JPS599047B2 - Color photographic light-sensitive material containing a new color former - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a color photographic material, and more specifically, the present invention relates to a color photographic material in which a substantially water-insoluble coloring agent is dissolved in combination with a high-boiling organic solvent or an auxiliary solvent that is substantially immiscible with water. The present invention relates to a color photographic material containing an image-forming color former dispersed in a silver halide emulsion.

As is well known, in subtractive color photography, an aromatic primary amine color developer is exposed to light...oxidation products of the color developer produced by reducing silver halide and yellow, magenta, and cyan colors. A color image is formed by oxidative coupling of an image-forming color former in a silver halide emulsion.

Generally speaking, α-acylacetanilide compounds are used as yellow color formers, and phenol or naphthol compounds are used as cyan color formers.

Furthermore, in the case of magenta coloring agents, pyrazolone, intazolone, cyanoacetyl compounds, etc. are known, and among these, pyrazolone compounds are particularly commonly used.

When these color formers are included in a photographic emulsion, there are two methods: the so-called alkali-soluble method in which the color former is dissolved in an aqueous alkaline solution and added to the emulsion, and the other is the so-called alkali-soluble method in which the color former is dissolved in a high-boiling organic solvent and emulsified and dispersed in the photographic emulsion. The droplet dispersion method is known, but compared to the former method, the latter method has better light resistance, heat resistance,
It has excellent moisture resistance, coupling reactivity, pigment granularity, and sharpness of black images. These coloring agents used in the oil droplet dispersion method must have properties such that the color image obtained in the emulsion or after color development processing satisfies chemical or physical conditions.

That is, firstly, a high-boiling organic solvent such as di5-butyl phthalate, tricresyl phosphate, N-N-diethyldodecanamide, phosphoric acid alkyl ester, etc. or a co-solvent;
For example, it has high solubility in methanol, ethanol, ethyl acetate, butyl acetate, tetrahydrofuran, etc., and there is no precipitation of the coloring agent when it is left at high concentration in the emulsion for a long time, when it is stored in a cold state, or after it is coated on a support. , secondly, the color image obtained by the coupling reaction with the oxidation product of the color developer is high and clear, and thirdly, the color image obtained by the coupling reaction has excellent spectral absorption characteristics, and those colors The image must be heat resistant, light resistant, and moisture resistant under harsh conditions; fourthly, the raw materials are cheap and easily available, and manufacturing is easy; and fifthly, it can sufficiently contribute to reducing environmental pollution. Although required, there are currently very few coloring agents that can satisfy these conditions. In the past, benzoyl-based acetanilide compounds were mainly used as yellow color formers, but many of these color formers have high coupling reactivity, but this can lead to increased fog, a decrease in concentration over time, or However, in recent years, α-alkyloyl acetanilide compounds, especially α-pivaloylacetanilide compounds, have been used, and these color-forming The agent has lower coupling reactivity than benzoyl-based acetanilide color formers, but the dye produced has excellent spectral properties and is stable against light, heat, and humidity, so further improvements were made. Many patents have been filed for equivalent color formers.

For example, US Patent No. 3408194, US Patent No. 34479
No. 28, No. 3644498, Special Publication No. 44-26590
No., JP 4737636, JP 49-12661
No., Special Publication No. 49-12660, Special Publication No. 49-1266
No. 2, Special Publication No. 48-25933, Japanese Patent Publication No. 48-663
No. 84, JP-A-48-29432, JP-A-48-66
There are various publications such as No. 835 and Special Publication No. 49-13576.
These are those in which one hydrogen of active methylene is substituted with a substituent that is quickly eliminated when forming a dye by reacting with the oxidation product of a color developer, and furthermore, the eliminated group is It is desirable to have high coupling reactivity without adversely affecting properties.

The advantage of these 2-equivalent color formers is that they require only 1/2 the amount of silver halide compared to conventional 4-equivalent color formers, and therefore the photosensitive layer can be made thinner, which is useful in the coating and drying process of color photosensitive materials. In recent years, yellow coloring has become popular due to its desirable advantages from the viewpoint of reducing the drying load, simplifying and speeding up the processing of the obtained glass and photosensitive materials, reducing environmental pollution, sharpening color images, and saving resources. Generally, two equivalents of the agent are used.

On the other hand, many magenta color formers generally have an acylamino group at the 3-position of the pyrazolone nucleus, and dyes obtained from these color formers ideally absorb only green light and do not absorb blue and red light. Although it must be completely transparent, in reality it absorbs some blue light, has secondary absorption on the short wavelength side, and very often has poor cut-off on the long wavelength side, which impedes color reproduction. , or the unreacted color forming agent turns yellow over time and contaminates the background color. Furthermore, they are often unstable to light, heat, and humidity. In recent years, many patents have been filed for color formers that have improved these drawbacks. For example, JP-A-49
-117034, JP 47-123033, JP 49-29639, JP 49-111631,
JP-A-4974028, JP-A-49-131125, JP-A-49-74027, JP-A-49-13113
No. 6, JP-A-50-60233, JP-A-50-207
There are various publications such as No. 23, and these mainly focus on the
The color image-forming dye obtained from this dye has low secondary absorption on the short wavelength side and has good sharpness on the long wavelength side, giving a so-called strong red dye, but it is stable against light, heat, and humidity. However, there are problems with solubility in high-boiling solvents or manufacturing methods, and there are very few that can satisfy the conditions as a color former.

The object of the present invention is to find new color formers that improve these drawbacks.

As a result of various studies, the present inventors have discovered a novel coloring agent represented by the following general formula.

In the general formula, Q represents a yellow color former residue or a magenta color former residue, and the active methylene group thereof may contain a group that is easily eliminated by an oxidized color developer.

R1 is a straight chain or branched alkyl group having 5 to 15 carbon atoms,
R2 represents a hydrogen atom or a straight chain or branched alkyl group having 5 to 15 carbon atoms. The color forming agent of the present invention dissolves easily in organic solvents (high-boiling point organic solvents or low-boiling point organic solvents), and a stable emulsified dispersion can be obtained at a high concentration.Also, despite having high coupling reactivity, there is no increase in fogging. The azomethine dye, which is stable against light, heat, and humidity, has a high density and clear color image, and has low secondary absorption compared to magenta color formers. Good sharpness on the long wavelength side, maximum absorption is λMax 538~5
It is a color forming agent that exists around 42 nm and has an advantageous hue in color reproduction compared to those having an acylamino group at the 3-position of the pyrazolone nucleus. Next, specific examples of compounds of the present invention will be shown, but the present invention is not limited thereto.

Yellow color forming agent The color forming agent of the present invention is inexpensive and easily available as a raw material, and can be easily produced with short manufacturing steps, thereby contributing to cost reduction.

These manufacturing methods are easier than reacting monosuccinic acid alkyl phenyl ester, which is obtained by heating and melting succinic anhydride and alkyl phenol without a solvent, with an amino compound by a conventional method to convert the monosuccinic acid alkyl phenyl ester into an acid chloride using phosphorus pentachloride or thionyl chloride. is condensed with good yield. Next, specific synthesis examples of the present invention will be shown.

Synthesis Example 1 Synthesis of succinic acid mono-2,4-di-t-pentyl phenyl ester Succinic anhydride 1707 and 2,4-di-t-pentylphenol 2437 were mixed and melted by heating at 200°C for 7 to 8 hours. After stirring and reacting, the paste-like reaction mixture is returned to room temperature and dissolved in ethyl ether to remove insoluble materials, the filtrate is concentrated, and the residue is recrystallized with petroleum ether to obtain white powder 3507.

Melting point 89-90℃, elemental analysis C2OH3OO4, theoretical value C% 71.82, H% 9.04, experimental value C% 71.61
, H% 9.00 Synthesis Example 2 Synthesis of succinic acid mono-3-pentadecyl phenyl ester In the same manner as in Synthesis Example 1, succinic anhydride 170y and 3-pentadecylphenol 304V were heated and melted, treated with ethyl ether, and then extracted from petroleum ether. Recrystallized.

Melting point 68-69℃, yield 370r, elemental analysis C25H4
OOi Theoretical value C% 74.22, H% 9.97, experimental value C% 73.97, H% 10.04 Synthesis example 3 (Exemplary color former Y-1) 2-chloro-5-(2.4 - Mix 9.27 g of (di-t-pentylphenoxycarbonylethylamide) aniline with 80 TILI of xylene and dropwise add 4.5 y of ethyl benzoyl acetate while heating and stirring. Distill the ethanol and xylene, and distill the residue into petroleum ether. When added, white crystals are obtained.

It was recrystallized from methanol. Melting point 85-87℃, yield 6
．． 77, Elemental analysis C35H4lO5N2Cl, theoretical value C
%69.38, H%6.82, N%4.42, experimental value C
%69.09, H%6.49, N%4.39Synthesis Example 4 (Exemplary Color Former Y-2) -2-chloro-5-(2,4-di-t-pentylphenoxycarbonylethylamide ) Aniline 237 was mixed with 200 TfL of xylene, 9.0 y of methyl pivaloyl acetate was added dropwise with heating and stirring, the resulting methanol and xylene were distilled off, and the residue was recrystallized from methanol.

Melting point 133-135℃, yield 26f, elemental analysis C33H
45O5N2Cll theoretical value C%67.73, H%7.7
5, N% 4.79, experimental value C% 67.91, H% 7.7
7, N% 4.80 Synthesis Example 5 (Illustrative Color Former Y-4) 2-chloro-5-(4-t-octylphenoxycarbonylethylamide)aniline 9.6r and xylene 701
Synthesis example 3 using n1 and methyl pivaloylacetate 4,2y
It was recrystallized from ethanol in the same manner as above.

Melting point 104-105℃, yield 10.7f7, elemental analysis C
3lH4,O5N2Cl. Theoretical value C%66, 83, H%
7.42, N% 5.03, experimental value C% 66,80, H%
7.40, N% 5.21 Synthesis Example 6 (Exemplary Color Former Y-10) α-2-Methoxybenzoyl-2-chloro-5-(2.
4-di-t-pentylphenoxycarbonylethylamide) acetanilide 6.4V in chloroform 60W1
1.5 f of sulfuryl chloride was added dropwise to the mixture at room temperature, and the mixture was reacted at the same temperature for 3.0 hours. Chloroform was distilled off under reduced pressure, and the residue was recrystallized from methanol.

Melting point 138-139℃, yield 4.87, elemental analysis C36
H4, O6N2Cl2, theoretical value C%64.57, H%
6, 32, N% 4.18, experimental value C% 64.77, H%
6,29, N% 4.21 Synthesis Example 7 (Illustrative Color Former Y-13) α-pivaloyl-2-chloro-5-(4-t-octylphenoxycarbonylethylamide)acetanilide 11.57 The mixture was dissolved in 80~chloroform, and 3.2V of sulfuryl chloride was added dropwise at room temperature. After reaction at the same temperature for 3 hours, chloroform was completely distilled off under reduced pressure, hexane was added to the residue, and the resulting crystals were recrystallized from methanol.

Melting point 130-132℃, yield 8.47, elemental analysis C3l
H4OO5N2Cl2, theoretical value C%62.94, H%
6.82, N% 4.74, experimental value C% 63.11, H%
6.79, N% 4.78 Synthesis Example 8. 51 (Exemplary Color Former Y-17) α-2-methoxybenzoyl-α-chloro-2-chloro-5-(2,4-di-t-pentylphenoxycarbonylethylamide) acetanilide 13.4f and carbonic acid Potassium 3.0r and 2-(ethoxycarbonyl)ethylpyridazine-3,6-dione 4.6V in acetone 60WLI
After refluxing for 3 hours, the mixture was poured into water, extracted with ethyl acetate, washed with dilute hydrochloric acid, washed with water, dried, ethyl acetate was distilled off, and the residue was purified by column chromatography.

Melting point 84-86℃, yield 5.4y, elemental analysis C45H,
, O8ON4Cll theoretical value C%62.88, H%6.9
1, N% 6.98, experimental value C% 62.91, H% 6.7
1, N% 6.99 Synthesis Example 9 (Exemplary color former Y-19) α-pivaloyl-α-chloro-2-chloro-5-(2.
4-di-t-pentylphenoxycarbonylethylamide) acetanilide 6.2t and succinimide 1.3V
and 1.5 f of potassium carbonate were mixed with 50 ml of acetone, refluxed for 3 hours, poured into water, extracted with ethyl acetate, washed with dilute hydrochloric acid, washed with water, dried, ethyl acetate was distilled off, and purified by column chromatography.

= groan? Hibiki} Nimu Akiko. 8 7.09, N% 6.16, experimental value C% 65.32, H%
6.87, N% 6.20 Magenta color former synthesis example 10 (Exemplary color former M-5) 1-(2.4.6-trichlorophenyl)-3-(5-
6.7 t of aminobenzamide)-5-pyrazolone and 2.0 P of anhydrous sodium acetate were mixed with 1 t of acetic acid and 30111 t of acetonitrile to form 4-t-mono-succinate at room temperature.
Drop 6.5V of octyl phenyl ester chloride,
After reacting at room temperature for 1.0 hour, the mixture was poured into water, and the precipitate was filtered, washed with water, dried, and then recrystallized with a mixed solvent of benzene-ligroin.

Melting point 131-132℃, yield 6.0V1 elemental analysis C34
H35O5N4Cl3, theoretical value C%59.52, H%
5.14, N% 8.17, experimental value C% 59.22, H%
5.14, N% 8.09 Synthesis Example 11 (Exemplary color former M-6) 1-(2.4.6-trichlorophenyl)-3-(2
-chloro-5-aminoanilino)-5-pyrazolone 12
．． 0t and 4.2f7 of anhydrous sodium acetate were mixed with 150d of acetic acid and 40d of acetonitrile to form succinic acid mono-3-
15.4 V of pentadecyl phenyl ester chloride was added dropwise, and after reacting at room temperature for 1.0 hour, the mixture was poured into water, and the precipitate was filtered, washed with water, dried, and then recrystallized from acetonitrile.

Melting point 105-106℃, yield 8.77, elemental analysis C4O
H48O4N4Cl4, theoretical value C%60.76, H%6
．． 12, N% 7.09, experimental value C% 61.02, H% 6
．． 10, N% 7.10 Synthesis Example 12 (Exemplary Color Former M-7
) 1-(2,4,6-trichlorophenyl)-3-(2-chloro-5-aminobenzamide)-5-pyrazolone 8
．． Recrystallization from benzene was carried out in the same manner as in Synthesis Example 10 using 01 and 9.0 r of succinic acid mono-4-nonylphenyl ester chloride.

Melting point 165-167℃, yield 5.211 Elemental analysis C3S
H36O. N4Cl4, theoretical value C%60.05, H%5
．． 33, N% 8.00, experimental value C% 60.07, H% 5
．． 40, N% 8.04 Synthesis Example 13 (Exemplary color former M-12) 1-(2,4,6-trichlorophenyl)-3-(dichloro-5-aminoanilino)-5-pyrazolone 8.1
The same procedure as in Synthesis Example 10 was carried out using 7.0f of succinic acid mono-4-nonyl phenyl ester chloride and recrystallization was performed using a benzene-ligroin mixture.

Melting point 113-114℃, yield 7.2r, elemental analysis C3,
H36O4N4Cl Theoretical value C%62.78, H%5
．． 58, N% 8.61, experimental value C% 62.49, H% 5
．． 60, N% 8.60 Synthesis Example 14 (Exemplary color former M-14) 1-(2.4.6-trichlorophenyl)-3-(2'
-chloro-5-aminoanilino)-5-pyrazolone8.
6V and succinic acid mono-2,4-di-t-pentylphenyl ester chloride 7.5V were carried out in the same manner as in Synthesis Example 10, and recrystallized with benzene-ligroin.

Melting point 154-156℃, yield 8.4y, elemental analysis C35
H38O4N4Cl Theoretical value C%58.34, H%5
．． 32, N% 7.78, experimental value C% 58.55, H% 5
．． 29, N% 7.77 The color former of the present invention is used in the oil droplet dispersion method, and is dissolved in a high boiling point organic solvent or an auxiliary solvent if necessary, and finely emulsified and dispersed in an aqueous gelatin solution containing a dispersion activator. do.

This dispersion was added to a silver halide photographic emulsion, and the resulting color former-containing color photographic emulsion was prepared by applying it to a support and drying it. When these light-sensitive materials were subjected to color development treatment after exposure by a known method, high-density, clear color images were obtained. The present invention will now be further explained with reference to Examples.

Example 1 Illustrative coloring agent Y-155.57 was dissolved in 7.2 rne of dibutyl phthalate and 13 d of ethyl acetate to prepare 60 d of a 10% gelatin aqueous solution containing a dispersing agent (5% aqueous solution of sodium dodecylbenzenesulfonate) 12111.
In addition, after finely emulsifying and dispersing by ultrasonic dispersion, ethyl acetate was distilled off, mixed with silver chlorobromide emulsion 607, diluted with water to a viscosity suitable for coating, coated on a support coated with a polyolefin material, and dried. A photosensitive material was created.

The image was then exposed through a continuous web and processed with the color developing agent described below to obtain a clear, high density yellow image. The absorption maximum wavelength was 447 nm. Color developer, development time: 4 minutes, temperature: 31'C After washing with water, normal bleach-fixing was performed to obtain a yellow image.

Example 2 Exemplary color formers Y-16 and Y-18 in 7.5×1
When a photosensitive material obtained in the same manner as in Example 1 using 0 to 3 mol of mol is subjected to color development, the maximum absorption wavelength is 44.
Clear yellow images with wavelengths of 7 nm and 448 nm were obtained.

The color former of the present invention thus obtained and the known color former A obtained by the same method as in Example 1 (α-pivaloyl-α-chloro-2-chloro-5 [α(2,4-di Fog, maximum density, and gamma value were compared using monot-pentylphenoxy)acetamide]acetanilide as a comparison sample.

As is clear from Table 1, the color former of the present invention is an excellent yellow color former with higher maximum density and gamma and less fog than the comparative color former.

Example 3 Representative color formers of the present invention (illustrative color formers Y-4, Y-7,
Y-13, Y-3, Y-19) and known coloring agent-B (α-
Benzoyl-2-chloro-5-(α-(2,4-di-t)
-Pentylphenoxy)acetamido)acetanilide, known color former 1C (α-pivaloyl 2-chloro-5
-{α-(2,4-di-t-pentylphenoxy)}acetanilide, known color former -D (α-pivaloyl α
-Chloro-2-chloro-5-[γ-(2,4-di-t-
pentylphenoxy)butyramide]acetanilide, known coloring agent-E (α-pivaloyl-α-1(4-carboxyphenoxy)-2chloro-5-[γ-(2,4-di-t-pentyl) Tables 2 and 3 show the amount of ethyl acetate required to completely dissolve color former 1.0y at 50°C using phenoxy)butyramide]acetanilide.

However, the exemplary color former Y-3 and known color former B in Table A above
is an α-aromatic acylacetanilide color former or Table B above.
Exemplary color former Y-4 and known color former -C are comparisons of α-aliphatic acylacetanilide color formers. However, Exemplary Color Former Y-7 and Exemplary Color Former Y in Table C above
-13 and known color former -D are α-chloroacetanilide color formers, and exemplary color former Y-19 and known color former -E in Table D above are color formers substituted with leaving groups other than chloro. This is a comparison.

As is clear from Tables 2 and 3 above, the color forming agent of the present invention has higher solubility in both active point methylene-substituted and active point non-methylene substituted color forming agents than the comparative known color forming agents, and can contribute to reducing the amount of coupler solvent. I understand that. Example 4 Exemplary color former M-66.4t was dissolved in 6.5 ml of tricresyl phosphate and 15 ml of ethyl acetate to form dispersion activator 1.
Add to 60 ml of a 10% aqueous gelatin solution containing 5 ml of gelatin, finely emulsify and disperse by ultrasonic dispersion, then ethyl acetate is distilled off under reduced pressure, and the resulting emulsion is mixed into silver chlorobromide emulsion 807 to obtain a viscosity suitable for coating. A color photosensitive material was prepared by diluting the solution with water to 100%, coating it on a support coated with a polyolefin material, and drying it.

The image was then exposed through a continuous web and subjected to color development, yielding a clear, high-density magenta image. Example 5
Exemplary color formers M-12, M-14, M-17 in 8X10-
3 mol is dissolved in 6 to 8 ml of tricresyl phosphate and 14 to 16 ml of ethyl acetate, and added to 60 WLI of a 10% gelatin aqueous solution containing a dispersion activator to emulsify and disperse finely.

This dispersion was mixed in silver chlorobromide emulsion 807, coated on a support, dried, and the resulting color light-sensitive material was subjected to color development processing to obtain a clear magenta image. Example 6 1-(2.4.6-trichlorophenyl)-3-[5{α
A color photosensitive material was prepared in the same manner as in Example 4 using 1-(2,4-di-1-t-pentylphenoxy)acetamide}benzamide]-5-pyrazolone (known color former A), and color development treatment was performed after exposure. This was used as a comparison sample.

Table 4 compares and summarizes the fog, gamma, maximum density, and maximum absorption of typical color formers of the present invention and known color formers.

As is clear from Table 4, the color former of the present invention exhibits higher coupling reactivity and less fog than known color formers, proving that it is an excellent color former.

The drawing shows a representative color former of the present invention (example color former Y-16C).
A), Y-15(B)) and a known coloring agent (α-pivaloyl α-chloro-2-chloro-5-{α-(2,4-di-t-
pentylphenoxy)acetamide}anilite'(.
This is a comparative diagram of the color development characteristic curves of Q), and it is clear that the silver halide photographic emulsion containing the color former of the present invention has excellent coupling reactivity.

[Brief explanation of the drawing]

The drawing shows the color former of the present invention (exemplary color former Y-16 curve).
4), Y-15 one curve (8)) and known color former (curve →
The color development characteristic curve of Q) is shown.

Claims (1)

[Scope of Claims] 1. A compound represented by the following general formula is contained in a silver halide photographic emulsion as an image forming color former, and an aromatic primary
A color photographic light-sensitive material characterized in that a color image is formed by color development using an amine-based color developing agent. General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ However, in the formula, Q represents a yellow color former residue or a magenta color former residue, and their active methylene groups are groups that are easily eliminated during oxidative coupling. May contain. R_1 represents a straight chain or branched alkyl group having 5 to 15 carbon atoms, and R_2 represents a hydrogen atom or a straight chain or branched alkyl group having 5 to 15 carbon atoms.