JPS6241264B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to styryl-type dyes, and more particularly to dyes useful as light-absorbing dyes for use in photographic materials, particularly silver halide photographic light-sensitive materials. In a photographic material, when incident light passes through its photosensitive layer, light is reflected by the interface between the photosensitive layer and the support or by photosensitive particles (such as silver halide particles) dispersed in the photosensitive layer. Light scattering, light diffusion, etc. occur in the photosensitive layer, resulting in images with extremely poor sharpness. Therefore, in order to prevent these developments, the hydrophilic colloid layer is colored with a dye to prevent irradiation, or by providing a so-called antihalation layer that colors the back surface of the support, reflected light,
It is known that image sharpness can be improved by absorbing scattered light, diffused light, and the like. The dye used here must not only absorb unnecessary light rays such as reflected light, scattered light, and diffused light occurring in the photographic material, but also must not have an adverse effect on various properties of the photographic material. For example, it is undesirable to desensitize or cause fog due to interactions with various additives contained in photographic materials, and it is also undesirable to cause stains due to residual dyes used after processing. Must not be. in general,
The following conditions can be cited as dyes that can be used in photographic materials. Firstly, it is preferably water-soluble, and has high solubility in water.Secondly, it has excellent stability in an aqueous solution with no decrease in concentration or discoloration over time.Thirdly, it must be subject to development processing. It must meet the following conditions: completely decolorized by the dye, that is, no staining with residual dye, and fourthly, it must be inert in the photographic material, that is, it must not cause any negative effects such as desensitization or fogging. No. Until now, many photographic dyes such as oxonol dyes, cyanine dyes, merocyanine dyes, hemicyanine dyes, and benzylidene dyes have been proposed. For example, U.S. Patent No. 2527783;
3247127, British Patent No. 933466, British Patent No. 1311884
oxonol dyes described in U.S. Pat. No. 49-114420, US Pat.
3182029, JP-A No. 50-28827, JP-A No. 51-3623, etc., styryl dyes, U.S. Patent No.
Merocyanine dyes described in 2493747, 2843486, 3615608, Japanese Patent Application Laid-open No. 14512, British Patent No. 584609, U.S. Patent No.
Examples include hemioxonol dyes described in various publications such as No. 3652289. However, at present, among these conventional dyes, there are very few that satisfy all of the above conditions. An object of the present invention is to provide a photographic dye that satisfies the above-mentioned conditions required for a photographic dye and exhibits particularly good decolorizing properties. Another object of the present invention is to provide a photographic material in which staining caused by residual coloring of photographic dyes after processing is improved. This object of the present invention is achieved by a photographic styryl dye represented by the following general formula. general formula In the formula, R ₁ is a sulfoalkoxy group (e.g., sulfopropoxy group, sulfobutoxy group, etc.), or

Represents [formula]. R ₄ represents an alkyl group (for example, methyl group, ethyl group, etc.), and R ₅
is an alkyl group (e.g., methyl group, ethyl group, etc.), or a chlorine atom, an alkoxy group (e.g.,
(methoxy group, ethoxy group, etc.), cyano group, alkyl group substituted with a sulfo group (e.g., 2-chloroethyl group, 2-cyanoethyl group, 2-methoxyethyl group, 2-sulfoethyl group, 3-sulfopropyl group, etc.) represents. R ₂ represents a hydrogen atom or a sulfoalkoxy group (eg, 3-sulfopropoxy group, 4-sulfobutoxy group, etc.).
R ₃ is an alkyl group (e.g., methyl group, ethyl group, etc.), or an alkyl group substituted with a hydroxy group, a sulfo group (e.g., 2-hydroxyethyl group, 3-sulfopropyl group, 4-sulfobutyl group, etc.), Phenyl group, or phenyl group substituted with an alkyl group (e.g., methyl group, ethyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, etc.), chlorine atom, carboxy group, sulfo group, nitro group, cyano group (For example, 4-chlorophenyl group, 3-chlorophenyl group, 4-sulfophenyl group, 2-chloro-5-sulfophenyl group, 4-carboxyphenyl group, p-tolyl group,
4-methoxyphenyl group, 4-cyanophenyl group, 4-nitrophenyl group, etc.). X represents a hydrogen atom or an alkyl group (for example, a methyl group). m is 1 or 2, n is 3 or 4
represents. M represents a monovalent cation (eg, sodium salt, potassium salt, ammonium salt, pyrimidium salt, etc.). The dye of the present invention represented by the above general formula uses hydroxybenzoic acid as a starting material, derives this into hydroxybenzoyl acetate, and further converts this β
- Easily produced by alkylating a ketoester type compound and then reacting it with a commonly known hydrazine to obtain a pyrazolone, and then reacting the pyrazolone with an aldehyde in an alcoholic solvent. can do. Next, specific examples of typical dyes of the present invention and their synthesis methods will be listed, but the present invention is of course not limited to these. Synthesis Example 1 [Above Exemplary Compound (1)] 1-phenyl-3-[4-(3-sulfopropoxy)phenyl]-5-pyrazolone sodium salt 4.0
g, 30 ml of methanol, and 1.7 g of P-dimethylaminobenzaldehyde were mixed, and the mixture was refluxed with stirring for 5 hours to precipitate red crystals. After cooling, it was collected by filtration and washed with methanol. The yield was 4.0g. Elemental analysis C ₂₇ H ₂₆ O ₅ N ₃ SNa Theoretical value N% 7.97 S% 6.07 Experimental value N% 8.04 S% 6.11 Synthesis example 2 [Exemplified compound 3] 1-(4-chlorophenyl)-3-[4-( 2.8 g of 3-sulfopropoxy)phenyl]-5-pyrazolone sodium salt, 25 ml of methanol, and 4.5 g of 2-methyl-4-(N-ethyl-N-chloroethylamino)benzaldehyde were mixed, and this was mixed with the above Synthesis Example 1. When treated in the same manner, a red dye was obtained. The yield was 4.2g. Elemental analysis C ₂₉ H ₂₈ O ₅ N ₃ Cl ₂ SNa Theoretical value N%6.73 S%5.13 Experimental value N%6.54 S%5.18 Synthesis example 3 [Said exemplary compound (7)] 1-(4-methylphenyl)-3- 3.9 g of [4-(3-sulfopropoxy)phenyl]-5-pyrazolone sodium salt, 30 ml of methanol, and 3.1 g of 2-methyl-4-(N-ethyl-N-2-sulfoethylamino)benzaldehyde sodium salt were mixed. When this was treated in the same manner as in Synthesis Example 1, a red dye was obtained. The yield was 3.2g. Elemental analysis C ₃₁ H ₃₃ O ₅ N ₃ S ₂ Na ₂ Theoretical value N% 6.59 S% 10.06 Experimental value N% 6.55 S% 10.34 Synthesis example 4 [Said exemplary compound (11)] 1-(2-hydroxyethyl)- 3-[4-(3-
3.6 g of sulfopropoxy)phenyl-5-pyrazolone sodium salt, 40 ml of methanol and 2-
1.7 g of methyl-4-(N,N-dimethylamino)benzaldehyde was mixed and the mixture was stirred under reflux for 2 hours to precipitate a red dye. After cooling, it was collected by filtration and washed with methanol. The yield is
It was 3.7g. Elemental analysis C ₂₄ H ₂₈ O ₆ N ₃ SNa Theoretical value N%8.25 S%6.32 Experimental value N%8.27 S%6.40 Synthesis example 5 [Said exemplary compound (17)] 1-(4-chlorophenyl)-3-[3 2.8 g of -(3-sulfopropoxy)phenyl]-5-pyrazolone sodium salt, 20 ml of methanol, and 1.0 g of 2-methyl-4-(N,N-dimethylamino)benzaldehyde were mixed, and the mixture was stirred under reflux for 2 hours. After cooling, the dye precipitated. This was collected by filtration and then recrystallized from 90% aqueous methanol. The yield was 1.8g. Elemental analysis C ₂₈ H ₂₇ O ₅ N ₃ ClSNa Theoretical value N%7.29 S%5.56 Experimental value N%7.20 S%5.62 Synthesis example 6 [Said exemplary compound (24)] 1-Phenyl-3-[4-(3- Sulfopropoxy)phenyl]-5-pyrazolone sodium salt 2.8
g, 32 ml of methanol and 2.0 g of P-(3-sulfopropoxy)benzaldehyde sodium salt were mixed, and the mixture was stirred under reflux for 5 hours.
Upon cooling, the dye precipitated. After filtering this
It was recrystallized from 90% aqueous methanol. The yield was 72%. Elemental analysis C ₂₇ H ₂₆ O ₉ N ₂ S ₂ Na ₂ Theoretical value N% 4.43 S% 10.13 Experimental value N% 4.38 S% 10.21 Synthesis example 7 Exemplified compound (25)] 1-(4-methylphenyl)-3- [3-(3-sulfopropoxy)phenyl]-5-pyrazolone sodium salt 3.2 g, methanol 35 ml and P-(3
-Sulfopropoxy)benzaldehyde sodium salt (2.5 g) was mixed and treated in the same manner as in Synthesis Example 1 to obtain a dye. Yield is 70%
It was hot. Elemental analysis C ₂₈ H ₂₈ O ₉ N ₂ S _{2 Na} 2Theoretical value N%4.33 S%9.91 Experimental value N%4.29 S%9.98 Maximum absorption wavelength (λmax) in an aqueous solution of the dye of the present invention shown in the above compound example ) are shown in Table 1.

The dyes of the invention can be used to color elements based on hydrophilic colloids, such as light-sensitive silver halide photographic emulsion layers or non-light-sensitive layers. Such a dye can be used at an appropriate concentration depending on the purpose; for example, when coloring a photographic emulsion layer, it is preferably added at a concentration of 1 to 3%. Hydrophilic colloids include gelatin (acid-treated gelatin, lime-treated gelatin, etc.), gelatin derivatives (phthalated gelatin, benzenesulfonylated gelatin, etc.), cellulose derivatives, dextran, alginic acid, glue, gum arabic,
Examples include starch, polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylic acid. These hydrophilic colloids contain various additives, such as hardeners (formaldehyde, divinylsulfone compounds, epoxy compounds, aziridine compounds, compounds containing active halogen atoms in the molecule, etc.), ultraviolet absorbers, mordants, and antiseptics. In addition to the oxidizing agent, antifoggants, stabilizers, chemical sensitizers, spectral sensitizers, and the like can be contained. The dye of the present invention has excellent solubility in water and is quickly and completely decolored, especially after development. In addition, it has a higher molecular absorption coefficient than conventional ones, has excellent stability over time in an aqueous solution, and has the characteristics of not having an adverse effect on photographic properties. Hereinafter, the present invention will be explained according to examples. Example 1 15 g of gelatin, 1 ml of 1% formalin aqueous solution and 2 ml of 10% saponin aqueous solution were dissolved in 220 ml of water,
To this was added 3 ml of each dye listed in Table 2 below as a 1% aqueous solution to prepare each colored gelatin solution. Each of these solutions was applied to a polyethylene-coated paper support and dried to prepare samples. As a comparative sample, a sample coated in the same manner using a known dye (a): 1-(4-sulfophenyl)-3-methyl-4-N,N-dimethylaminobenzylidene-5-pyrazolone was used. The visible spectra of these samples were measured. Next, each sample was immersed in the following developer solution at 20° C. for 30 seconds with stirring, washed with water for 1 minute, dried, and the visible spectrum was measured again. The decolorization rate was calculated from the optical density before treatment (D ₁ ) and the optical density after treatment (D ₂ ) at the maximum absorption wavelength of each sample using the following formula, and the decolorization properties of each sample were compared. These results are shown in Table 2 below. Decolorization rate Decolorization rate (%) = D ₁ - D ₂ /D ₁ ×100 Composition of developer Metol 3.0 g Anhydrous sodium sulfite 45 g Hydroquinone 12 g Anhydrous sodium carbon 80 g Potassium bromide 2 g Add water to make a total volume of 1 liter.

【table】

[Table] As is clear from the above table, the dye of the present invention is superior in decolorizing property compared to the comparative dye. Example 2 The above-mentioned exemplary compound of the present invention ( Add 2 ml of the 1% aqueous solution of 1), 1 ml of the 1% formalin aqueous solution, and 2 ml of 10% saponin, coat this with metallic silver on a polyethylene-coated photographic paper support at a density of 2.0 g/m ² , and dry. A sample was prepared. In addition, in place of exemplified compound (1), each exemplified compound
Each sample was created in the same manner except that (2), (5), (7), (17), and (24) were used. A comparative sample was prepared in exactly the same manner except that the comparative dye (a) used in Example 1 was used in place of the dye of the present invention used in each of the above samples. When each sample was subjected to ordinary black-and-white development processing, the comparison sample exhibited a pale pink color, but the sample of the present invention showed no color staining due to residual dye.

Claims (1)

[Claims] 1. A photographic styryl dye represented by the following general formula. general formula (In the formula, R ₁ represents a sulfoalkoxy group or [Formula]. _{R 4} represents an alkyl group, and R ₅ represents an alkyl group or an alkyl group substituted with a chlorine atom, an alkoxy group, a cyano group, or a sulfo group. R ₂ represents a hydrogen atom or a sulfoalkoxy group. _{R 3} represents an alkyl group, or an alkyl group substituted with a hydroxy group or a sulfo group,
phenyl group, or alkyl group, alkoxy group,
Chlorine atom, carboxy group, sulfo group, nitro group,
Represents a phenyl group substituted with a cyano group. X represents a hydrogen atom or an alkyl group. m represents 1 or 2, and n represents 3 or 4. M represents a monovalent cation. )