JPS6049302B2 - Color photographic material for two-bath processing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new color photographic light-sensitive material which is suitable for two-bath processing consisting essentially of color development and bleach-fixing without finally using a stabilizing bath. The present invention relates to a novel color photographic light-sensitive material in which a stabilizing bath processing step can be omitted from the color processing step without causing background color staining or fading of the dye image.

Conventionally, in the manufacturing method of color photographic materials, various lipophilic photographic additives (
In the presence of surfactants, for example, oil-soluble couplers, ultraviolet absorbers, antioxidants, fluorescent brighteners, and other oil-soluble compounds are dissolved in high-boiling solvents such as dibutyl phthalate and tricresyl phosphate. An oil protection method is known in which oil droplets containing photographic additives are finely and uniformly dispersed in a colloid liquid by mechanically emulsifying the photographic additive using a homogenizer or a colloid mill.

Such oil-in-water dispersions are disclosed in US Pat. No. 2,269, for example.
No. 158, No. 2272191, No. 2322027
No. 2360289, No. 2801170, No. 2801171, No. 2852382, No. 36
No. 19195, British Patent No. 115159, West German Patent No. 1143707, etc. Color photographic materials produced using this oil protection method not only improve the stability of couplers and dye images, but also absorb light because the fluorescent brightener and ultraviolet absorber are present in an amorphous state in an organic solvent. becomes sharper and can enhance the absorption effect. After image exposure, the color photographic light-sensitive material produced by this method is processed in a color developing bath containing an aromatic primary amine developing agent, a bleach-fixing bath containing a silver oxide solvent and an oxidizing agent, and, if necessary, a bleach-fixing bath containing a silver oxide solvent and an oxidizing agent. Depending on the situation, it is treated with an intermediate wash bath, a final wash bath, and a stabilization bath.

As is well known, the stabilizing bath is an aromatic primary amine developer that remains in the color photographic light-sensitive material after processing. - It is used to prevent background color staining and fading of dye images due to the effects of drugs and their oxidation products. , tartaric acid), formaldehyde, and fluorescent brighteners. The above organic acids! A fluorescent brightener is used to acidify a color photographic light-sensitive material to prevent the oxidation of the remaining developing agent, and a fluorescent whitening agent is used to hide the background color stain that has occurred, thereby reducing the apparent background color stain and pigments. This prevents the image from fading. In addition, formaldehyde is used in the final bath when designing color photographic materials so that the developing agent and its oxidation products do not remain in the color photographic material during processing, and specifically in order to swell the photographic coating layer during processing. It is used to harden the swollen coating layer. Therefore, stabilizing baths are always used in conventional color processing processes.
Now, one of the reasons why the aromatic primary amine developing agent and its oxidation products remain in the color photographic light-sensitive material after color processing is the presence of the above-mentioned high boiling point solvent. Other causes include the physical properties of the film of the color photographic material. The remaining developing agent is immediately oxidized in the air, which reacts with unreacted caprano to generate background color staining. At the same time, the presence of oxidized developing agent causes fading of the dye image by reducing the dye. Therefore, by improving the persistence of aromatic primary amine developing agents and their oxidation products in color photographic materials, it is possible to omit the treatment with a stabilizing bath, and in this case, it is possible to omit the treatment with a stabilizing bath. If there were a color photographic material that could prevent background color staining and fading of dye images, it would be extremely useful in terms of shortening processing time.

In general, methods for preventing background color staining and fading of dye images after processing include, for example, U.S. Pat.
A method of incorporating a hydroquinone derivative into a color photographic light-sensitive material is known, as described in Japanese Patent Publication No.

However, this method relies on preventing the oxidation of the remaining developing agent, and does not essentially improve the persistence of the developing agent, so it is not possible to omit the stabilizing bath from the color processing process. Can not. It is also well known to use a large amount of the above-mentioned hydroquinone derivatives, but even in this case, the effect of omitting the stabilizing bath from the color processing step has not been achieved. Rather, the sensitivity and contrast decrease due to the use of large amounts of hydroquinone derivatives,
Others require large amounts of high-boiling solvents to maintain sufficient solubility, resulting in increased film thickness of the applied layers, increasing the tendency of the photographic element to curl, as well as increasing developer permeability. There are concerns that this may worsen the situation. One object of the present invention is to provide a color photographic material in which the persistence of an aromatic primary amine developing agent and its oxidation product in the color photographic material after processing is improved.

Another object of the present invention is to provide color solvent examples (1) without causing background color staining or fading of dye images after processing.
(G-n-hexyl phthalate) Solvent example (2) (G-n-heptyl phthalate) Solvent example (3) (G-n-octyl phthalate) Solvent example (4) (G-t-octyl phthalate) Solvent example (5) (n -Hexyl-n-octyl phthalate) Solvent example (6) (Di-n-decyl phthalate) Solvent example (7) (Di-n-dodecyl phthalate) Among these high-boiling compounds, R1 in the general formula
And those in which R2 has 6 to 8 carbon atoms are particularly excellent in improving the fading resistance of dye images in color photographic materials after processing.

Two or more of these compounds can be used in combination. Further, these high boiling point solvents can be used in combination with other high boiling point solvents or low boiling point solvents. Specific high boiling point solvents include triphenyl phosphate, tricresyl phosphate, diphenyl-mono p-t-butylphenyl phosphate, monophenyloozy p-t-butylphenyl phosphate, tri-p-t-butylphenyl phosphate, and tri-p-t-butylphenyl phosphate. 0-phenyl phenyl phosphate, di-pt-butylphenyl mono(5-t-butyl-2-phenylphenyl) phosphate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate,
Benzyl phthalate, butyl benzyl phthalate, β-ethoxyethyl phthalate, ethylene glycol monobenzyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether monoacetate, diethylene glycol monoethyl ether,
Diethylene glycol diethyl ether, ethylene glycol monophenyl ether, benzyl benzoate,
Ethyl palmitate, methyl abietate, β-ethoxyethyl sebacate, β-ethoxyethyl maleate,
Examples of low boiling point solvents include β-ethoxyethyl adipate, ethylene glycol dilaurate, heptadecanol, n-hexanol, and octyl alcohol. pionate, nitromethane, nitroethane, chloroform, methanol, ethanol, acetonitrile, dimethylformamide, dioxane, acetone,
Examples include methyl ethyl ketone, ethylene glycol, diethylene glycol, and diethylene glycol monoethyl ether. As the lipophilic photographic additive used in the present invention, any of those used in ordinary color photographic materials can be used.

Typical lipophilic additives are listed below, but are not limited to these, of course. ○Oil-soluble yellow couplers, such as those represented by the following general formula [Y].

General formula [Y] (wherein R3 is an alkyl group, alkenyl group, aryl group, or heterocyclic nuclear group which may have a substituent, R4 is a cyano group, and N- which may have a substituent) Phenylcarbamyl group, Y is -CO one group, -SO2 one group, -N= group, -CH=
The group or -C... group represents a nonmetallic atomic group necessary to complete a 4- to 6-membered nitrogen-containing heterocyclic nucleus.

) Specific examples of such yellow couplers include the following.

These yellow couplers are covered by West German Published Patent No. 20579.
Specification No. 41, Specification No. 216381, JP-A-47
-26133 Publication, Publication No. 48-29432, Publication No. 4
No. 8-66834, No. 48-66835, No. 48-94432. Publication No. 49-122? It is described in Japanese Patent Publication No. 49-10736.

○Oil-soluble magenta couplers, such as those represented by the following general formula [M].

General formula [M] (wherein R is a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an alkoxy group, or an acylamino group; R6 is a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an alkoxy group, an acylamino group; Carbamoyl group, sulfamoyl group, alkylsuccinimide group, alkoxycarboxamido group, alkoxycarboalkylamino group, alkylaminocarboalkylamino group, aralkoxycarboalkylamino group, each of which may have a substituent;
Examples of such magenta couplers include arylamine/carboalkylamino groups, aralkylaminocarboalkylamino groups, etc.

These magenta couplers are described in U.S. Patent No. 368,451.
Publication No. 4, British Patent No. 1183515, Special Publication No. 4
0-6031 Publication, Japanese Patent Publication No. 40-6035, Japanese Patent Publication No. 15754-1975, Japanese Patent Application Publication No. 2963-1972, Japanese Patent Publication No. 53437-1977, Japanese Patent Publication No. 49-1988
It is described in JP-A No. 17034, JP-A-49-123033, etc.

0 oil-soluble cyan couplers, such as those represented by the following general formula [C].

General formula [C] (wherein R,, R8 and R9 are hydrogen atoms, halogen atoms, alkyl groups, aryl groups or alkoxy groups, RlO and Rll are hydrogen atoms, alkyl groups or alkoxy groups, R
l.

represents a hydrogen atom or an alkyl group, and X represents an atom or group that is removed by pulling. )) Specific examples of the cyan coupler include the following. These cyan couplers are described in U.S. Pat.

25 In addition, oil-soluble ultraviolet absorbers can include, for example, etc., and oil-soluble antioxidants can include, for example, (1
7) 2-t-butylhydroquinone (18) 2◆5-di-t-butylhydroquinone (19
)2-Sec-octylhydroquinone (20)2-t
-Octylhydroquinone (21) 2-methyl-5-t
-Octylhydroquinone (22) 2,5-di-t-octylhydroquinone (23) 2,5-diSec-octylhydroquinone (24) α-tocopherol (25) β-tocopherol (26) 2,2,4-trimethyl-6 -Hydroxy 7
-t-butylchroman, etc. can be mentioned.

These oil-soluble UV absorbers are disclosed in U.S. Patent No. 268551.
Trowel, No. 2739888, No. 2784087, No. 3250617, No. 3253921, No. 33
No. 52681, No. 3533794, No. 36925
No. 25, West German Patent No. 108790? , West German Published Patent No. 20492, West German Published Patent No. 2151098, Japanese Unexamined Patent Publication No. 1973
-1026, and antioxidants are described in U.S. Patent Nos. 2336327, 2360290, and 240
No. 3721, No. 2418613, No. 270471
No. 3, No. 2728659, No. 2732300,
Same No. 2735765, Same No. 3432300, Same No. 3
No. 573050, No. 3574627, Special Publication No. 1974-
No. 20977, No. 50-23813, JP-A-51-6
It is described in each publication No. 024.

Other oil-soluble fluorescent brighteners include, for example, U.S. Pat.
Compounds described in Publication No. 0738 and the like can be used.

As the oil-soluble antihalation or antiirradiation dye, compounds described in US Pat. No. 3,651,494 and the like can be used. The oil-in-water dispersion used in the present invention desirably contains a hydrophilic colloid substance. As the hydrophilic colloid substances, all those commonly used as binders for photographic layers can be used. Specifically, gelatin, gelatin derivatives (e.g. acetylated gelatin, phthalated gelatin, succinated gelatin, etc.), albumin, collodion, gum arabic, agar, alginic acid, cellulose derivatives (e.g. alkyl esters of carboxy cellulose, hydroxyethyl cellulose, carboxy methyl cellulose, etc.), synthetic resins (
For example, polyvinyl alcohol, polyvinylpyrrolidone,
acrylic acid, ethyl acrylate copolymers, etc.). Such a dispersion can be prepared by a method similar to the known oil protection method described above.
In the present invention, a color photographic coating solution is prepared by mixing this oil-in-water dispersion with an aqueous gelatin solution or a silver halide photographic emulsion, and this is coated onto a support by a conventional method. Any known silver halide emulsion can be used. Silver halide grains are composed of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide, etc., and are described in U.S. Pat. No. 2,592,250. The silver halide grains may be converted halide type silver halide grains such as those of the internal latent image type or the surface latent image type. Silver halide emulsions are prepared using sulfur sensitizers (e.g. ammonium thiosulfate,
Chemical sensitizers such as allylthiourea, gold sensitizers (e.g., potassium chloroaurate, potassium gold thiocyanate, etc.), or reduction sensitizers (e.g., stannous chloride, etc.), stabilizers (
For example, 5-hydroxy-1,3●C●7-tetrazaindene, etc.), hardening agents (for example, formaldehyde, mucochloric acid, triazines, divinylsulfonic acid, aziridines, etc.), coating aids (saponin, etc.), etc. It can contain. The color photographic material of the present invention can be produced by coating a support with a coating layer containing a silver halide emulsion spectrally sensitized to various wavelength ranges and a suitable filler as described above.

Examples of sensitizing dyes used in blue-sensitive emulsions include U.S. Pat.
No. 161331, No. 3149105, British Patent No. 4
2455Cf3, No. 660408, No. 74211
Typical examples include cyanine dyes, simple cyanine dyes, merocyanine dyes, mono-composite cyanine dyes, and combinations of these described in various publications.

Furthermore, blue-sensitive emulsions containing no spectral sensitizer can also be used. Examples of the multiplying dye used in green-sensitive emulsions include U.S. Pat. No. 1,939,201, U.S. Pat.
Typical examples include cyanine dyes, carbocyanine dyes, merocyanine dyes, composite cyanine dyes, and combinations thereof described in Publication No. 45763 and British Patent No. 50594, and red-sensitive emulsions. Examples of sensitizing dyes used in
No. 234, No. 2270378, No. 2442710
Typical examples include those described in Publications No. 245,462-inch, and Publication No. 277,628-inch. Furthermore, U.S. Patent Nos. 2,213,995 and 2,493,748
No. 2519001, West German Patent No. 9290 (4)
The cyanine, merocyanine or composite cyanine dyes described in each of the publications No. ) can be advantageously used in blue-sensitive emulsions, green-sensitive emulsions and red-sensitive emulsions. Suitable supports for use in the color photographic material of the present invention include, for example, cellulose acetate film, cellulose ester film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, glasses, baryta paper, metals, polyolefins such as polyethylene, polypropylene, etc. After coating with a synthetic paper or the like, a synthetic paper or the like can be applied.

The color photographic material according to the present invention can be processed using a two-bath process consisting essentially of color development and bleach-fixing without using a stabilizing bath.

In this two-bath treatment, an intermediate washing step can be introduced between the color development step and the bleach-fixing step, and a final washing step can be introduced after the bleach-fixing step, if necessary. The two-bath treatment is preferably carried out at a high temperature of 30°C or higher and in a short period of time. At this time, color development is
Aromatic primary amine developing agents, such as 4-amino-N
-N-diethylaniline, 4-amino-3-methyl-N
●N-diethylaniline, 4-amino-3-methyl-N
-ethyl-N-(β-methylsulfonamidoethyl)
Aniline, 4-amino-3-methyl-N-ethyl-N-
It is processed with a known alkaline color developer containing a sulfate or hydrochloride such as (β-hydroxyethyl)aniline in a proportion of 3 to 10 yI'. This color developer may contain known additives such as benzyl alcohol, alkali metal sulfides, bromides, iodides, hydroxylamine sulfuric acid or hydrochloride, triethanolamine, and the like. Bleach-fixing can also be carried out using silver halide solvents such as sodium thiosulfate, potassium thiosulfate, ammonium thiosulfate, sodium thiocyanate, ammonium thiocyanate, organic diol fixing agents (such as 3-thia 1,5-pentanediol, 3,6- Jichia 1/8
-octanediol, etc.) and silver halide oxidizing agents, such as iron (■)-aminopolycarboxylic acid complex salts, cobalt (■
) complex salt, iron(■)-polycarboxylic acid complex salt, etc., using a known bleach-fix solution. Examples of aminopolycarboxylic acids include nitrotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylene glycol bis(aminoethyl ether)tetraacetic acid, diaminopropanoltetraacetic acid, N-hydroxyethylethylenedi)aminetriacetic acid, ethyliminodipropionic acid, etc. , polycarboxylic acids include malonic acid, ethylmalonic acid,
Tartaric acid, malic acid, diglycolic acid, etc. can be mentioned. This bleach-fix solution may also contain various known additives. 5. The color photographic light-sensitive material subjected to the two-bath treatment may be dried in a conventional manner.

Next, the present invention will be explained with reference to examples (including comparative examples), but these are representative examples of the present invention, and the present invention is not limited to these. .

Example 1 A yellow coupler [the above-mentioned exemplified compound (4)] was used as a comparative sample.
)] was dissolved in a mixed solvent of 30q of tricresyl phosphate and 30y of ethyl acetate at 70°C, and the resulting solution was dissolved into an aqueous solution of 400g of 20y of gelatin and 0.8d of sodium dodecylbenzenesulfonate.
ml and stirred for 3 minutes using a homogenizer to obtain a dispersion.

After treating this dispersion with an evaporator to remove ethyl acetate, it was mixed with 40 Da of silver iodobromochloride and 50 Da of gelatin.
After adding a hardening agent to the gelatin emulsion containing y and adjusting the pH to 7.0, the coating solution was coated on 170 da 1 rr1 photographic base paper laminated with polyethylene film with a silver content of 50 mg. Sample 1 was prepared by coating and drying to give a coating density of /100 cd. In contrast, as samples of the present invention, in place of tricresyl phosphate 30f used in Sample 1, the high boiling point solvent compounds of the present invention (1), (2), (3), (4), Sample 2 was prepared in the same manner as Sample 1 above, except that 30 dabs each of (5) and (7) were used.
~7 was prepared.

After wedge exposure of these samples, a yellow image was obtained by standard processing as described below.

For the yellow image obtained, 10 gE = 1. o and 10
The color density at gE=0.0 was measured. The results are shown in Table 1. In addition, each sample was subjected to the following background color contamination treatment without wedge exposure, and the blue light density was measured using a Ratten 94 filter, and the amount of developing agent remaining in the sample was measured colorimetrically. It was measured by the method. The results are shown in Table 1. The color developer was prepared according to the following recipe. Color developer 4 -(N-ethyl-N-P-methanesulfonamidoethyl)amino-2-methylaniline sulfate 5 dabenzyl alcohol 20 ml 15 ml ethylene glycol Anhydrous sodium carbonate 35 y Anhydrous sodium sulfite 3 Potassium dabromide 0.6 y Hydroxylamine A bleach-fix solution was prepared by adding 3 parts of sulfate and water to a total volume of 11 parts according to the following recipe.

Bleach-fix solution Ammonium thiosulfate 120 das Anhydrous ammonium sulfite 20 f Sodium iron(11) ethylenediaminetetraacetate 80 da
According to Table 1, in which di-sodium diethylenediaminetetraacetate was added to make a total amount of 11, samples 2 to 7 according to the present invention had high color development and good photographic properties.

“Also, it can be seen that the sample according to the present invention has a low residual amount of developing agent after processing, and at the same time, the occurrence of background color staining is low.Example 2 As a comparative sample, cyan coupler
] 30y was dissolved in a mixed solvent consisting of 20y of dibutyl phthalate and 50y of ethyl acetate at 700C. The resulting solution was added to 400TfL1 of an aqueous solution containing 20y of gelatin and 0.8y of sodium dodecylbenzenesulfonate, and stirred for 3 minutes with a homogenizer. A dispersion liquid was obtained.

This dispersion was left in an evaporator for 3 minutes to remove ethyl acetate, and then gelatin containing 40 y of silver chlorobromide and 50 y of gelatin was spectrally sensitized with a common red-sensitizing dye. A coating solution was prepared by adding it to a photographic emulsion. A normal hardener is added to this coating solution, and the pH is adjusted to 7. O
170zo/100cT1. which was adjusted to 170zo/100cT1. The amount of silver on the photographic base paper is 30
Sample 8 was prepared by coating and drying to give m9/100c. In contrast, as a sample according to the present invention, sample 8
Samples 9 to 12 were prepared in the same manner as Sample 8, except that 30 da each of the above-mentioned illustrative solvents (1), (2), (31 and (6)) was used in place of 20 da of dibutyl phthalate used in did.

These samples were subjected to the same exposure, standard treatment, and background color staining treatment as in Example 1 above.

10gE=1.0 and 10t for the obtained cyan image
The color density of =0.0 was measured. The results are shown in Table 2. In addition, as a fading test, these cyan images were exposed to sunlight in September for 13 hours (enough to fade the standard amount of dye of grade 4 on the blue scale), and then the initial density was determined using a Latten 92 filter. The fading properties of the dye image were observed by measuring the faded density values at points 0.5 and 2.0. The ground color contamination density was measured in the same manner as in Example 1 above. These results are shown in Table 2. Table 2 shows that Samples 9 to 12 according to the present invention have high color development and good photographic properties and fade resistance.

In particular, Samples 9 to 11 showed excellent results in terms of fading resistance. It is also seen that the samples according to the present invention have a low amount of developing agent remaining after processing, and at the same time, the occurrence of background color staining is low.
Example 3 As a comparative sample, 0.01 mol of cyan coupler [the above-mentioned exemplified compound (10)] and 0.002 mol of 2,5-Z-t
- Octylhydroquinone to dibutyl phthalate 15f
and ethyl acetate at 70°C.
The resulting solution was added to an aqueous solution consisting of 150 cc of 5% gelatin solution and 0.3 y of sodium dodecylbenzenesulfonate, and stirred three times using a homogenizer to obtain a dispersion.

This dispersion was left in an evaporator for 3 minutes to remove ethyl acetate, and then added to 400 cc of a 0.15 mol silver chlorobromide gelatin emulsion spectrally sensitized with a common red sensitizing dye. A coating solution was prepared. This coating liquid was coated onto photographic base paper in the same manner as in Example 2 to obtain Sample 13. In contrast, a sample according to the present invention was prepared in the same manner as Sample 13, except that 15 y of each of solvents (3) and (6) shown in Example 2 above were used in place of 15 y of dibutyl phthalate used in Sample 13. Samples 14 and 15 were prepared.

These samples were subjected to the same exposure and standard processing as described above, and the cyan images obtained were subjected to the same fading test as in Example 2 to measure the fading resistance.

Claims (1)

[Scope of Claims] 1. In a color photographic light-sensitive material, an in-water solution is formed by dissolving a lipophilic photographic additive using a compound represented by the following general formula and emulsifying a solution obtained in a hydrophilic colloid liquid. It is characterized by containing an oil droplet-type colloidal dispersion in at least one coating layer on a support, and is suitable for two-bath processing consisting essentially of color development and bleach-fixing without using a final stabilizing bath. color photographic material. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. )