JPS6039300B2 - Photographic styryl dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a styryl-type dye having a pyrazolone ring, and more particularly to a dye useful as a light-absorbing dye for use in photographic materials, particularly silver halide photographic light-sensitive materials.

When incident light passes through the photosensitive layer of a photographic material, light is reflected or scattered by the interface between the photosensitive layer and the support or by the photosensitive particles (such as silver halide particles) dispersed in the photosensitive layer. , light diffusion, etc. occur in the photosensitive layer, and the resulting image has extremely poor sharpness. Therefore, in order to prevent these phenomena, an anti-irradiation layer or an anti-halation layer that absorbs reflected light, scattered light, diffused light, etc. is created by coloring the hydrophilic colloid layer with a dye or by coloring the back surface of the support. It is known that the sharpness of images can be improved by providing layers. 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 cause desensitization or fogging due to interaction with various additives contained in photographic materials, and contamination due to residual dyes used after processing is undesirable. No. In general, the following conditions can be mentioned for dyes that can be used in photographic materials. Firstly, it should be water soluble (high solubility in water), secondly it should have excellent stability in an aqueous solution with no decrease in concentration or discoloration over time, and thirdly It satisfies the following conditions: it must be completely decolorized by the development process, that is, it must not cause staining due to residual dye, and fourthly, it must be inert in the photographic material, that is, it must not have any negative effects such as desensitization or fogging. There must be. Many photographic dyes have been proposed so far.

For example, US Pat. No. 2,527,783, US Pat. No. 32,471
No. 27, British Patent No. 933466, British Patent No. 1311884
oxonol dyes described in various publications such as U.S. Patent No. 2298733 and U.S. Patent No. 3
No. 182029, JP-A-50-128827, JP-A No. 51-
Styryl dyes described in US Pat. No. 3623, etc., US Pat. No. 2,493,747, US Pat.
Examples include merocyanine dyes described in Japanese Patent No. 5608 and Tokusei No. 50-14512, and hemioxonol dyes described in British Patent No. 58460, US Patent No. 365228y, and other publications. However, at present, there are very few dyes from these subcontractors 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 that a photographic dye should have, has particularly improved stability over time in an aqueous solution, and exhibits good water running 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.

In the general formula, R represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc.).

R, is an alkyloxy group having at least one sulfo group (for example, 3-sulfopoxy group, 4-S R6 small butoxy number, etc.).

R7 However, R6 and R7 are substituted or unsubstituted alkyl groups (e.g., methyl group, ethyl group, 2-cyanoethyl group,
2-chloroethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-sulfoethyl group, 3-sulfopropyl group, etc.), and at least one of R6 and R7 is an alkyl group having at least one sulfo group (for example, 2-
'Nasulfoethyl group, 3-sulfopropyl group, etc.).

R2 is a hydrogen atom or an alkyloxy group having at least one sulfo group (e.g., 3-sulfopropoxy group, 4-sulfobutoxy group, etc.), and R3 and R4 are lower alkyl groups (e.g., methyl group, ethyl group, n-propyl group). group, n-butyl group, n-amyl group, jso-propyl group, t-amyl group, etc.) or substituted or unsubstituted aryl group (e.g., phenyl group, chlorophenyl group, dichlorophenyl group, tolyl group, methoxyphenyl group, nitrophenyl group) groups, cyanophenyl groups, naphthyl groups, etc.),
R5 represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, n-propyl group, n-amyl group, t-butyl group, etc.). The photographic styryl dye of the present invention is
A pyrimidinyl pyrazolone derivative obtained by reacting a sulfate, carbonate or nitrate of aminoguanidine with an alkyl or substituted or unsubstituted a-IJ-loyl acetate in the presence of sodium alcoholate is reacted with an aldehyde derivative and an alcohol such as methanol or ethanol. It can be produced in good yield by reacting in a solvent or a solvent such as dimethylformamide.

This method is described, for example, in Japanese Patent Publication No. 52-50796, “
It is described in "Chemical Abstract G (Chemical Abstract)", 4th Kyogajaku, 195 Buddha, p. 165, etc. The pyrimidinyl pyrazolone derivative (intermediate) used in producing the dye of the present invention is shown below.

Compound Examples Next, specific examples of the photographic styryl dye of the present invention and typical dye synthesis examples are shown below.

Dye Example Synthesis Example 1 [Said Compound Example (P-1)] Aminoguanidine sulfate 37 and ethyl acetoacetate 83
The mixture was mixed over 300 ml of methanol and refluxed for 3 hours.

After dissolving, sodium methylate (metallic sodium 18 ml, anhydrous methanol 300 ml) was added, and after refluxing again for 3 hours, methanol was distilled off, and the mixture was dissolved in water 700 ml and acidified with hydrochloric acid while cooling. White crystals were thus obtained. This was recrystallized from water. Yield: 46 yen, melting point: 2
01 to 20 were rated ○ (decomposition). Elemental analysis C9th,
o02N4 Theoretical value N%27.17 Experimental value N%
27.15 Synthesis Example 2 [Above Exemplary Compound (P-7)] 37 grams of aminoguanidine sulfate and 41 grams of ethyl acetoacetate were mixed on 300 grams of methanol and refluxed for 3 hours while stirring.

After dissolving, sodium methylate (17 parts of sodium metal and 300 parts of anhydrous methanol) and 57 parts of methyl pivaloyl acetate were added and the reaction was again carried out under reflux for 3 hours, then the methanol was distilled off and the water was dissolved in 600 parts of water. [Additionally, the mixture was acidified with hydrochloric acid while cooling. In this way, white crystals were obtained. This was recrystallized from water. Yield: 51 oz, melting point: 93-94 oo
It was hot. Elemental analysis C, 2nd, 602N4 Theoretical value N% 25.91 Experimental value N% 25.89 Synthesis example 3 [
Said exemplary dye (D-1)] 1-(4-hydroxy-6-methyl-2-pyrimidinyl)-3-methyl-5-pyrazolone 4.1 and 4-(N,
Mix 7.6 liters of N-B-disulfoethyl)aminobenzaldehyde sodium salt with 100 ml of methanol and reflux under stirring. After q hours, the precipitated dye was cooled and concentrated, and recrystallized from 80% aqueous methanol.

The yield was 5.2 days. Elemental analysis C2 Rainbow 2.08N
5S2Na2 Theoretical value N% 12.3% 11.26 Experimental value N% 12.34S% 11.44 Synthesis example 4 [Said exemplary dye (D-4)] 1-(4-hydroxy-6-methyl-2-pyrimidinyl) -3-Methyl-5-pyrazolone 2.1 hours, 2-methyl-14-(N-ethyl-N-8-sulfoethyl)aminobenzaldehyde sodium salt 2.8 hours, and methanol 50 hours
It was mixed on the ship's side and refluxed and melted while pouring.

After 2 hours, the precipitated red crystals were collected and washed with methanol.

The yield was 2.0 yen. Elemental analysis C2, day 2405
N4SNa Theoretical value N%11.99S%6.86 Experimental value N%12.03S%6.70 Synthesis example 5 [Said exemplary dye (D-13)] 1-(4-hydroxy-6-phenyl-2-pyrimidinyl)-3- Methyl-5-pyrazolone 20 and 2-methyl-41 (N-
When 2.8 g of ethyl-N-8-sulfoethyl)amide/penzaldehyde sodium salt and 40 g of methanol were mixed and treated in the same manner as in Synthesis Example 4, a red-brown dye with a weight of 2.4 g was obtained.

This was recrystallized from 80% diluted ethanol. Elemental analysis C26 day 2605N5SNa Theoretical value N% 10.83 S% 4.96 Experimental value N% 10.90 S% 5.11 Synthesis example 6 [The above exemplary dye (D-22)] The above synthesis example 5
Similarly, 1-(4-hydroxy-6-t-butyl-2-
pyrimidinyl)-13-methyl-5-pyrazolone 2.8 and 2-methyl-41(N,N-di-B-sulfoethyl)
After mixing 4.0 g of aminobenzaldehyde sodium salt with 50 g of methanol, the mixture was refluxed for 2 hours and then filtered to precipitate crystals.

This was recrystallized from 80% bottle water ethanol. Yield is 3
．． It was the 6th evening. Elemental analysis C24th 2808N5S2
K2 theoretical value: N% 10.66S% 9.76 Experimental value: N% 10.81S% 9.66 It can be used to color the color layer.

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 conductors, dextran, alginic acid, glue, gum arabic,
Examples include starch, polyvinyl alcohol, polypynylpyrrolidone, and polyacrylic acid. These hydrophilic colloids include various additives, such as hard boat agents (formaldehyde, divinyl sulfone compounds, epoxy compounds, aziridine compounds, compounds containing active halogen atoms in their molecules, etc.), and ultraviolet absorbers. , a carrier agent, an antioxidant, and other substances such as an antifoggant, a stabilizer, a chemical sensitizer, an optical sensitizer, and the like. The dye of the present invention has excellent solubility in water and is rapidly and completely decolored, especially during development. In addition, it has a higher molecular extinction coefficient than those in which a phenyl group or an alkyl group is substituted at the 1st position of the pyrazolone nucleus, has excellent stability over time in an aqueous solution, and has features that do not adversely affect photographic properties. are doing. Next, examples of the present invention are shown below.

Example 1 220 parts of water, 15 parts of gelatin, 1 part of 1% formalin aqueous solution, 2 parts of 10% saponiso, and the aforementioned dyes (D-4), (D-7), (D-13) of the present invention ), (D-1
A colored gelatin aqueous solution containing three 1% aqueous solutions of 7) and (D-24) was prepared.

This aqueous gelatin solution was applied to a polyethylene-coated paper support and dried. On the other hand, as a comparative sample, 1-(4-
sulfophenyl)-3-methyl-4-(N,N-dimethylaminobenzylidene)-5-pyrazolone (comparative dye A
), 11(sulfopropyl)13-methyl-41(N,
An aqueous gelatin solution was prepared using N-dimethylaminobenzylidene)-5 pyrazolone (comparative dye 8) in the same manner as above. In order to examine the stability of each sample during rising, the optical density was measured when an aqueous solution of each sample was maintained for two periods under conditions of 5000 ml and 80% relative humidity. These results are shown in Table 1 below.
Shown below. The numerical values in the table are: fading rate (%) = optical density at that time - optical density after time XI.

〇Represented by optical density at that time.

Table 1 As is clear from the above table, the dye of the present invention (Sample No. 1
It can be seen that dyes 6) to 6) have better stability over time in an aqueous gelatin solution than the comparative dyes (sample Nos. 7 to 8).

Example 2 A silver halide photographic emulsion 100 of the present invention was prepared using a silver halide photographic emulsion 100 containing 40% silver chloride and 60% silver bromide, calculated as metallic silver, and 50% gelatin. The exemplary dye (D
-1) 1% aqueous solution 2' and 1% formalin aqueous solution 1 and 10 saponin 2' were added, and this was placed on a polyethylene-coated photographic paper support with a metal wire so as to give a concentration of 2.0 m/s. A sample was prepared by applying the solution to the surface and drying it.

Moreover, in place of the exemplary dye (D-1), each exemplary dye (D
-8), (D-15), (D-17), (D-26),
Each sample was created in the same manner except that (D-29) was used.

In addition, as a comparative sample, comparative dye A used in Example 1 above was used.
Each sample was prepared in exactly the same manner except that it was used in place of the dye of the present invention used in each of the above samples.

When each sample was subjected to 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. Example 3 5 x 10-5 moles of each of the dyes listed in Table 2 below were dissolved in 50 ml of distilled water, and after this was left at room temperature for 5 days, each aqueous dye solution was diluted with water to the specified concentration. The optical density was measured.

These results are shown in Table 2 below. The numerical values in the table are the fading rates (
%). Furthermore, Comparative Dye A used in Example 1 was used as a comparative sample. Table 2 As is clear from the above table, the dye samples of the present invention (No. 9 to
It can be seen that dye No. 13) has superior stability over time in an aqueous solution compared to the comparative dye (sample No. 14).

Claims (1)

[Claims] 1. A photographic styryl dye represented by the following general formula ▲
There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents a hydrogen atom or a lower alkyl group. R_1 is an alkyloxy group having at least one sulfo group, or ▲ There are mathematical formulas, chemical formulas, tables, etc.) R_7 is a substituted or unsubstituted alkyl group, R_6 and R_
At least one of 7 represents an alkyl group having at least one sulfo group. ) is shown. R_2 represents a hydrogen atom or an alkyloxy group having at least one sulfo group, R_3 and R_4 represent a lower alkyl group or a substituted or unsubstituted aryl group, and R_5 represents a hydrogen atom or a lower alkyl group. )