JPS6156501B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for forming a yellow image on a silver halide color photographic light-sensitive material, and more particularly to a method for forming a yellow image with extremely good image storage stability. In color photography, it is already well known that, after exposure, a photographic light-sensitive material containing a coupler is color-developed with a developer containing an aromatic primary amine developer to form a dye image. Among the couplers used in this technique, yellow couplers have active methylene groups that serve to couple with the oxidation products of aromatic primary amine developing agents to form yellow dyes. When this active methylene group is unsubstituted (i.e., active site unsubstituted yellow coupler), 1
To form a molecular dye, silver halide 4
Because it requires a molecule, it is called a 4-equivalent coupler. On the other hand, it is also possible to make the same dye as the unsubstituted coupler from the so-called active point substitution type yellow coupler in which one of the hydrogen atoms of the active methylene group is substituted with a substituent such as a halogen atom such as a chlorine atom. Are known. In this case, substituent components such as halogen atoms are eliminated during the color development reaction, and two molecules of developed silver halide can form one molecule of dye, so these couplers are called 2-equivalent couplers. There is. As for the skeleton structure of yellow couplers, benzoylacetanilides were previously widely used, but recently bivaloylacetanilides have become mainstream. This shift to bivaloylacetanilides is mainly due to the fact that the light resistance of images is better than that of benzoylacetanilides. Even the yellow dye images derived from the thus improved bivaloylacetanilides do not have sufficient fastness to satisfy social demands for image archivability. As a technique for improving the light resistance of such yellow images, firstly, since yellow images are particularly sensitive to light in the ultraviolet region, a widely used method is to incorporate an ultraviolet absorber into an intermediate layer etc. for the purpose of removing this ultraviolet light. It is being done. These ultraviolet absorbers are
−10466, No. 42-26187, No. 48-5496, No. 48
Hydroxybenzotriazole derivatives are known as described in specifications such as No.-41572 and JP-A-50-87326. However, when these ultraviolet absorbers are emulsified and dispersed and used in color photographic materials, the low solubility of these compounds in organic solvents causes the precipitation of crystals, which has a negative impact on the manufacturing process and photographic properties. Because of this, the amount added is limited, making it impossible to obtain satisfactory light resistance. On the other hand, there is a method of containing an image stabilizer in the environment of yellow dye, and Japanese Patent Publication Nos. 48-31256 and 48-31625
The publication contains bisphenols, U.S. Patent No.
3432300, 3574627, etc., 6-hydroxychromans are used, and Japanese Patent Publication No. 49-20977 describes the use of 6,6'-dihydroxy-2,2'-bissuhilochromans, etc. Proposed. However, although these compounds are certainly effective in improving the light resistance of macenta dyes, they not only have no effect on yellow dyes, but some even promote photobleaching. Furthermore, it is well known that the light resistance of dyes varies depending on the type of high-boiling organic solvent (boiling point of 175° C. or higher) commonly used for coupler dispersion. However, the effect of improving light resistance by changing the high boiling point solvent is extremely small. Therefore, the reality is that no satisfactory method has been found for improving the light fastness of yellow dye images. A first object of the present invention is to provide a method for hardening yellow images that is simple and highly effective. A second object of the present invention is to provide a color photographic material in which the photobleaching of yellow dye images is significantly improved. Other objects of the invention will become clearer from the description below. As a result of various studies, the inventors found that water at 20°C
A silver halide color photographic light-sensitive material containing at least one yellow coupler represented by the following general formula emulsified and dispersed using at least one high-boiling organic solvent having a solubility of 0.1 g or more per 100 g is subjected to color development. It has been found that the above object can be achieved by removing 90% or more of the content of the high-boiling organic solvent from the light-sensitive material before processing. [General formula] However, X is a group that is eliminated during the color development reaction, R ₁ is hydrogen, halogen, or an alkoxy group, and R ₂
is −NHCO・R ₃ , NHSO ₂・R ₃ or −COO・R ₃
(R ₃ represents an optionally substituted alkyl group.)
represents. Representative examples of the yellow coupler represented by the above general formula include the following. These yellow couplers are disclosed in, for example, West German Published Patent Application No. 2057941, West German Published Patent Application No. 2163812, Japanese Unexamined Patent Publication No. 47-26133, Japanese Unexamined Patent Publication No. 48-29432, Japanese Unexamined Patent Publication No. 50-65231, No. 51-3631, Japanese Patent Publication No. 1973
−50734, JP-A-51-102636, JP-A-51-
No. 33410, JP-A-48-66835, JP-A-48-94432
It can be synthesized according to the method described in JP-A-49-1229, JP-A-49-10736, JP-B-52-25733, etc. In the present invention, one of these yellow couplers may be used alone or two or more thereof may be used in combination. The amount of these couplers added is 1 silver halide.
It is preferable to add 10 to 300 g per mole, but the amount may be varied depending on the purpose of application. Representative examples of high boiling point organic solvents used in the present invention include the following.

【table】

[Table] The high boiling point organic solvent for the yellow coupler in the present invention may be either one type of high boiling point organic solvent having a solubility in water at 20°C of 0.1 g or more or a combination of two or more types. It may also be used in combination with a high boiling point solvent whose solubility in water at 20°C is less than 0.1 g; 0 to 50% of high boiling point organic solvent that is less than 0.1g
Preferably, it is % by volume. It is preferable to add hydroquinone derivatives together with the yellow coupler and high-boiling organic solvent used in the present invention for the purpose of preventing staining and color mixing. Typical hydroquinone derivatives include the following specific examples. (H-1) 2,5-di-t-octylhydroquinone (H-2) 2-t-octyl-5-methylhydroquinone (H-3) 2,6-di-n-dodecylhydroquinone (H-4) 2-n-dodecylhydroquinone (H-5) 2,2'-methylenebis-5,5'-di-t-butylhydroquinone (H-6) 2,5-di-n-octylhydroquinone (H-7) 2 -Dodecylcarbamoylmethylhydroquinone (H-8) 2-(β-n-dodecyloxycarbonyl)ethylhydroquinone (H-9) 2-(N,N-dibutylcarbamoyl)hydroquinone (H-10) 2-n-dodecyl- 5-chlorohydroquinone (H-11) 2-octadecyl-5-methylhydroquinone (H-12) 2,5-di-(P-methoxyphenyl)hydroquinone (H-13) 2-t-octylhydroquinone (H- 14) 2,5-Dichloro-3,6-diphenylhydroquinone These hydroquinone derivatives may be used alone or in combination of two or more, and the amount added is usually preferably 0.01 to 10 mol per mol of coupler, particularly 0.05 to 3 mol is preferred. The yellow coupler used in the present invention and the above hydroquinone derivative are both hydrophobic, and it is preferable to mix and dissolve them together and disperse them. First, the solubility of these mixtures in 100g of water at 20℃ is 0.1.
g or more, or a mixed solvent of the high boiling point organic solvent and the low boiling point water-insoluble organic solvent, or a mixed solvent of the high boiling point organic solvent and the low boiling point water-soluble organic solvent, and this solution is Fine oil droplets are dispersed in an aqueous solution of hydrophilic colloid such as an aqueous gelatin solution by ultrasonic or mechanical methods. In this case, in order to improve dispersibility or stability of the dispersion, it is necessary to add a surfactant as an emulsifier (for example, sodium dodecylbenzenesulfonate) to the hydrophilic colloid solution. Furthermore, if necessary, there is also a method of heating the dispersion under reduced pressure to remove the low-boiling organic solvent. The low boiling point solvent that can be used together with the high boiling point solvent as a cosolvent in the present invention is disclosed in U.S. Patent No. 2801170.
The low boiling point organic solvents include the following. (1) Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, isopropyl acetate, ethyl formate, nitromethane, carbon tetrachloride,
Low-boiling organic solvents substantially insoluble in water, such as chloroform, etc. (2) Methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate,
Water-soluble organic solvents such as methanol, ethanol, acetonitrile, dimethylformamide, dioxane, etc. As the color developing agent used for the color development in the yellow image forming method of the color photographic material of the present invention, aromatic primary amine compounds such as N,N-diethyl-p-phenylenediamine, N-ethyl-N
-Hydroxyethylparaphenylenediamine, 4
-(N-ethyl-N-hydroxyethyl)amino-2-methylaniline, 4-(N-ethyl-N-
β-methanesulfonamidoethyl)amino-2-
Methylaniline, 4-(N,N-diethyl)amino-2-methylaniline, 4-(N-ethyl-N
-methoxyethyl)amino-2-methylaniline and their sulfates, hydrochlorides, sulfites, p-
Examples include toluene sulfonate. The color developing solution may contain an alkali metal sulfite, carbonate, bisulfite, chloride, bromide, or iodide. In addition to the color development process, color photographic processing processes include bleaching, fixing, washing, and stabilization. In the present invention, the type, order, number, temperature, and time of these processing steps may be changed as appropriate to achieve the purpose. In the forming method of the present invention, the high boiling point organic solvent according to the present invention is used in processing steps including color development, such as color development, bleach-fixing, water washing, stabilization or color development,
It flows out from the sensitive material into each processing solution during processing steps such as bleaching, fixing, washing, and stabilization. The processing conditions vary depending on the type of high-boiling organic solvent contained in the photosensitive material, the content of the high-boiling organic solvent, etc., and cannot be determined unconditionally, but the processing temperature, processing time, etc. in each of the above processing steps, etc. This can be determined by making an appropriate selection. In addition, when actually carrying out the present invention, for example, a photosensitive material is experimentally processed under certain conditions, and the high boiling point organic solvent content before processing and the residual rate of high boiling point organic solvent after processing are determined. The elution rate of the boiling point organic solvent may be calculated, the results may be fed back to find processing conditions according to the present invention, and the processing may be performed under those conditions. Various silver halide salts such as silver chloride, silver iodobromide, and silver chloroiodobromide are used in the color photographic emulsion used in the present invention. It may be optically sensitized with dyes, etc., and may contain ordinary photographic additives such as fog suppressants, stabilizers, antifouling agents, polymeric additives for improving physical properties, hardeners, coating aids, etc. It may be The light resistance of color images can be further improved by incorporating an ultraviolet absorber into the color photographic material used in the present invention. The silver halide color photographic emulsion of the present invention may contain various photographic additives such as those mentioned above, if necessary, and then be coated with cellulose acetate, cellulose nitrate, A silver halide color photographic light-sensitive material is obtained by coating it on a support such as a synthetic resin film such as polycarbonate, polyethylene terephthalate or polystyrene, baryta paper, polyethylene-coated paper, or a glass plate. The silver halide color photographic emulsion of the present invention can be applied to all kinds of coupler-containing internal color photographic light-sensitive materials such as color negative films, color positive films, color reversal films, and color papers. EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited thereto. Example 1 The following layers were sequentially coated on a support 4 made of polyethylene-coated paper from the support side.

[Table] After completely dissolving liquids A and B having the above composition at 60°C, add liquid A to liquid B, stir for 5 minutes in a homomixer, and then use a homogenizer to disperse the average particle size of oil droplets. Dispersion was carried out until the diameter was approximately 0.2μ. This dispersion was mixed into a blue-sensitive silver halide emulsion (silver chloroiodobromide emulsion containing 1 mol% silver iodide and 80 mol% silver bromide) containing photographic additives such as a hardener and a spreading agent. Gelatin per mole of silveride
Contains 400g of sensitizing dye per mole of silver halide It is sensitized using 2.5×10 ^-4 mol and contains 1 mol of silver halide), and coated so that the coated silver amount is 400 mg/m ² . (Layer 2) Gelatin layer (protective layer) Fifteen types of samples were prepared by changing and combining the yellow coupler (a) and high boiling point organic solvent (b) in the above coupler dispersion recipe as follows. (a) Yellow coupler 1 Comparison coupler 2 Exemplary coupler (Y-7) 3 Exemplary coupler (Y-19) (b) High boiling point organic solvent 1 High boiling point organic solvent for comparison
Solubility in 100g of water at 20°C Dibutyl phthalate 0.01g or less 2 Di-2-ethylhexyl phthalate 3 Tricresyl phosphate 0.01g or less 4 Exemplary high-boiling organic solvents HBS-1 5 HBS-10 As above Using a sensitometer (KS-7 model manufactured by Konishiroku Photo Industry Co., Ltd.), the 15 types of samples prepared in the above were exposed to blue light through a light wedge, and then processed according to the following processing steps. Ta. [Processing process] Processing time Temperature color development 3.5 minutes 31℃ Bleach-fixing 1.5 minutes 31℃ Washing with water 3.0 minutes 31℃ [Processing process] Processing time Temperature color development 5.0 minutes 23℃ Bleach-fixing 2.0 minutes 23℃ Washing with water 4.0 minutes 23℃ The composition of the treatment liquid used in each treatment step is as follows. Color developing composition: N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 4.0g Hydroxylamine sulfate 2.0g Potassium carbonate 25g Sodium chloride 0.1g Sodium bromide 0.2g Anhydrous sodium sulfite 2.0g polyethylene glycol (average degree of polymerization 400) 3.0ml Add water to make 1, and adjust the pH to 10.0 using sodium hydroxide. Bleach-fix solution composition: Ethylenediaminetetraacetic acid sodium salt 60.0g Ammonium thiosulfate 100g Sodium bisulfite 20.0g Sodium metabisulfite 5.0g Add water to make 1, and adjust to PH7.0 using sulfuric acid. Table 1 shows the results of measuring the maximum reflection density of the yellow dye image and the light resistance of the yellow image for each sample obtained using a photoelectric densitometer (Model PDA-60, manufactured by Konishiroku Photo Industry Co., Ltd.).

【table】

[Table] However, the light resistance in the table is when exposed to light for 20 days using a xenon fade meter at a temperature of 24.5℃ and a relative humidity of 45% at a light intensity of 500 foot candela.
It is expressed as the residual rate (%) at an initial concentration of 1.0. On the other hand, for each of these samples, the residual rate of the high boiling point organic solvent after treatment was investigated using the following method. Finely chop 1 m ² of each raw sample (sample before processing) into proteolytic enzyme pronase (manufactured by Kaken).
Add to 0.05% aqueous solution 2 at 38°C and dissolve.
This aqueous solution is extracted with ethyl acetate 2, and the high boiling point organic solvent therein is quantitatively analyzed by gas chromatography. This amount is defined as Amg/m ² . Next, the high boiling point organic solvent in the sample after the treatment is quantitatively analyzed using the same procedure as above for the sample after all the treatment steps. This amount is defined as Bmg/m ² . Therefore, the elution rate of the high boiling point organic solvent in the treatment process is expressed as follows: Elution rate = A - B / A × 100 (%) The high boiling point solvent after the treatment process for each sample obtained in this way The elution rate is shown in Table 2.

【table】

[Table] From Table 2, the elution rate of the high boiling point solvent was less than 90% in all samples in the treatment process, and the effect of the present invention could not be obtained. On the other hand, in the processing process,
Only when HBS-1 and HBS-10 were used as high boiling point solvents, an elution rate of 90% or more was shown. On the other hand, in Table 1, when comparing the light resistance of the yellow dyes obtained by the treatment process and the treatment process for Samples 9, 10, 14, and 15, it can be seen that the light resistance was significantly improved in the treatment process. Also,
Looking at each coupler block, the comparison coupler showed no improvement in light resistance due to the high boiling point organic solvent, and was treated using an exemplary coupler in a treatment step that eluted 90% or more of the high boiling point organic solvent before treatment. A significant improvement in light resistance was observed only when As a further supplement, the treatment process and the treatment conditions give almost the same maximum concentration, but as can be seen from Table 2, in the treatment process, the combination of the high boiling point organic solvent according to the present invention and the yellow coupler according to the present invention (sample No. 9, 10, 14, 15), the elution rate of high-boiling organic solvents is less than 90%, and as can be seen from Table 1, the improvement in light resistance is not sufficient. It can be seen that the object of the present invention cannot be achieved under the conditions of the processing step. Example 2 On a support made of polyethylene-coated paper, the following layers were sequentially coated from the support side. Layer 1 A blue-sensitive silver halide emulsion containing a yellow coupler was coated in the same manner as Layer 1 of Example 1, and the amount of silver coated was
Apply at a concentration of 400mg/ ^m2 . Layer 2 Gelatin layer (intermediate layer) Layer 3 A green-sensitive silver halide emulsion containing macenta coupler (silver chlorobromide emulsion containing 80 mol% silver bromide, containing 500 g of gelatin per mol of silver halide, Sensitizing dye per mole of silver halide Sensitized using 2.5×10 ^-4 mol of phthalic acid di-
The following macenta coupler dissolved and dispersed in 2-ethylhexyl (containing 2×10 ^-1 mol per mol of silver halide) was coated so that the amount of coated silver was 500 mg/m ² . Layer 4 Ultraviolet absorbing layer coated so that the amount of ultraviolet absorber is 700 mg/m ² (The following ultraviolet absorbers were dissolved and dispersed in dinonyl phthalate in equimolar ratios) Layer 5 Red-sensitive silver halide emulsion containing cyan coupler (silver chlorobromide containing 80 mol% silver bromide, containing 500 g of gelatin per mole of silver halide, sensitizing dye per mole of silver halide) The following cyan coupler was sensitized using 2.5×10 ^-4 mol and dissolved and dispersed in dinonyl phthalate. (containing 2×10 ^-1 mol per mol of silver halide) was coated so that the amount of coated silver was 500 mg/m ² . Layer 6 Gelatin layer (protective layer) dry film thickness 1μ Here, a sample was prepared by dispersing the yellow coupler used in Layer 1 as shown in Table 3.

[Table] However, the comparison yellow coupler in Example 2 (☆
mark) is was used. The 15 types of samples prepared as described above were exposed to blue light through a light wedge using a sensitometer in the same manner as in Example 1, and then treated according to the same processing steps as in Example 1. Summer. Table 4 shows the results of measuring the yellow dye image, maximum reflection density, and light resistance of the yellow image for each of these samples. However, the light resistance in the examples is 40 at a light intensity of 500 foot candela using a xenon fademeter at a temperature of 24.5°C and a relative humidity of 4%.
It is expressed as the residual rate at an initial concentration of 1.0 when subjected to a daily exposure test.

[Table] Next, Table 5 shows the elution rates of the high boiling point organic solvents after the treatment steps for these samples.

【table】

【table】

[Table] From Tables 4 and 5, the solubility of the yellow coupler represented by the general formula of the present invention in water at 20°C is
Samples made by emulsification and dispersion using 0.1g or more of a high-boiling organic solvent (sample numbers 8, 9, 10, 13,
14, 15), it was confirmed that the light resistance could be significantly improved only when a treatment was performed to elute 90% or more of the content of the high-boiling organic solvent before treatment.

Claims (1)

[Scope of Claims] 1. Contains at least one yellow coupler represented by the following general formula emulsified and dispersed using at least one high-boiling point organic solvent having a solubility in 100 g of water at 20°C of 0.1 g or more. A yellow image characterized in that 90% or more of the content of the high-boiling organic solvent before processing is removed from the light-sensitive material by subjecting the silver halide color photographic light-sensitive material to a processing step including color development. How to form. [General formula] (In _the formula _,
is −NHCO・R ₃ , −NHSO ₂・R ₃ , or −
COO·R ₃ (R ₃ is an alkyl group). )