JPH01541A - Silver halide photographic material containing oxonol dye - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of the Invention] The present invention relates to a silver halide photographic light-sensitive material containing a dye, and in particular, it has good spectral characteristics by containing a specific oxonol dye, and This invention relates to a silver halide photographic material that does not cause any inconvenience.

[Background of the Invention 1] Silver halide photographic materials (hereinafter sometimes abbreviated as photosensitive materials) use specific materials for filters, halation prevention, irradiation prevention, or sensitivity adjustment of photographic emulsions. For the purpose of absorbing wavelengths of light,
A dye is contained in a photosensitive material.

Dyes used for such purposes must have good absorption spectrum characteristics according to the purpose of use, be completely decolorized during photographic processing, and have no residual color contamination from the dye after photographic processing, and must be compatible with photographic emulsions. It must satisfy various conditions, such as not having any negative effects such as fog or desensitization, having excellent stability over time in solutions or photographic materials, and not discoloring or fading.

To date, many efforts have been made with the aim of finding dyes that satisfy the above conditions, and a large number of dyes have been proposed. For example, British Patent No. 506.385,
U.S. Patent No. 3,247,127, Japanese Patent Publication No. 1983-
Oxonol dyes described in Japanese Patent Publication No. 22069 and Japanese Patent Publication No. 43-13168, U.S. Patent No. 1, 84
Styryl dye represented by No. 5.404, U.S. Patent No. 2
．． There are merocyanine dyes represented by US Pat. No. 493.747, cyanine dyes represented by US Pat. No. 2.843.486, and the like. However, the reality is that there are very few good dyes that satisfy all of the above conditions and can be used in photographic materials.

[Object of the Invention] The object of the present invention is to provide a photosensitive material that satisfies the above conditions, that is, has a good absorption spectrum, is decolored during development processing, and has extremely little residual color contamination after processing.

An object of the present invention is to provide a silver halide photographic light-sensitive material containing a dye that is inert to photographic emulsions.

[Structure of the Invention] The above objects of the present invention have been achieved by a silver halide photographic material containing an oxonol dye represented by the following general formula.

General formula (I> In the formula, R1 and R2 each represent a heterocyclic group or an aryl group. R3 and R4 each represent an alkyl group, a heterocyclic group, or an aryl group, and the above multigroup is at least one water-soluble group. has.

Ll, L2. L3. L4 and L5 each represent a methine group. kl and ni2 each represent an integer of ○ or 1.

[Specific Structure of the Invention] Examples of the aryl group represented by each of R1 and R2 include substituted or unsubstituted groups such as phenyl group, naphthyl group, p-tolyl group, p-methoxyphenyl group, etc. In particular, aryl groups substituted with electron-withdrawing groups (eg, cyano groups, sulfamoyl groups, sulfonyl groups, sulfo groups, phosphono groups, carboxy groups, carbamoyl groups) are preferred.

The Wi elementary ring group represented by each of R1 and R2 includes, for example, a 2-furyl group, and also includes those having a substituent.

Each of R3 and R4 is an alkyl group having at least one water-soluble group as a substituent (e.g. propyl group,
n-butyl group, etc.), a heterocyclic group having at least one type of water-soluble group as a substituent (e.g., thiazolyl group, etc.), or an aryl group having at least one type of water-soluble group as a substituent (e.g., phenyl group, etc.). be.

In addition, in each of R3 and R, the water-soluble groups include, for example, a sulfo group, a carboxy group, a phosphoric acid group, a phosphorous acid group, a sulfuric acid ester group, an ammonium group, etc.
Among these, the acid group may be in a free state, and an alkali metal or alkaline earth metal (e.g. Na, M(
1, Ca) May form a salt with a certain cation such as LtNH4.

The methine group represented by L1 to L5 is an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, isopropyl group, tert-butyl group, etc.) or an aryl group (e.g., phenyl group, tolyl group, etc.). This includes those replaced with .

Below, the oxonol dye represented by the general formula (I) (
Hereinafter, typical examples of the "oxonol dye of the present invention" will be shown, but the present invention is not limited thereto.

Ki-□ 1st bottom margin M-L-no So, NH, H2 to S2 Margin below ·knee (Zl) I So, K So, to ○=mouth.

1 mountain 2 f zo
0Q×
z× 2 It can be synthesized by a condensation reaction.

General formula (TI) General formula (III) In the formula, r<', R2, L1. L2. L3. L4゜L5
, k+ and 2 are each defined similarly to general formula (I). R3' is a hydrogen atom or a halogen atom (II
4 represents an electron-withdrawing group such as a fluorine atom, chlorine atom, bromine atom, etc.), a cyano group, a trifluoromebyl group, and an electron-withdrawing group such as a dicarbonyl group. iodide, verchlorate, D-toluenesulfonate, methylsulfonate, ethylsulfonate, etc.). q represents O or 1.

Examples of the base present in the condensation reaction include pyridine, piperidine, triethylamine, triethanolamine, morpholine, ammonia, and potassium acetate.

Examples of solvents for the compounds include alcohols (e.g., methanol, ethanol, etc.), ethylene glycol, ethylene glycol monoalkyl ethers (e.g., ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, etc.), acetonitrile, dimethyl sulfoxide, amides. (For example, dimethylformamide, dimethylacetamide, acetamide, N-methylpyrrolidone, etc.) are used.

The reaction temperature can be appropriately selected from the temperature range from 0° C. to the boiling point of the solvent used.

Further, the pyrazolone derivative represented by the general formula (n), which is a reaction reagent, is suitably used in a molar amount approximately twice that of the compound represented by the general formula (1).

Furthermore, the pyrazolone derivative represented by the general formula (I) was prepared by Richard H. Willey (R1chard, H.).

Will), Ball Willy (Paul, Will)
y) "Pyrazolone Compounds, Pyrazolidone Compounds and Their Derivatives""PYRAZOLONES".

PYRAZOLIDONES AND DERIVAT
IVES” [INTER3CIENCEPUBLISHER3
) Published, 1964] Matc Ha British Patent No. 58517
It can be synthesized using the manufacturing method described in the specification of No. 80 and the like.

In the light-sensitive material of the present invention, the oxonol dye of the present invention can be preferably used as an irradiation-preventing dye by being contained in the photosensitive emulsion layer, and can also be contained in the non-photosensitive hydrophilic colloid layer. It can also be used as a filter dye or an antihalation dye. Moreover, depending on the purpose of use, two or more types of dyes can be used in combination. As a method for incorporating the oxonol dye of the present invention into a silver halide emulsion layer or other hydrophilic colloid layer, a method used in conventional silver halide photographic materials can be used.

In general, dyes or organic or inorganic alkali salts of dyes are dissolved in water to form a dye/aqueous solution with an appropriate concentration, then added to a coating solution and coated onto a support using various methods. Dyes can be included in the material.

The content of the oxonol dye of the present invention can be changed as appropriate depending on the purpose of use, but is generally 1 to 800II1g per 112 areas of the light-sensitive material.

The light-sensitive material of the present invention includes supports used in the photographic industry, hydrophilic colloids, methods for producing silver halide emulsions, various additives,
Any layer structure can be used. The silver halide grains used in the present invention have a grain size of 0.1 μm to 10 μm.
Any one of m is included, and the crystal habit is not particularly limited.

[Example] Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 Color photosensitive materials for printing were prepared in the manner described below, and after these samples were exposed in a quadrilateral manner, they were processed using the following color developer and bleach-fix solution to evaluate the performance of each dye image formed. It was measured.

[Preparation of Sample] A paper support whose surface was coated with polyethylene containing anatase titanium oxide as a white pigment was subbed with gelatin, and then the following layers were sequentially coated to prepare a sample.

1st layer: Blue-sensitive silver chlorobromide emulsion layer Yellow Nocopla (Y-1) and 2 Coating was carried out using an emulsified dispersion prepared by dissolving 5-tert-1 ctylhydroquinone in dioctyl phthalate and adding surfactants (saponin and 5-1).

Second layer: First intermediate layer was coated using an emulsified dispersion prepared by dissolving 2.5-di-tert-octylhydroquinone in dioctyl phthalate.

Third layer: Green-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 1 mol % of silver bromide sensitized using sensitizing dye 5D-2, magenta coupler (M-1) and 2. 5-Jert-t Cuti/L/A Emulsified dispersion prepared by dissolving hydroquinone in dioctyl phthalate and adding surfactants (saponin and 5-1) and aqueous dye solution (AI-1>) It was painted using.

4th layer: 2nd intermediate layer The following ultraviolet absorbers ((JV-1) and 2,5-ZT
Coating was carried out using an emulsified dispersion prepared by dissolving ert-octylhide 0quinone in dioctyl phthalate.

5th layer: Red-sensitive silver chlorobromide emulsion layer A silver chlorobromide emulsion containing 2 mol% of silver bromide sensitized using sensitizing dye 5D-3, cyan coupler (C-1) and 2, 5-Jert-O') H) An emulsified dispersion prepared by adding tt hydroquinone dissolved in dioctyl phthalate, and further adding a surfactant (saponin and 5-1) and an aqueous dye solution shown in Table 2. It was painted using.

6th Layer: Protective Layer An emulsified dispersion prepared by dissolving the following ultraviolet absorber (UV-1) in dioctyl phthalate was used to coat the layer.

7th WJ: Preserve! J layer A hardener (H-1>) was added to gelatin for coating.

The components of each layer (maa per 100 cf) are shown in Table 1.

Below is the margin N″−゛′−Nino C.I. V-1 CsH++(t> SD, -1 CI(.

H2C=CHS02CH20CHffiSO2CH=C
H2. Based on the above layer structure, the dye in the red-sensitive silver chlorobromide emulsion layer (fifth layer) was changed to produce sample 1 shown in Table 2.
-18 were prepared and evaluated as shown below.

■Fog measurement An unexposed sample was processed by the method described in Example 2 of JP-A No. 58-134836, and the fog [)-
Reflection with white light using a 122-type densitometer 111
I measured the degree.

■Evaluation of residual color contamination In order to investigate the degree of color contamination due to residual color of the dye after development processing, N-ethyl-N to β-methanesulfonamidoethyl-3-methyl-4 was extracted from the color developing solution used in the treatment in -Aminoaniline 1 A solution from which the IliiH salt was removed was prepared, and the same experiments and measurements as in ① were conducted. The results of (1) and (2) are shown in Table 2.

Margin below 1.

Table 2 below: Meeting i? 1 □ □ 1 Comparative dye A SO2 total SO2 In Table 2 above, each number for the dye is the amount of cloth per 100 cm' (1
g).

It is clear from Table 2 that the whiteness desired for a color photosensitive material for printing requires that the fog be less than o, oos, and the samples of the present invention satisfy this requirement. In addition, almost no color contamination due to residual color of the dye, which is observed in samples containing comparative dyes, is observed.

That is, it has been found that the dye according to the present invention has extremely little adverse effect on the emulsion.

Example 2 A silver chlorobromide emulsion with a silver bromide content of 8 mol % and rhodium chloride added at 1 x 10-5 mol per mol of silver halide was prepared by a simultaneous mixing method by aging at 45°C for 40 minutes. Desalting and redispersion were performed to obtain a monodisperse emulsion with an average particle size of 0.23 μI. Rhodium chloride was dissolved in a sodium chloride solution and added to the halide solution.

Add thiosulfate to the emulsion thus prepared!・Chemical ripening was carried out for 30 minutes at 50" C, and 6-methyl-4-hydroxy-1°3.38.7-titrazaindene was added as a stabilizer. Next, the dyes shown in Table 3 were added to this emulsion. Furthermore, 1-phenyl-5-mercaptotetrazole was added as an antifoggant, the following polyethylene oxide compound (m = 20.1 + n = 15) was added as a suitable point adjuster, and saponin was added as a spreading agent.

The emulsion thus prepared was divided into two parts, one part of which was immediately coated and dried, and the remaining part was allowed to stagnate at 40°C for 10 hours. It was applied to the film base and dried.

The film base used was a polyethylene terephthalate base with latex (n-butyl terephthalate, [-butyl terephthalate, ethyl hydroxy terephthalate, and styrene in the ratio of 30:20, respectively).
25:25 copolymer) and coated with an aqueous gelatin solution containing saponin as a spreading agent.

On the emulsion layer coated on the film base as described above, an aqueous gelatin solution containing a spreading agent (saponin) was coated and dried to form a protective layer 1. Roughly, protective layer 1 is coated with an aqueous gelatin solution containing the dye shown in Table 3, a spreading agent (saponin), a hardening agent (mucochloric acid), and polyvinylpyrrolidone, and dried to form protective layer 2. The above dye was added to an aqueous gelatin solution in an amount of 1 mmol per 1f of light-sensitive material.

Safelight test on the sample obtained in this way.
We also conducted performance deterioration tests by forced deterioration.

(Safelight test) Fluorescent lamp for preventing fading (Toshiba FL40SW-NU) approx. 30
Irradiate for 60 minutes under 0 lux, process with the following developer,
Fog density was measured.

The ° samples used here were samples coated immediately after the emulsion preparation described above (T-1>) and emulsion stagnation (40°C, 10 hours).
This is a post-coated sample (T-2).

(Forced Deterioration Test) The imitation obtained by coating immediately after preparing the emulsion described above was used as a blank (T-3>), and the coated sample was further heated at a temperature of 50'C and a humidity of 7.
The sample (T-4) which had been forcibly degraded by being left in the middle of an atmosphere of 0% R)I for two days was evaluated as follows. It was exposed to light using a bright room printer (HMW-215 manufactured by Oak Seisakusho) and processed with the following developer.

(Developer formulation) Hydroquinone 151] Adduct of formaldehyde and sodium bisulfite so g Potassium sulfite 49 Potassium carbonate
500 boric acid
2g potassium bromide
2g triethylene glycol 49G
EDTA-2Na 1 (1 diethanolamine 795-nitroindazole 6 mg polyethylene glycol (average molecular ff 1150G) 0.
40 Sodium hydroxide 1g Add water and 1! shall be.

The developing conditions were 27° C. for 1 minute and 40 seconds.

The results are shown in Table 3.

Comparative Dye C Comparative Dye As is clear from Table 3, Samples 20 to 23 of the present invention can achieve low sensitivity that can be handled as photosensitive materials for bright room use, and require a long time in the manufacturing process of photosensitive materials. It can be seen that there is very little safelight deterioration due to stagnation of the coating solution, the contrast is high, and the sensitivity and gradation of the photosensitive material are stably maintained during storage.

[Effect of the invention J] The present invention provides a halogen containing dye that has a good absorption spectrum, is decolored during development processing, has extremely little residual color staining after processing, and is inert to photographic emulsions. We were able to provide a silver oxide photographic material.

Claims (1)

[Scope of Claims] A silver halide photographic material characterized by containing an oxonol dye represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^2 each represent a heterocyclic group or an aryl group. R^3 and R^4 each represent an alkyl group or a hetero It represents a ring group or an aryl group, and each of the above groups has at least one type of water-soluble group. L^1, L^2, L^3, L^4 and L^5 each represent a methine group.k^ 1 and k^2 each represent an integer of 0 or 1.)