JPS5832702B2 - Color Genzo Yoso Seibutsu - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color developing composition for silver halide color photographic light-sensitive materials, and more specifically to a composition for color development of silver halide color photographic light-sensitive materials, which can be made into an extremely highly concentrated alkaline aqueous solution and which can be used to develop silver halide color photographic light-sensitive materials in color. The present invention relates to a color developing composition containing a color developing agent that is capable of forming a color photographic image of excellent quality when developed.

Generally, in order to process a silver halide color photographic light-sensitive material to form a color photographic image, the light-sensitive material is imagewise exposed and developed with a developing composition containing a p-phenylenediamine-based developing agent. A method is used in which a developing agent is oxidized at the same time as silver halide is reduced to silver, and the resulting oxidation product is combined with a coupler to form an image-like dye corresponding to the developed silver. .

A method of forming a color image by developing with a developing composition containing a color developing agent as described above includes, for example, imagewise exposing a silver halide color photographic light-sensitive material containing a non-diffusible coupler, and then coloring it. There is an internal development method in which a color negative image is formed by processing with a developing composition containing a developing agent, followed by desilvering and fixing, and after imagewise exposing a silver halide color photographic light-sensitive material that does not contain a coupler. There is an external development method in which a developing composition containing a color developing agent and a diffusible coupler is processed, followed by desilvering and fixation to form a negative color image, and there is also an internal or external silver halide color photographic method. After imagewise exposure of the material, a first black-and-white development is carried out, and the remaining silver halide emulsion is then uniformly re-exposed and treated with an internal or external color developing composition, followed by desilvering and fixing. There is a method of forming an inverted color photographic image using

Recently, such silver halide color photographic light-sensitive materials have come to be continuously processed using automatic processing machines for processing large amounts of silver halide materials within a short period of time.

As described above, rapid processing is required, and color images obtained through development processing are also desired to have high density and excellent image quality.

Furthermore, conventionally, in order to create a color developing composition containing a p-phenylenediamine-based developing agent, a dissolving device is used each time a development process is performed, and a great deal of labor, cost, and time is required to prepare developing chemicals, especially for color development. The main drug is dissolved.

If the developing chemicals, especially the developing agents, could be dissolved in advance in a concentrated solution, such as a sodium sulfite aqueous solution that acts as a preservative, and if this concentrated solution could be stored stably, it would be possible to meet the demand. The most convenient method is to dilute it as appropriate.

If a concentrated aqueous solution of a color developing agent can be easily prepared in this way, a developing composition with a high developing ability can be easily prepared using this solution.
Therefore, it is also possible to carry out efficient color development using this.

In the past, various attempts have been made to improve the solubility in alkaline aqueous solutions by using color developing agents such as p-phenylenediamine hydrochloride, sulfate, and p-toluenesulfonate, but these efforts have not yet been put to practical use. The reality is that no satisfactory color developing agent has been found which has excellent image-forming properties and is highly soluble in alkaline aqueous solutions.

By containing a color developing agent with high solubility in an alkaline aqueous solution, the present invention can form an extremely highly concentrated alkaline aqueous solution, and therefore can efficiently process silver halide color photographic light-sensitive materials. The present invention also provides a color developing composition capable of forming color images with high density and excellent image quality.

The present inventors have discovered that the above object can be achieved by incorporating a compound represented by the following general formula into a color developing composition.

[In the formula, R1 and R2 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may have a substituent (however, R1 and R2 may form a heterocycle together with a nitrogen atom, and the substituted alkyl group is , such as hydroxyalkyl group, aminoalkyl group, alkoxyalkyl group, acylamidoalkyl group,
(carbamylalkyl group, alkylsulfonamidoalkyl group, aryloxyalkyl group, etc.); R
3, R4゜R5 and R6 are a hydrogen atom, a hydroxy group, an amino group, an alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or an alkyl group having 1 to 6 carbon atoms which may have a substituent ( However, R6 may form a 5- or 6-membered ring together with R1, and the substituted alkyl group includes, for example, a hydroxyalkyl group, an aminoalkyl group, an acylamidoalkyl group, or an alkylsulfonamidoalkyl group); Number of carbon atoms: 2-20
The alkyl group and n represent a positive integer of 1 to 4.

] That is, the color developing agent according to the present invention represented by the above general formula has a lower sulfite content than conventionally known color developing agents such as the hydrochloride, sulfate or p-toluenesulfonate of para-phenylenediamine compounds. It has excellent solubility in alkaline aqueous solutions such as I-IJum, sodium carbonate, or sodium hydroxide.

Therefore, it is possible to create a high-density color developing composition depending on the purpose, and it is not only possible to develop at a faster speed, but also has excellent desilvering properties during processing. In addition, the color image obtained by processing has good color purity of the dye, has little capri, and has high density.

In addition, since it dissolves in an alkaline aqueous solution at a high concentration, it becomes possible to handle the developing composition in the form of a so-called kit.
It is extremely convenient for manufacturing and sales and for handling by consumers.

Furthermore, the color developing agent according to the present invention is highly soluble in an alkaline aqueous solution such as sodium sulfite, which acts as a preservative, and has excellent preservability. It is stored not as a powder but as a concentrated solution and transported from the manufacturer to the consumer, who can dilute it appropriately and supply it to a developing device for use.

When supplied to a developing device, it is mixed with a concentrated aqueous solution of other development auxiliary chemicals and diluted as appropriate to prepare a developing composition.

Therefore, there is no need to spend a large amount of money to prepare a stirring device and spend time and effort to dissolve powdered chemicals every time development is carried out, which is the case in the past. can be created.

In order to handle such concentrated solutions, it is desirable to reduce the water content as much as possible and increase the concentration to the highest level that provides a stable solution, and the present invention provides a color developing agent and a developing composition that meet this purpose. It is possible to provide

Specific compounds of the color developing agent represented by the above general formula according to the present invention include (1) N,N-diethyl-4-aminoaniline-p-ethylbenzenesulfonate (2) N,N-diethyl-4-aminoaniline-p-ethylbenzenesulfonate; 3-Methyl-4-aminoaniline-p-ethylbenzenesulfonate (3) N-
Ethyl-N-methoxyethyl-3-methyl-4-aminoaniline-p-ethylbenzenesulfonate (4) N-ethyl-N-hydroxyethyl-3-methyl-4-aminoaniline-p-ethylbenzenesulfonate ( 5) N-ethyl-N-(2-(methylsulfonamido)ethylio3-methyl-4-aminoaniline-p-ethylbenzenesulfonate (6) N,N-diethyl-3-methylsulfonamidoethyl-4- Aminoaniline-p-ethylbenzenesulfonate (7) N,N-bismethoxyethyl-3-methyl-4-
Aminoaniline-p-ethylbenzenesulfonate (8) N-methyl-N-(2-(2-methoxyethoxy)ethylio3-methyl-4-aminoaniline-p-ethylbenzenesulfonate (9) N-ethyl- N-(2-(2-methoxyethoxy)ethylio3-methyl-4-aminoaniline-p-ethylbenzenesulfonate 00)N-ethyl-N-(1-methyl-2-methoxy)
Ethyl-3-methyl-4-aminoaniline-p=ethylbenzenesulfonate αυ N-ethyl-N-(2-(2-(2-methoxyethoxy)ethoxy)ethyl)-3-methyl4-aminoaniline-p -Ethylbenzenesulfonate (12) N,N-bis-(2-(2-methoxyethoxy)ethylio3-methyl-4-aminoaniline-p-ethylbenzenesulfonate (13) 2-methyl-4-morpholinoaniline -p
-Ethylbenzenesulfonate (14) 6-amino-1-ethyl-1,2,3,4-tetrahydro-quinoline-p-ethylbenzenesulfonate (15+N,N-diethyl-4-aminoaniline-〇-
Ethylbenzenesulfonate (L6) N-ethyl-N-methylsulfonamidoethyl-3-methyl-4-aminoaniline-m-ethylbenzenesulfonate (17) NjN-diethyl-3-methyl-4-aminoaniline-p -Propylbenzenesulfonate (18)
N-ethyl-N-methoxyethyl-3-methyl-4-
Aminoaniline-p-propylbenzenesulfonate (19) N-ethyl-N-(2-(2-methoxyethoxy)ethylio3-methyl-4-aminoaniline-
p-Propylbenzenesulfonate (20) N-ethyl-N-hydroxyethyl-3-methyl-4-aminoaniline-p-butylbenzenesulfonate (21) N-ethyl-N-methylsulfonamidoethyl-3 -Methyl-4-aminoaniline-p-butylbenzenesulfonate (22) N-ethyl-N-(2-(2-methoxyethoxy)ethylio3-methyl-4-aminoaniline-
p-Butylbenzenesulfonate (23) N-ethyl-N-hydroxyethyl-3-
Methyl-4-aminoaniline-p-octylbenzenesulfonate (24) N-ethyl-N-(2-(methylsulfonamido)ethylio3-methyl-4-aminoaniline-p
-Dodecylbenzenesulfonate (25) N-ethyl-N-methylsulfonamidoethyl-3-methyl-4-
Aminoaniline-p-hexadecylbenzenesulfonate (26) N-ethyl-N-methoxyethyl-3-methyl-4-aminoaniline-p-octadecylbenzenesulfonate and the like can be mentioned.

Examples of raw materials used to synthesize the color developing agent of the present invention include N-alkylaniline, N-alkyl-3-alkylaniline, N-alkyl-3-alkoxyaniline, and N-alkyl-3-alkylsulfonamide. N-monoalkyl- such as aniline, N-alkyl-3-acylamidoaniline, N-alkyl-3-hydroxyaniline, N-alkyl-3-alkylsulfonamidoalkylaniline or N-alkyl-3-acylamidoalkylaniline Substituted anilines can be used manually, in which case these N-monoalkyl-substituted anilines are combined with, for example, alkyl halides, alkoxyalkyl halides, alkylsulfonamidoalkyl halides, carbamylalkyl halides, halogenated The corresponding N,N-disubstituted aniline is produced by reacting with a halide such as acylamidoalkyl, halogenated hydroxyalkyl, ■-halogen-2-(2-methoxyethoxy)ethane, and ■-halogen-1-methyl-2-methoxyethane. or alcohols such as methyl alcohol, ethyl alcohol, flobyl alcohol, methyl alcohol, and octyl alcohol, and their alkyl groups are alkoxy groups, alkylsulfonamino groups,
Alcohols substituted with acylamido groups, hydroxyl groups, etc., alkylene glycols such as diethylene glycol, triethylene glycol, flopylene glycol, cyfropylene glycol, and their monoalkyl ethers are reacted with P-toluenesulfonic acid halide. The corresponding p-toluenesulfonic acid ester can be synthesized, and then the corresponding N,N-disubstituted aniline can be synthesized and used by reacting it with the N-monoalkyl-substituted aniline.

Also, 3-alkylaniline, 3-alkoxyaniline, 3
- Anilines such as alkylsulfonamide aniline, 3-acylamidoaniline, 3-hydroxyaniline, 3-hydroxyalkylaniline, 3-alkylsulfonamidealkylaniline, or 3-acylamidoalkylaniline, and the above-mentioned halide or p-4 toluene N,,N-disubstituted aniline can be synthesized and used by reacting it with a sulfonic acid ester.

To synthesize the color photographic developer according to the present invention from the N,N-disubstituted aniline, first, a diazonium compound obtained by diazotizing substituted or unsubstituted aniline is added to the N,N-disubstituted aniline. Coupling is performed to synthesize an azo dye, which is then hydrogenated using a catalyst such as palladium-carbon or nickel to synthesize the corresponding p-phenylenediamine compound, or the N,N-disubstituted aniline The corresponding p-phenylenediamine compound can be synthesized by nitrosating and then reducing the same.

In order to convert the thus obtained p-phenylenediamine compound into an alkylbenzene sulfonate, the free p-phenylenediamine compound is reacted with an alkylbenzene sulfonate, and the salt is crystallized by cooling. All you have to do is precipitate it.

It is also possible to synthesize a desired alkylbenzenesulfonic acid salt of a p-phenylenediamine-based compound by neutralizing a known hydrochloride or sulfate of a p-phenylenediamine-based compound and then adding an alkylbenzenesulfonic acid thereto.

Next, a specific synthesis example of the color developing agent used in the present invention is shown below.

Synthesis Example 1 [Synthesis of Exemplified Compound (1)] N,N-diethylaniline was nitrosated, and this was reduced with iron powder to produce the known 4-amino-N,N-diethylaniline (B, P, 105°/3 mmHg) was obtained.

5 ml of methyl alcohol was added and dissolved in 7 g of this, and the calculated amount of p-ethylbenzene sulfonic acid was dissolved in 20 liters of methyl alcohol and mixed to cause an exothermic reaction.

After cooling with water, 200 ml of ethyl acetate was added to precipitate crystals.

The crystals were separated from each other and reconsolidated in a mixed solvent of methyl alcohol and ethyl acetate to obtain the desired compound.

The melting point was 205-207°C, and the yield was about 85%.

Synthesis Example 2 [Synthesis of Exemplified Compound (4)] A known sulfate of N-ethyl-N-hydroxyethyl-3-methyl-4-aminoaniline was dissolved in sodium carbonate to obtain a free amine.

A calculated amount of a methyl alcohol solution of p-ethylbenzenesulfonic acid was added to the free amine thus obtained to cause a reaction, and ethyl acetate was gradually added to precipitate crystals, which were then filtered and dried. White powdery crystals were obtained.

The yield was about 80% with a melting point of 180-182°C.

Synthesis Example 3 [Synthesis of Exemplified Compound (5)] The known sulfate of N-ethyl-N-(2-(methylsulfonamido)ethyl)-3-methyl-4-aminoaniline was neutralized with sodium carbonate to form the free Obtained amine.

A calculated amount of methyl alcohol solution of p-ethylbenzenesulfonic acid was added to the amine thus obtained to cause a reaction, and then ethyl acetate was gradually added to precipitate crystals, which were then overdried to form a white powder. Obtained crystals.

The melting point was 172-174°C and the yield was about 85%.

Synthesis Example 4 [Synthesis of Exemplified Compound (24)] The free amine obtained in Synthesis Example 3 was reacted with a calculated amount of p-dodecylbenzenesulfonic acid dissolved in methyl alcohol, and then ethyl acetate was gradually added. After the crystals were precipitated, they were overdried to obtain white powdery crystals.

The melting point was 134-138°C and the yield was about 60%.

The other exemplified compounds can also be synthesized in the same manner as in the above synthesis example by using the corresponding p-phenylenediamine compound and the corresponding alkylbenzenesulfonic acid.

To prepare a color developing composition containing a developing agent used in the present invention, for example, the developing chemicals are divided into several groups, and a concentrated aqueous solution, a so-called kit, is prepared for each group.

Such kits are commercially stocked, sold and shipped to consumers who can mix and dilute the designated types of kits to create the desired developer composition.

Examples of such kits include [A kit] color developing agent sodium sulfite Add water to make 11.

[B kit]

Sodium carbonate 250-400g Sodium sulfite 40-70g Sodium bicarbonate
50-7]9 Sodium bromide
10-20g potassium iodide 5-15
g Add water to make 11.

[C kit]

hydroxyamine sulfate sulfuric acid 200-400g 5-10g 200-30 (1 100-200mg (for pH adjustment) Add water to make 11.

There are various products such as
Adjust and use so that H is 9.0 to 11.0.

It is commercially, economically and conveniently for each kit used at this time to be as concentrated as possible from the viewpoint of handling, and in particular, in the A kit, the color developing agent is dissolved in an aqueous solution of, for example, sodium sulfite or sodium carbonate. The most important point in determining commercial value is the level of solubility that can be achieved while maintaining storage stability.

The color developing composition of the present invention can be applied to any of conventional internal and external color negative/positive, reversal and other silver halide color photographic light-sensitive materials.

EXAMPLES Next, the present invention will be explained in more detail using Examples, but the embodiments of the present invention are not limited thereby.

The p-phenylenediamine compound used in Examples 1 and 2 has the following structure among the free bases of the color developing agent represented by the above general formula according to the present invention.

(However, substituents R1, R2 and R4 are specifically shown in Tables 1 and 2.

) Example 1 To a solution prepared by dissolving 3.3 g of anhydrous sodium sulfite in 11 water, the alkylbenzene sulfonate of p-diphenylenediamine compound according to the present invention as listed in Table 1 was added little by little under stirring to saturate the solution. Solutions were prepared and used as samples (sample/% 1, 3, and 5).

Separately, for comparison purposes as listed in Table 1, sulfates and p-toluenesulfonates of p-phenylenediamine-based compounds were dissolved in the sodium sulfite aqueous solution to prepare a saturated solution, which was then used as a comparative sample (sample/ 162,4 and 6)
And so.

The number of grams and number of moles of the color developing agent contained in these samples and Comparative Sample No. 11 were measured, and the values are shown in Table 1.

It can be seen from Table 1 that the sample according to the present invention has a lower solubility in an aqueous sodium sulfite solution than the comparative sample.

Example 2 An alkylbenzene sulfonate of a p-phenylenediamine compound according to the present invention as shown in Table 2 was dissolved in a pH 10 phosphate buffer solution 11c to which 3.3 g of sodium sulfite was added, thereby adjusting the pH value. The pH was adjusted to 10 by adding sodium hydroxide.

This operation was repeated until the color developing agent reached its solubility limit, and the resulting saturated solutions were used as samples (Samples 7, 11 and 14).

Separately, a comparative sample (
Sample A68 y 9 t 10 t 12.13 and 1
5) was obtained.

The number of grams and number of moles of the color developing agent contained in the samples thus obtained and comparative samples were measured, and the values are shown in Table 2.

Table 2 shows that the sample has significantly better solubility in a pH 10 buffer solution than the comparative sample.

Example 3 On a paper support laminated with polyethylene colored with T io 2, 6μ/100ci of silver iodobromide and JP-A-1988
A blue-sensitive gelatin emulsion layer containing a diffusion-resistant a-pivalyl acetanilide type 2-equivalent yellow coupler described in Japanese Patent Publication No. 29432, silver chlorobromide of 4/100 d and JP-A-48-27930. A green-sensitive gelatin emulsion layer containing a diffusion-resistant 5-pyrazolone type magenta coupler described in the publication, and a diffusion-resistant phenol described in U.S. Pat. A silver halide color photographic paper on which a gelatin emulsion layer containing a type cyan coupler was continuously coated was prepared and used as a development sample.

This sample was subjected to wedge exposure through blue, green, and red filters in the usual manner, and then exposed as described below.
Developer solution (4) and developer solution (0) according to the present invention using the following exemplified compounds, and developer solution (B) and developer solution (D) using the following two types of developer for comparison. Processed with
Thereafter, samples with four types of color images were prepared by processing with the following bleach-fix solution and stabilizing solution.

[Processing process]

color development bleach fixing washing with water Stabilization [Developer for color photography] benzyl alcohol Sodium hexametaphosphate anhydrous sodium sulfite sodium bromide 5, Ornl.

3.00g 1.8F1 1.41 Processing time 3 minutes 30 seconds 1 minute 30 seconds 2 minutes 0 seconds 1 minute 0 seconds 31°C Potassium bromide 0.50 g Borax (
Na2B4O7* 10H20) 39.109 0.01 mol of the following color photographic developing agent Add water to make it 11, and adjust the pH to 10 with sodium hydroxide.
, adjusted to 3.

[Bleach-fix solution]

Iron ammonium ethylenediaminetetraacetate 61.0g 2-ammonium ethylenediaminetetraacetate 5.0
g Ammonium thiosulfate 124.5P Sodium metabisulfite 13. ．． Sodium bisulfite 271 Water was added to make up to 11, and the pH was adjusted to 6.5.

[Stabilizing liquid]

Glacial acetic acid (trihydrate) 2011Ll 800TrLl of pure water was added, and the pH was adjusted to 3.5 to 4.0 using sodium acetate trihydrate.

The three color densities of yellow, magenta and cyan were measured for these samples using a PD-7R densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.), and the photographic performance obtained is shown in Table 3.

Note that the sensitivity is a relative value when the sensitivity of the comparison sample is set as 100.

Table 3 shows that when a silver halide color photographic light-sensitive material is processed with a color developer containing a developing agent according to the present invention, the sensitivity, fog, and maximum color image density are all lower than that of a color developer containing a comparative developing agent. It can be seen that the results are superior to those treated with .

Example 4 Using a multilayer silver halide color photographic light-sensitive material Sukura Color ■ film (manufactured by Konishiroku Photo Industries Co., Ltd.), three-color separation wedge exposure of blue light, green light, and red light was performed, and then 38 cm was exposed according to the following processing steps. Processing was carried out at °C using the E color developer of the present invention and the comparative F color developer, fixer and stabilizing solution having the following formulations.

The films obtained by this treatment were designated as Sample E and Comparative Sample F.

[Processing process]

Color development 3 minutes 15 seconds Bleaching 6 minutes 30 seconds Development 3 minutes 15 seconds Fixing 6 minutes 30 seconds Washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds [E color development] Exemplary compound (4L, 9.6g
Anhydrous sodium sulfite 0.14g Hydroxyamine 1/2 sulfate 1.98g Sulfuric acid
0.76■ Anhydrous potassium carbonate
28.85g anhydrous potassium sulfite
5.10g potassium bromide
1.16.9 Sodium chloride
0.14g nitrilotriacetic acid trisodium salt (monohydrate) 3. ．． 20.9* Potassium hydroxide 1.48g Water was added to make the solution to 11.

[F color developer]

N-ethyl-N-hydroxyethyl-3-methyl- in place of color developing agent exemplified compound (4) in E color developer
It was prepared in the same manner as the E color developer except that 4-aminoaniline sulfate was used.

[Bleach solution]

Ethylenediaminetetraacetic acid iron ammonium salt 100°0g Ethylenediaminetetra 10. og diamimonium acetate ammonium chloride bromide 150.0g glacial acetic acid
The pH was adjusted to 11 by adding 10.0 TIL water, and the pH was adjusted to 6.0 using ammonia water.

[Fixer]

Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to make 11.
The pH was adjusted to 6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5M Konidax (manufactured by Konishiroku Photo Industry Co., Ltd.) 7.5ml
Add water to make it 11.

Separately, a comparative sample was prepared in the same manner as the sample except that F color developer was used instead of E color developer.

The cyan, magenta, and yellow image maximum density, sensitivity, and fog values of the three-color separation images of the sample thus obtained and the comparative sample were measured, and these values are shown in Table 4.

Note that the sensitivity is a relative value when the comparative sample is taken as 100.

It can be seen from Table 4 that the samples using the color developing agent of the present invention have higher sensitivity and maximum sensitivity than the comparative samples.

Further, as a result of comparative studies of the exemplified compounds (8) and (22) and the free base sulfates of these compounds, similarly good results were obtained.

Claims (1)

[Scope of Claims] 1. A color developing composition characterized by containing a color developing agent represented by the following general formula. General formula [wherein R1 and R2 are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent (however, R1 and R2 may form multiple rings together with a nitrogen atom); R37R4J
R5 and R6 are a hydrogen atom, a hydroxy group, an amino group, an alkoxy group, an acylamido group, a sulfonamide group, an alkylsulfonamide group, or an alkyl group having 1 to 6 carbon atoms that may have a substituent (however, R .1ζ may form a 5- or 6-membered ring); R7 has 2 to 20 carbon atoms
The alkyl group and n represent a positive integer of 1 to 4. ]