JPS5926939B2 - Silver halide photographic material - Google Patents

Description

[Detailed description of the invention] The present invention relates to photographic dyes.

More particularly, the present invention relates to oxonol dyes useful as dyes for coloring photographic layers and derived from 5=isoxazolone, and photographic light-sensitive materials containing the same. In photographic light-sensitive materials, the photographic emulsion layer (mainly to prevent irradiation) or other layers (for example, filter layer or antihalation layer) is colored in order to absorb light in a specific wavelength range. . These layers to be colored are often comprised of hydrophilic colloid layers, and it is therefore advantageous to use water-soluble dyes in order to carry out this coloring effectively.

Examples of such dyes include British Patent No. 506385, Japanese Patent Publication No. 39-22069 No. 13168, and Japanese Patent Application Laid-open No. 48
-Oxonol dyes having a pyrazolone nucleus as described in US Pat. No. 85130; Oxonol dyes having a barbituric acid nucleus as described in US Pat.
No., British Patent No. 1278621 and French Patent No. 140158
Other oxonol dyes as described in No. 8;
British Patent No. 584609, US Patent No. 3540887,
No. 3615546, No. 3687670, French patent 1
Benzylidene (or cinnamylidene) pyrazolone dyes such as those described in No. 350311 and No. 1421679: British Patent No. 1075653 (for the general formula (2)), British Patent No. 1153341, British Patent No. 1284730, and French Patent No. 1401588 ( Although merocyanine dyes such as those described in general formula (2) have been proposed, they have a negative effect on photographic emulsions and are not easy to bleach or dissolve in photographic processing, making them difficult to use for coloring photographic layers. It is still insufficient as a dye.

An oxonol dye for coloring photographic layers having an isoxazolone nucleus is known from Japanese Patent Publication No. 44-27063. However, these dyes are nearly inert to photographic emulsions and are resistant to photographic processing. ``Although it is easily decolorized, it has poor solubility in water, and it has been difficult to incorporate it into a photographic layer in an amount necessary for the purpose of light absorption.'' The first object of the present invention is to: An object of the present invention is to provide a dye for coloring a photographic layer, which is an oxonol dye having an isoxazolone nucleus and having improved solubility in water.

A second object is to provide a water-soluble oxonol dye that is also soluble in organic solvents such as alcoholic acids and esters.

A third object of the present invention is to provide a photographic material containing the above-mentioned oxonol dye.

These objects can be effectively achieved by using in silver halide photographic light-sensitive materials an oxonol dye represented by the following general formula (1) and consisting of an isoxazolone nucleus having a phenyl group substituted with a sulfopropionamide group. can be achieved. [Wherein, X represents a hydrogen atom, a halogen atom, an aliphatic group, an alkoxy group or an alkoxy group.

L is a methine group, M is a cation, n is 1, 2 or 3
represents. ] To explain general formula (1) in detail,
X is a hydrogen atom, a halogen atom (e.g. chlorine atom, bromine atom, etc.), an aliphatic group, preferably an alkyl group having 1 to 5 carbon atoms {e.g. M represents a hydrogen atom, an alkali metal (e.g. sodium, potassium ), alkaline earth metals (e.g. calcium, barium, etc.),
It represents a cation such as ammonia and an organic base (eg, triethylamine pyridine, piperidine, etc.), and among them, sodium ion and potassium ion are preferred.

Lho, methine group [In this specification, it is used to include not only unsubstituted methine group but also substituted methine group, -L-(L=Lh''] Any of L in 4 is , an alkyl group having 1 to 3 carbon atoms (e.g., methyl group, ethynole group, etc.), an aryl group (e.g., phenyl group, etc.), an aralkyl group (e.g., phenethyl group, etc.), or a halogen atom (e.g., chlorine atom, bromine atom, etc.). Among them, an unsubstituted methine group or a methyl-substituted methine group is preferable.The substitution position of the sulfopropionamide group to the phenyl group is preferably the meta or para position.

Using the oxonol dye of the present invention (a) Provide appropriate spectral absorption characteristics depending on the purpose of use.

(b) It is photochemically inert (that is, it does not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense) and therefore does not cause, for example, a decrease in sensitivity, latent image regression, or fog.

(c) Since it is easily decolorized in the photographic processing process and easily dissolved and removed, no harmful coloration remains on the photographic material after processing.

(d) It is easy to include in the photographic layer the amount necessary for the purpose of light absorption.

There are advantages such as

The oxonol dye represented by the general formula (1) has the following formula:
X has the same meaning as in the general formula.

] and (b) ethyl orthoformate, N-
N-diphenylformamidinobenefic acid salt (yielding monomethine oxonol), trimethoxypropane, tetramethoxypropane, malonaldehyde dianyl hydrochloride (or its mesomethyl substituted product) (yielding trimethine oxonol) or glutaconaldehyde dianinole hydrochloride (yielding pentamethine oxonol), etc. with a base (e.g., triethylamine, pyridine,
It can be obtained by condensation in the presence of an aliphatic or aromatic tertiary amine such as morpholine. The reaction temperature varies depending on the applied reaction time and the type of reactants, but is preferably 00 to 120°C, and the reaction time is 5 minutes to 6 hours.

Furthermore, the molar ratio of the reactant (5) used is preferably determined by the general formula (
) is 1 to 5 times that of the reactant.

The compound represented by the general formula () is an isoxazolone represented by the following general formula () and the β-
During this addition reaction, the reaction mixture (preferably molar ratio 1:1).

Preferably, benzene, toluene, dioxane, etc. are used as the inert solvent.

The method for synthesizing isoxazolones represented by the general formula () is described in J. Anler. Chem. SOc. Dandan,
504 (1928) or J. Chem. SOc. l
952, 3428.

Further, β-sulfopropionic anhydride represented by the formula () is described in J. Amer. Chem. SOc. ldan, 2393
(1940). Some specific examples of oxonol dyes used in the present invention and their synthesis examples are listed below. Synthesis Example 1 Synthesis of Dye 1 3-[4'-(γ-Sulfopropionamido)phenyl]-5-isoxazolone 3.1f A mixture of 5 ml of ethyl orthoformate and 20 ml of pyridine was stirred under reflux for 30 minutes.

Then, a methanol solution of 1.07% of anhydrous potassium acetate
After adding m1 and stirring for 5 minutes under heating (50 to 60°C), the mixture was cooled with water. The precipitated yellow crystals were collected, washed with ethanol and acetone, and dried to obtain the desired dye 2.47. This dye was dissolved in water, methanol, and ethanol, and its maximum absorption wavelength was 425 nm in water and 425 nm in methanol. Synthesis Example 2 Synthesis of Dye 2 3-[41-(γ-Sulfopropionamido)phenyl]-5-isoxazolone 3.1f7 and malonaldehyde dianyl hydrochloride 1.47 were added to 15ml methanol.
．． The mixture was dissolved in a mixture of 15 ml of N-N-dimethylformamide and 3 ml of triethylamine, and heated and stirred on a hot water bath for 2 hours.

Next, 10 m of methanol solution of 1.0 y of anhydrous potassium acetate
1 was added thereto, heated for 5 minutes (50-6'C) and stirred, and then cooled with water. The precipitated red colored crystals were collected, washed with acetone and dried to obtain the desired dye 2.6y. This dye was well soluble in water and methanol, and the maximum absorption wavelength was 513 nm in water and 521 nm in methanol. Synthesis Example 3 Synthesis of Dye 3 3-[4'-(γ-Sulfopropionamido)phenyl]-5-isoxazolone 3.17, glutaconaldehyde dianyl hydrochloride 1.27, N-N dimethylformamide 15ml, methanol A mixture of 15 ml and 4.0 ml of triethylamine was stirred at 10-15°C for 3 hours.

Then, 1.07 methanol solution of anhydrous potassium acetate
Add 0ml of acetone, stir for 10 minutes, then add 200ml of acetone.
When added, dark blue crystals were precipitated. The crystals were collected, washed with acetone, and dried to obtain dark blue crystals 2.67. This dye was well soluble in water, methanol, and ethanol, and the maximum absorption wavelength was 608 nm in water and 618 nm in methanol. Synthesis Example 4 Synthesis of Dye 5 3 A mixture of 3-[3'-(γ-sulfopropionamido)phenyl]-5-isoxazolone, 5 ml of ethyl orthoformate, 10 ml of glacial acetic acid, and 8 ml of triethylamine was heated in an oil bath at 100 to 105°C. The mixture was heated and stirred for 30 minutes.

Next, a methanol solution of 1.07 anhydrous potassium acetate 10
After adding m1 and stirring for 10 minutes, the mixture was cooled with water.

The precipitated yellow-brown crystals were collected, washed with isopropanol and acetone, and dried to obtain the desired dye 2.17. This dye dissolves in water, methanol, and ethanol, and the maximum absorption wavelength is 425 nm in water and 42 nm in methanol.
It was 5 nm. Synthesis Example 5 Synthesis of Dye 8 3-[4'-methoxy-3'-(γ-sulfopropionamido)phenyl]-5-isoxazolone 3.4f7
, malonaldehydedianil hydrochloride 1.4f, methanol 15mi, . N●N-dimethylformamide 15ml
A mixture of 3 ml of 1 triethylamine was heated and stirred on a water bath for 2 hours.

Next, 10 ml of methanol solution of 1.07 anhydrous potassium acetate
1 was added, heated and stirred for 5 minutes, and then cooled with water. The precipitated reddish brown crystals were collected, washed with acetone and dried to obtain the desired dye 2.6y.

This dye was well soluble in water, methanol, and ethanol, and the maximum absorption wavelength was 513 nm in water and 521 nm in methanol. Synthesis Example 6 Synthesis of Dye 9 3-[4'-methoxy-3'-(γ-sulfopropionamido)phenyl]-5-isoxazolone 3.4f1
Glutaconaldehyde dianyl hydrochloride 1.47, methanol 15ml, . N-N-dimethylformamide 15m
A mixture of 4 ml of 11 triethylamine was stirred in a water bath for 2 hours.

Next, 10 ml of methanol solution of 1.07 anhydrous potassium acetate
After stirring for 10 minutes, 200 m2 of acetone was added. Collect the precipitated blue crystals, wash with acetone,
After drying, dark blue crystals 2.87 were obtained. This dye is water,
It was dissolved in methanol and ethyl acetate, and the absorption maximum wavelength was 608 nm in water and 618 nm in methanol.

Next, regarding other oxonol dyes, The values are shown below.

The oxonol dye of the present invention can be incorporated into a coating solution for a silver halide photographic emulsion layer, a filter layer, and/or an antihalation layer by a conventional method.

The amount of dye used is sufficient to color the photographic layer;
Those skilled in the art can easily select this amount as appropriate depending on the purpose of use. The antihalation layer is provided between the photographic emulsion layer and the support or on the surface of the support, and a colored layer is provided on the surface opposite to the photographic emulsion layer. When there are multiple photographic emulsion layers such as in a multilayer color light-sensitive material, hydrophilic protective colloids constituting an antihalation layer between these layers include, for example, gelatin, casein, polyvinyl alcohol, and polyN-vinylpyrrolidone. ,
Carboxymethyl cellulose, sodium alginate, etc. can be used, and gelatin is particularly preferred. Other photographic additives such as coating aids and hardeners may be added to the dye dispersion prior to coating. Supports for photographic materials, coating methods, photographic additives, photographic emulsion manufacturing methods, photographic processing methods, etc.
145125), page 27, line 1 to page 66, line 12, and "Research Disclone Earth"
(Reseav'ChDisclOsures) Magazine/F
692, pp. 107-110 (December 1971 issue) can be applied.

Example 1 Gelatin 807 was dissolved in water 11, and 80 ml of a 5% aqueous solution of poly(diethylaminoethyl methacrylate) was added thereto.
, 30 ml of 10% aqueous solution of saponin, 2 ml of chromium alum
% aqueous solution and 400 ml of a 2% aqueous solution of the dye 2 of the present invention described above were respectively added to prepare a dye gelatin solution.

The above dye gelatin solution was coated on a cellulose acetate photographic support to form an antihalation layer.

On top of that, anthitro 11-ethyl-3,3/-bis(
sulfopropyl) naphtho[1,2-d]thiacarbocyanine hydroxide and 9-ethyl-3,3'-bis-(
A silver chlorobromide emulsion (approximately 17 mol% silver bromide) that has been spectrally sensitized panchromatically in combination with (sulfobutyl) zelenacarbocyanine hydroxide is coated, a protective gelatin layer is formed on top of the silver chlorobromide emulsion, and plate making is carried out. Created photographic materials. A contact screen (1
133 lines per inch) was brought into close contact with light wedge exposure, and developed for 3 minutes at 2'C using a developer with the following composition.
It was fixed, washed with water, and dried according to a conventional method.

The photographic material after processing showed almost no contamination in the unexposed areas.

In addition, a halftone image with excellent edge gradient was obtained. Example 2 Poly(diethylaminoethyl methacrylate) 27 was added to a 10% gelatin aqueous solution 5007, and then the dye 2 of the present invention or the dye known in Japanese Patent Publication No. 44-27063 (methyl substituted with sulfopropionamide-substituted phenyl group) was added. 100 ml of a 2% methanol solution of Dye 2 (same as Dye 2 except for the base) was added to each, and mucochloric acid and saponin were added to each to prepare dye gelatin solutions.

The dye gelatin solutions were each coated onto a cellulose triacetate photographic support and dried to form a 1.6 micron antihalation layer.

A panchromatically spectrally sensitized fine-grain silver chlorobromide emulsion (approximately 40 mol % silver chloride) was coated thereon in the same manner as in Example 1, and a protective gelatin layer was further provided to produce a photographic material. . Photographic material 1 (containing the dye according to the invention) and photographic material 2 (containing the known dye) thus produced were subjected to a sensitometric exposure for 5 minutes at 20°C using a developer having the following composition: Develop and fix according to conventional methods,
Washed with water and dried.

Composition of developer add water The results obtained are shown in Table 1.

In Table 1, the transmittance is the transmittance at the spectral absorption peak wavelength of each dye in the unexposed area.

Claims (1)

[Scope of Claims] 1. A silver halide photographic photosensitive material containing an oxonol dye represented by the following general formula (I) and consisting of an isoxazolone nucleus having a phenyl group substituted with a sulfopropioamide group. material. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) [In the formula, X is a hydrogen atom, a halogen atom, an aliphatic group, or an alkoxy group, L is a methine group, M is a cation, and n is an integer 1
, 2 or 3, respectively. ].