JPS603171B2 - color photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color photographic material and a method for producing the same.
In particular, it relates to a halogenated magnetic color photographic light-sensitive material that can be subjected to high-temperature development processing of 3,000 or more times and has improved properties such as color capri suppression and hue constancy without impairing deterioration in sensitivity or tone, and a method for producing the same. .

As is well known, color photography using the subchromic method generally consists of oxidation products of a color developer produced by reducing silver halide exposed to an aromatic primary amine color developer, yellow, magenta, and cyan. A color image is formed by oxidative coupling in a silver halide emulsion with a color coupler that forms a color image.

At this time, color fog (also called color contamination) occurs due to various factors, such as air oxidation, which causes the color developer to oxidize, and the product reacts with the color coupler to form a dye, or the color developer It is well known that this is caused by the oxidation products of oxidation products diffusing into other layers to form pigments. In order to suppress the formation of such colored fog, for example, US Pat.
No. 00, No. 2728659, British Patent No. 55825
The method described in Publications No. 8 and the like has been proposed. Color fog has been suppressed by conventional methods by adding large amounts of compounds, such as 2,5-di-normal octylhydroquinone described in US Pat. No. 2,360,290, to photographic emulsions.

According to recent research by the present inventors, when such a compound is used alone, the formation of colored fog can be more effectively suppressed as the amount used increases; It has been found that this problem is accompanied by a deterioration in color development and the hue of the developed dye, and this problem is particularly severe in the case of magenta couplers. On the other hand, if the amount of the above-mentioned compounds used is reduced, the color fog suppressing effect will be drastically reduced. An object of the present invention is to provide an improved color photographic material. Another object of the present invention is to effectively suppress the formation of colored fog, and to improve the deterioration of the coloring property and hue of the colored pigment, which have been sacrificed in order to suppress the formation of colored fog. Our objective is to provide color photographic materials.

Another object of the present invention is to provide a color photographic material suitable for high-temperature development* of 30 qo or higher.
Other objects of the invention will be readily apparent to those skilled in the art from the following description. The present invention provides at least one tocopherol derivative compound represented by the following general formula (1) and the general formula (
This is a color photographic material characterized by containing at least one hydroquinone derivative compound represented by 0).

General formula (1) (wherein R,, R2 and R3 represent a hydrogen atom or a methyl group.

) General formula (0) (wherein R4 represents an alkyl group having 4 to 18 carbon atoms, and R5 represents a hydrogen atom or an alkyl group having 4 to 18 carbon atoms.

) Here, the photographic component of a color photographic light-sensitive material refers to a material composed of at least various layers including a silver halide color photographic emulsion layer containing at least a color coupler and a photosensitive silver halide; In a preferred embodiment of the present invention, each of tone-, green- and red-sensitive silver halide photographic emulsions has respective photographic emulsion layers with yellow, magenta and cyan couplers added thereto, optionally with a bleachable yellow color between each emulsion layer. It can be applied to multilayer color photographic materials provided with a filter layer, intermediate layer, subbing layer, top protective layer, etc.

The silver halide photographic emulsion used in the present invention can contain various hydrophilic substance colloids (alone or in combination) as vehicles or binders.

Suitable hydrophilic substances include natural products such as gelatin, gelatin derivatives, cellulose derivatives, dextran, polysaccharides such as gum arabic, and water-soluble polyvinyl compounds such as various water-soluble synthetic vinyls such as polyvinyl alcohol, polyvinylpyrrolidone, and acrylamide polymers. Polymers can be used. The above-mentioned hydrophilic substances include aziridine hardeners and other 1,3-pis(1-aziridinylsulfonyl) agents described in US Pat.
-propane, 1-(1-aziridinylcarponyl)-3
-Aziridine hardeners such as (1-aziridinylsulfonyl)benzene, U.S. Pat. No. 3,316,095;
Isoxazolium salt hardeners described in each publication No. 21313 and other 2,5-dimethylisooxazolium perchlorate, 2-ethyl-5-phenylisooxazolium-3'-sulfonate, 2-methyl -5-isooxazolium salt hardener such as p-tolylisoxazolium-3'-sulfonate, Belgian Patent No. 6864
Hardening can be carried out using vinyl sulfone hardeners, epoxide hardeners, and triazine hardeners described in Japanese Patent Publication No. 47-6151 and the like. As the silver halide photographic emulsion according to the present invention, various emulsions such as silver chlorobromide, silver bromide, silver chloroiodobromide, and silver iodobromide emulsions can be used.

Such silver halide photographic emulsions can be coated with a color coupler as described below and coated on a wide variety of supports. As a support, cellulose sulfate film,
Cellulose ester film, polypynylacetal film, polystyrene film, polyethylene terephthalate film, polycarbonate film, glass,
Includes paper, metal, etc. Typically, flexible supports are used, especially paper supports. The paper support is partially acetylated and/or made of a polyolefin polymer.
In particular, it can be coated with polyethylene, polypropylene, etc. The silver halide emulsions according to the invention preferably consist of blue-, green- and red-sensitive silver halide emulsions.

The emulsion is spectrally sensitized to the desired blue, green, and red light by adding respective sensitizing dyes that absorb in the green and red colors, and optionally a sensitizing dye that absorbs in the blue color, respectively. Sensitizing dyes for this purpose are well known. Examples include cyanines, merocyanines, complex merocyanines, complex cyanines, holopolar cyanines, styryls, hemicyanines, oxonols, and hemioxonols. Also, if desired,
These various dyes are used in combination. In a preferred embodiment of the present invention, the silver halide photographic emulsions used in the present invention include U.S. Pat.
Patent No. 2410, chemical sensitization method using natural active gelatin or sulfur compound described in each publication, ruthenium, rhodium described in U.S. Patent No. 244806,
Chemical sensitization method using noble metals such as palladium, iridium, and platinum, U.S. Patent Nos. 2,399,083 and 2,642
Chemical sensitization method using gold salts (potassium chlorooleite, potassium aurithiocyanate, potassium chlorooleate, auricul trichloride, and 2-oresulfobesozothiazole methochloride) described in No. 361 publications, US patent Chemical sensitization using a reducing agent such as tin chloride described in No. 2487850, polyamines described in U.S. Patent No. 2518698, or U.S. Patent No. 162349 and No. 1602592 A silver halide photographic emulsion prepared by the chemical sensitization method using the unstable selenium described above can be applied. It can also be applied to halogenated radiographic emulsions prepared by combining various chemical sensitization methods, if desired. Next, the general formula (
The tocopherol derivative compound represented by 1) and the hydroquinone derivative compound represented by general formula (b) are listed below, but the present invention is of course not limited to these. Tocopherol Derivative Compound Example Q Tocopherol 8 Tocopherol Sortocopherol 6 Tocopherol Gotocopherol Hydroquinone Derivative Compound Example 2,5-T-tertiarybutylhydroquinone 2,5
- Jeter Shiary Amyl Hydroquinone 2- Yuichi Shiary Aluminum Hydroquinone 2,5- Jeter Shiary Octyl Hydroquinone 2-
Yuichi Shiaryoctyl-5-tertiarybutylhydroquinone 2-isooctadecylhydroquinone 2-Normaldodecylhydroquinone 2,5-di-NormalOctylhydroquinone 2-NormalOctylhydroquinone 2,5-DiNormalAmylhydroquinone The above-mentioned compounds according to the present invention Such tocopherol derivative compounds and hydroquinone conductor compounds are effectively added to the components of color photographic materials.

At this time, tocopherol derivative compounds may be used alone or in combination with hydroquinone derivative compounds, lower alcohols such as ethyl alcohol, acetone, or those insoluble in these, low boiling point organic solvents such as ethyl acetate, butyl acetate, chloroform, etc. (or) It is dissolved in a high-boiling organic solvent such as tricresyl phosphate, dibutyl phthalate, etc., and added to an aqueous gelatin solution containing an activator such as sodium dodecylbenzenesulfonate, and then finely divided using a homogenizer or an ultrasonic disperser. After dispersion, the low boiling organic solvent is removed before addition into the photographic component. At this time, the amount added is not particularly limited compared to conventional ones and can be used in a wide range, but generally the tocopherol derivative compound according to the present invention is 1 x 10-3 to 1 mol per 1 mol of silver halide. , preferably 1×10-1 to 7×lo-1 mol, and the hydroquinone derivative compound is generally used in an amount of 1×1 to 1 mol of silver halide.
0-5 to 1 mol, preferably 2×10-3 to 2×10-
Used at 2 mol. The tocopherol derivative compound and the hydroquinone derivative used in the present invention, when incorporated into a photographic component, may be added in the same layer or in separate layers, and/or may be added in separate layers. .
Each of the above compounds may be added at any step up to the time of coating the emulsion on a support, but it is preferable to add them to a chemically ripened emulsion. Various color couplers can be used in the color photographic material according to the present invention.

Examples of the compounds are listed below, but the invention is of course not limited to these. Cyan Coupler Magenta Coupler Yellow Coupler - In preferred embodiments of the invention, these color couplers are made of high boiling point organic solvents that are poorly miscible with water and have a boiling point of 17,500 or higher, such as di-n-butyl phthalate, triphenylphosphthalate, etc. ate, benzyl phthalate, tri-o-cresyl phosphate, mono-phenyl-di-p-t-butylphenyl phosphate, diphenyl-mono-p-t-butylphenyl phosphate, mono-phenyl-di-o-chlorophenyl phosphate, diethyl laurylamide, etc. and/or low-boiling organic solvents such as ethyl acetate, cyclohexanone, 61-n-butyl ethoxycetylacetate, etc. or organic solvents that are easily miscible with water, such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, glycerin. , tetrahydrofuran, diethylene glycol monoacetate, diacetone alcohol, acetonitrile, methyl isobutyl ketone, etc., this coupler solution is finely dispersed in the above-mentioned hydrophilic substance, and this dispersion is mixed with a silver halide photographic emulsion. urge

The tocopherol transfer compound and hydroquinone transfer compound according to the present invention can be contained in such a hydrophilic substance, and the above compounds can also be contained in the coupler solution. The color photographic material according to the present invention can be developed with a color developer containing an aromatic primary amine color developer.

Typical color developers are 3-acetamido-4-amino-N,N-diethylani-1', p-amino-N-8
-Hydroxyethylaniline sulfate, p-amino-N-ethyl-N-8-hydroxyethylaniline, N
, N-dimethyl-p-phenylenediamine, 2-amino-5-diethylaminotoluene, 4-amino-3-methyl-N-ethyl-N-8-methanesulfonamide doethylaniline, 4-amino-N-ethyl-3-methyl-N
-(B-sulfoethyl)aniline, 4-amino-3-methyl-(N-ethyl-N-6-hydroxyl)aniline, and the like. Further, following such a development step, a desilvering step well known in the art (for example, Japanese Patent Publication No. 48
A method using a Brix bath described in Publication No. 328 is used. ) and rinsing process, and if desired, hardening, stopping,
Auxiliary steps such as stabilization and finishing steps can be introduced to form color images. As mentioned above, the color photographic light-sensitive material according to the present invention can be any material as long as both the tocopherol derivative compound and the hydroquinone derivative compound represented by the above general formula are contained in the photographic constituent elements. There may be.

In the color photographic light-sensitive material of the present invention, the tendency of color capri formation is significantly reduced, and, unexpectedly, the deterioration of the color development property and the hue of the developed dye is eliminated. Furthermore, even if the process time of prix grade and water wash grade after color development is shortened by 1/2 to 1/9 compared to the conventional process, the tendency to produce yellow dye in the ground color (unexposed area) is eliminated. This can advantageously shorten the processing time. Therefore, according to the present invention, tocopherol transfer compounds and hydroquinone derivative compounds can be used in extremely wide ranges of addition amounts. It is also unexpected that when a hydroquinone derivative compound is used in combination with a tocopherol transfer compound, the branched alkyl-substituted hydroquinone achieves the intended effects of the present invention better than when the hydroquinone derivative compound is a straight-chain alkyl-substituted hydroquinone. It's about achieving your goals advantageously. However, even when a direct mirror alkyl-substituted hydroquinone is used in combination with a tocopherol derivative compound, the effect is extremely significant compared to when each is used alone. Such a surprising mechanism of synergistic effects due to the combination of tocopherol derivatives and hydroquinone transfer compounds, and the fact that branched alkyl-substituted hydroquinones are superior to direct mirror alkyl-substituted hydroquinones in terms of the above-mentioned synergistic effects. Although the mechanism is not yet clear, the combination described above is extremely advantageous in photographic technology. Hereinafter, the present invention will be explained with reference to examples.

Example 1 A spectrally sensitized silver chlorobromide emulsion containing 0.1 mol of silver chlorobromide was prepared.

The magenta coupler (M-6) log described above was dissolved in a mixture of 15 parts of tricresyl phosphate and 30 parts of ethyl acetate, and this solution was dissolved in a 10% gelatin solution 200M.
and 5% sodium dodecylbenzenesulfonate solution (15), mixed at 50 qo and finely dispersed with an ultrasonic disperser, was added to the above silver chlorobromide emulsion, and divinyl sulfone (CH2CHS02CH2S02CH
Sample 1 was prepared by adding 10 parts of a 10% acetone solution of =CH2) and then coating it on a polyethylene-coated paper support. Adding 1 of divinyl sulfone to the above silver chlorobromide emulsion
Before adding the 0% acetone solution, add the magenta coupler (
M-6) A solution of 1 female and 2 groups of o-tocopherol dissolved in a mixed solvent of 15 parts of tricresyl phosphate and 30 parts of ethyl acetate was added and dispersed, and Sample 2 was prepared in the same manner as Sample 1 above. It was created.

Instead of the Q-tocopherol used when preparing Sample 2, a mixture of tricresyl phosphate 15 and ethyl acetate 30 was added to the 2,5-tertiary octylhydroquinone (0-4) described above. Sample 3 was prepared in the same manner as Sample 2 above, except that .7 g of the solution was used. Sample 4 (product of the present invention) was prepared by adding one side of Q tocopherol from which Sample 2 was prepared, and 0.5 g of 2,5-tertiary octylhydroquinone. Sample 5 (product of the present invention) prepared using the above-mentioned base material was prepared using 2-normal dodecyl hydride described above in place of the 2,5-tertiary octylhydroquinone used when preparing Sample 4 above. Rokinone (Rho 7) 0. It was prepared in the same manner as Sample 4 above, except that a tether was used.

Sample 6 (product of the present invention) was prepared by adding 1 female magenta coupler (M-6) and 15 g of Q tocopherol to the silver chlorobromide emulsion before adding a 10% acetone solution of dipynyl sulfone.
15' of tricresyl phosphate and 3' of ethyl acetate
A solution of 2,5-tertiary octylhydroquinone is added and dispersed in a mixed solvent, and then applied to a paper support coated with polyethylene. The base was dissolved in a mixed solvent of 0.5 parts of tricresyl phosphate and 1 part of ethyl acetate, mixed with 5 parts of 5% gelatin solution and 1 part of 5% sodium dodecylbenzenesulfonate, and subjected to ultrasonication. It was created by applying finely dispersed material using a dispersion machine.

Gelatin was hardened with divinyl sulfone in the same manner as the sample above. Next, after each of the above samples 1 to 6 was wedge exposed, it was processed according to the following method to determine the fog density,
Specific sensitivity and ratio ratio (r) were measured by conventional methods.

In addition, in order to examine the stability of samples 1 to 6 over time, the temperature was 50°C.
After being stored for 9 hours under conditions of 80% relative humidity and 80% Celsius, it was exposed and processed in the same manner as above, and the maximum density, fog density and hue were measured. The results are shown in the table below-
Shown in 1. Treatment process Temperature Time 1. Coloring phenomenon 32C 4 minutes 2. Bleach fixing 32C I minute 30 seconds 3. Wash with water 28C 2 minutes 4. Stabilizer 32C I min5. Rinse 28C 5 seconds 6. dry
Drying, color development, bleach-fixing and stabilizing solutions were carried out according to the following procedures.

[Color developer]

[Bleach-fix solution] [Stabilizer] Table 1 (However, the fog density in Table 1 is the value when 3 is ○ and developed for 8 minutes.

The display in the hue field is as follows. a...extremely good with no change b...good with no change c...some change d...significant change) As is clear from Table 1 above, tocopherol derivatives It can be seen that when the compound and the hydroquinone derivative are used together, they are extremely superior to when each is used alone.

Example 2 Samples 7 to 10 were prepared in the same manner using the cyan coupler 1 described above instead of the magenta coupler used in Example 1.
It was created.

However, the tocopherol derivative compound is y as described above.
-Tocopherol, hydroquinone derivative compound is 2
, 5-jetarsiallyamylhydroquinone was added to the spectrally sensitized silver chlorobromide emulsion in the amounts shown in Table 12 below. Samples 7 to 10 were treated in the same manner as in Example 1. The results are shown in Table 2 below. Table 2 * Artcopherol ** 2,5-Jitane Yaryamylhydroquinone (However, a to d are the same as those shown in Table 1 above, and the same markings were used in the Examples below.

) Example 3 A silver chlorobromide emulsion containing 0.1 mol of silver chlorobromide was prepared in accordance with U.S. Pat.
Example 1 of Publication No. 642361 (However, silver chlorobromide was used in place of silver iodobromide.

) A silver chlorobromide emulsion was prepared by chemically sensitizing the surface of silver chlorobromide grains. Yellow coupler (Y
-1) Dissolve 2 females in a mixed solvent of 40% dibutyl phthalate and 70% ethyl acetate, and mix this solution at 50q0 with a solution consisting of 250% gelatin solution and 30% 5% sodium dodecylbenzenesulfonate. Sample 11 was prepared by adding the dispersion to the above silver chlorobromide emulsion and coating it on a paper support coated with polyethylene. The gelatin was also hardened with divinyl sulfone. In the same manner as in Example 1, 6-tocopherol as a tocopherol derivative compound and 2-tertiary octyl-5 as a hydroquinone derivative compound were added to the surface-chemically sensitive silver chlorobromide emulsion used in Sample 11 above. Samples 12 to 14 were prepared by adding tert-tertiary butylhydroquinone (Rho 5) in the amount shown in Table 3 below.
It was created.

Samples 11 to 14 were treated in the same manner as in Example 1 and then measured. The results are shown in Table 3 below.
Table 3 ※※※Tocopherol※※※※2-tertiary octyl-5-tertiary butyl-rehydroquinone Example 4 Magenta prepared in Examples 1 to 3 above on a paper support coated with polyethylene. Silver chlorobromide emulsions containing couplers, cyan couplers and yellow couplers are sequentially prepared in Table 4 below.
It was applied as follows.

Gelatin was hardened with dipinyl sulfone. Samples 15 to 18 were prepared by adding Q-tocopherol and 2,5-tertiary octylhydroquinone to the silver chlorobromide emulsion in the amounts shown in Table 4 below. After performing the same treatment, each sample was measured. The results are shown in Table 5 below. Table 4A: Q-Tocofer L Rule B: 2,5-Jetan Yaryokuti "Rehydroquinone Table 5 As is clear from the above table, the color photographic material (Sample 18) according to the present invention has a It can be seen that the effect of the present invention is superior to the sample using each of the tocopherol derivative compound and the hydroquinone derivative compound alone, and the effect of the present invention is particularly remarkable in the ortho layer (containing the magenta coupler).

Example 5 A spectrally sensitized silver chlorobromide emulsion containing 0.1 mol of silver chlorobromide was prepared and the magenta coupler (
M-6) 1 female was dissolved in a mixture of 15 Z of tricresyl phosphate and 30 Z of ethyl acetate, and this solution was dissolved in 10
A solution consisting of 200% gelatin solution and 15% 5% sodium dodecylbenzenesulfonate solution was mixed at 50°C, finely dispersed with an ultrasonic disperser, and added to the above silver chlorobromide emulsion. Q tocopherol 1 chick and 2,
5-Tertiary Octyl Hydroquinone 0. The chicks were dissolved in a mixed solvent of 5% tricresyl phosphate and 10% ethyl acetate, 10% gelatin solution 50% and 5% sodium dodecylbenzenesulfonate solution 5% and dispersed finely with an ultrasonic disperser. Sample 19 was prepared by coating the resulting emulsion on a polyethylene-coated paper support.

The gelatin was hardened with 10' of a 3% solution of triethylene phosphoramide in acetone. In addition, as comparative samples, samples 20 and 21 containing no Q-tocopherol and 2,5-tertiary octylhydroquinone were prepared, respectively, and processed in the same machine as Example 1. The results are shown in Table 6 below. Table -
6 Example 6 Solutions consisting of the following compositions were mixed and dissolved by heating, and these were mixed into a solution consisting of 80 parts of 10% gelatin solution and 1 part of 5% sodium dodecylbenzenesulfonate solution.
The mixture was mixed at 0'' and finely dispersed using an ultrasonic dispersion agent to obtain a dispersion.

Sample 22 was prepared by adding this dispersion to the silver chlorobromide emulsion used in Example 2 above.

As a comparison sample, one containing no Q-tocopherol and 6-tocopherol was prepared and designated as Sample 23, and 2,5-
Sample 24 was prepared without containing Jeter Shary-amylhydroquinone. Each sample was processed in the same manner as in Example 1 above. The results are shown in Table 7 below. Table-7

Claims (1)

[Scope of Claims] 1. A color photographic light-sensitive material comprising, on a support, a photographic component having at least a silver halide color photographic emulsion layer containing at least a color coupler and a photosensitive silver halide, The following general formula (
1. A color photographic material comprising at least one tocopherol derivative compound represented by I) and at least one hydroquinone derivative compound represented by general formula (II). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_3 represent hydrogen atoms or methyl groups.) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ( In the formula, R_4 is an alkyl group having 4 to 18 carbon atoms, R
_5 represents a hydrogen atom or an alkyl group having 4 to 18 carbon atoms. )2 In the hydroquinone derivative compound represented by general formula (II), R_4 is a branched alkyl group having 4 to 18 carbon atoms, and R_5 is a hydrogen atom or a branched alkyl group having 4 to 18 carbon atoms, Claim 1 Color photographic material as described. 3. The color photographic material according to claim 1, wherein the tocopherol derivative compound is α-tocopherol. 4. The color photographic material according to claim 2, wherein the tocopherol derivative compound is α-tocopherol. 5. The hydroquinone derivative compound is selected from 2,5-tertiary-amylhydroquinone, 2,5-tertiary-octylhydroquinone, and 2-tertiary-octyl-5-tertiary-butylhydroquinone. A color photographic material according to claim 2. 6 The hydroquinone derivative compound is 2,5-diter
The color photographic light-sensitive material according to claim 3, which is selected from tertiary-amylhydroquinone, 2,5-tertiary-octylhydroquinone, and 2-tertiary-octyl-5-tertiary-butylhydroquinone. .
7. A method for producing a color photographic light-sensitive material comprising, on a support, a photographic component having at least a silver halide color photographic emulsion layer containing at least a color coupler and a photosensitive silver halide, comprising at least one type of photographic material. A silver halide color photographic emulsion is prepared using a high boiling point organic solvent and/or
A hydrophilic compound containing at least one tocopherol derivative compound represented by the following general formula (II) and at least one hydroquinone derivative compound represented by the general formula (II), a color coupler contained in a low boiling point organic solvent. A method for producing a color photographic material, characterized in that it contains a dispersion obtained by finely dispersing a substance. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2.R_3 represent hydrogen atoms or methyl groups.) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ( In the formula, R_4 is an alkyl group having 4 to 18 carbon atoms, R
_5 represents a hydrogen atom or an alkyl group having 4 to 18 carbon atoms. )8 In the hydroquinone derivative compound represented by general formula (II), R_4 is a branched alkyl group having 4 to 18 carbon atoms, and R_5 is a hydrogen atom or a branched alkyl group having 4 to 18 carbon atoms. A method for producing a color photographic material according to item 7.