIS BROWN, Primary Examiner

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Classifications
U.S. Classification430/373, 430/376, 430/470
International ClassificationG03C7/413
Cooperative ClassificationG03C7/413
European ClassificationG03C7/413