JPH06332103A - Photographic spectrally sensitizing dye - Google Patents

Abstract

PURPOSE:To provide the photographic spectrally sensitizing dye high in sensitivity and small in color stains due to residual dyes and in fog. CONSTITUTION:The photographic spectrally sensitizing dye is characterized by being represented by the formula in which each of Z<1> and Z<2> is a 5- or 6-membered atomic group necessary to form an N-containing hetero ring: each of R<1> and R<2> is, independently, optionally substituted alkyl or such alkenyl; each of R<3>-R<6> is, independently, optionally substituted alkyl, such alkenyl, or such aryl; each of L<1>-L<5> is, independently, a methine group; each of (m) and (n) is, independently, 0 or 1 but is not 0 at the same time; and X is a counter ion.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a spectral sensitizing dye for photography, and more particularly to a dye useful as a sensitizing dye used in a silver halide photographic light-sensitive material.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material is required to have high sensitivity in different specific wavelength regions depending on its intended use. As one of the manufacturing techniques for such a silver halide photographic light-sensitive material, various types of cyanine dyes and merocyanine dyes are added to a silver halide photographic emulsion, and a wavelength longer than the unique light-sensitive wavelength region of the silver halide is used. It is generally well known that, in the range, the sensitivity in a specific wavelength range is extremely effectively increased.

When spectral sensitization is applied to a silver halide photographic emulsion with a dye, it must satisfy not only the spectral sensitizing effect and the increase in sensitivity but also the following requirements. . (1) The spectral sensitization range is appropriate. (2) Stable photographic characteristics are maintained during storage of the light-sensitive material. (3) No stain or fog caused by the residual dye administered for spectral sensitization after development. (4) No bad interaction with other photographic additives. However, although quite a large number of cyanine and merocyanine dyes are known to date, few of the dicarbocyanines that impart photosensitivity in the red region satisfy the above requirements such as sensitization and photographic characteristics. It's a reality.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent spectral sensitizing dye for photographic use which satisfies the above-mentioned various requirements.

[0005]

As a result of various investigations, the present inventors have found that the sensitizing dye represented by Chemical formula 1 is an excellent dye satisfying the above object.

In the formula, Z ¹ and Z ² each represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. Specific examples of these (for convenience, shown by the name of the raw material tertiary base) include, for example, benzoxazole ring, naphthoxazole ring, benzothiazole ring, naphthothiazole ring, benzoselenazole ring, naphthoselenazole ring, quinoline ring, benzoline. There is a quinoline ring, an indolenine ring, a benzoindolenine ring, a benzimidazole ring, a naphthimidazole ring, etc. Further, as an example of Z ¹ when m is 0, and as an example of Z ² when n is 0, Examples thereof include an oxazoline ring, an oxazole ring, a thiazoline ring, a thiazole ring, and a thiazine ring. Further, the carbon atom of these heterocycles includes a halogen atom (eg, chlorine, bromine atom, etc.), an alkyl group (eg, methyl, ethyl, n-).
Propyl, n-butyl, t-butyl, n-amyl group, etc.), alkoxy group (eg, methoxy, ethoxy, n
-Propoxy group, etc.), hydroxy group, trifluoromethyl group, cyano group, alkanesulfonyl group (eg, methanesulfonyl, ethanesulfonyl group, etc.), sulfamoyl group (eg, sulfamoyl, N, N-dimethylsulfamoyl, piperidyl) And a substituent such as an aryl group (eg, phenyl, methoxyphenyl group, etc.) may be attached. R ¹ and R ² are each independently a substituted or unsubstituted alkyl group (eg, methyl, ethyl, n-propyl, i-propyl, n-butyl, n-amyl group, β-hydroxyethyl, γ-hydroxypropyl). , Β-acetoxyethyl, γ-acetoxypropyl, β-methoxyethyl, γ-methoxypropyl, carboxymethyl, β-
Carboxyethyl, γ-carboxypropyl, δ-carboxybutyl, ω-carboxypentyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, β-methoxycarbonylethyl, γ-methoxycarbonylpropyl, δ-methoxycarbonylbutyl, β-sulfoethyl, γ- Sulfopropyl, γ-sulfobutyl, δ-sulfobutyl, benzyl, phenethyl, p-carboxybenzyl, p-sulfophenethyl and the like) and alkenyl (eg allyl). R ³ , R ⁴ , R ⁵ , R
⁶ independently represents a substituted or unsubstituted alkyl group (synonymous with R ¹ and R ² ), an alkenyl group (R ¹ ,
R ² ), an aryl group (eg, phenyl,
(Eg, tolyl, methoxyphenyl group, etc.), among which an alkyl group having 6 or less carbon atoms is preferable. L ¹ , L ² ,
L ³ , L ⁴ and L ⁵ each independently represent a substituted or unsubstituted methine group, which may be bridged with each other to form a 5- or 6-membered substituted or unsubstituted carbocyclic ring. good. m and n each independently represent an integer of 0 or 1, but they never become 0 at the same time. X is a counter ion (eg, chlorine, bromine, iodine, perchloric acid, benzenesulfonic acid, p
-Toluenesulfonic acid, methylsulfuric acid, ethylsulfuric acid, potassium, sodium, pyridinium, triethylammonium ion, etc.), which forms an inner salt when it is part of the dye molecule itself.

Specific examples of the sensitizing dye represented by Chemical Formula 1 used in the present invention are shown below. However, the sensitizing dye used in the present invention is not limited to these.

[0008]

[Chemical 2]

[0009]

[Chemical 3]

[0010]

[Chemical 4]

[0011]

[Chemical 5]

[0012]

[Chemical 6]

[0013]

[Chemical 7]

[0014]

[Chemical 8]

[0015]

[Chemical 9]

[0016]

[Chemical 10]

Next, among the dyes represented by the chemical formula 1 of the present invention,
A typical synthesis example will be described.

Synthesis of Chemical Formula 7

7.4 g of 6-amino-2-methylmercaptobenzoxazole and 30 ml of pyridine were mixed,
5.1 g of methanesulfonyl chloride was added dropwise while keeping the internal temperature at 10 ° C or lower. After removing the cold bath at the same temperature for 15 minutes and stirring for 1 hour, the reaction mixture was cooled to 400 m with ice water.
It was poured into 1 l. Then, the target component was extracted with ethyl acetate (75 ml × 3 times). Wash the organic layers together (2
(00 ml × 3 times) and dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and 2-methylmercapto-6-methylsulfonamidobenzoxazole: intermediate A8.
8 g was obtained. (Melting point 117 to 120 ° C.)

0.52 g of intermediate A and 0.3 of dimethyl sulfate
0 g was mixed and heated at a bath temperature of 100 ° C. for 30 minutes. Then 3-ethyl-5,6-dimethyl-2- (3,5,5
-Trimethyl-2-cyclohexene-1-ylidene) methylbenzothiazolium perchlorate 0.85 g, acetic anhydride 1 ml, DMF 8 ml were added, and the bath temperature was 100 ° C again.
After heating to homogenize, triethylamine 1.4 ml
Was added. After reacting for 3 minutes, isopropyl ether 60m
1 was added, cooled, stirred well, and then the supernatant was removed by decantation. 15 ml of methanol was added to the residue, and the mixture was heated under reflux for 5 minutes. After allowing to cool, the precipitated crystals are filtered, washed with methanol and dried to give a melting point of 259 ° C.
0.10 g of (decomposed) green-blue crystalline powder was obtained. The absorption maximum of the methanol solution was 626.5 nm.

The silver halide photographic emulsion in which the sensitizing dye represented by Chemical Formula 1 used in the present invention is used is a silver chloride, silver bromide, silver chlorobromide, silver iodobromide prepared by a conventional method. , Silver chloroiodobromide or the like.

To add the sensitizing dye represented by Chemical Formula 1 of the present invention to these silver halide photographic emulsions, methanol, ethanol, acetone, cellosolve, pyridine and dimethylformamide, which are optionally miscible with an aqueous solution or water. Can be added alone or as a solution of a mixed solvent. In addition, it is generally preferable to add these sensitizing dyes to the silver halide photographic emulsion immediately after the completion of the second ripening. The addition amount varies depending on the type of sensitizing dye or the type of silver halide photographic emulsion, but it can be used in a wide range of about 4 to 1,200 mg per 100 g in terms of silver nitrate.

The silver halide photographic emulsion in which the sensitizing dye represented by Chemical Formula 1 of the present invention is used includes noble metal sensitization, sulfur sensitization, reduction sensitization and sensitization combining them or polyalkylene oxide compounds. It may be added.

The silver halide photographic emulsion in which the sensitizing dye represented by Chemical Formula 1 of the present invention is used may be spectrally sensitized with other sensitizing dyes, for example, known cyanine and merocyanine dyes, if necessary. Well, further by known methods stabilizers, surfactants, hardeners, optical brighteners, ultraviolet absorbers,
Additives such as filter dyes, anti-irradiation dyes, anti-halation dyes, preservatives, plasticizers, matting agents, color couplers and the like can be contained. Further, when used in a light-sensitive material for stabilizing processing, a developing agent or its precursor can be contained.

Examples of the protective colloid of the silver halide photographic emulsion in which the sensitizing dye represented by Formula 1 of the present invention is used include gelatin, gelatin derivatives such as phthalated gelatin and malonated gelatin, cellulose derivatives, and soluble starch. , Water-soluble polymers and the like.

The support coated with the silver halide photographic emulsion using the sensitizing dye represented by the formula 1 of the present invention is, for example, baryta paper, plastic laminated paper, synthetic paper, cellulose triacetate, polyethylene terephthalate. Resin films and the like can be used. If necessary, an undercoat layer and an antihalation layer may be provided on these supports by a known method.

[0027]

EXAMPLES The present invention will be specifically described below with reference to examples.

To a silver chloride emulsion prepared by a conventional method for producing a silver halide photographic emulsion, 1.2 ml of 0.05% DMF solution of sensitizing dyes 11, 12, and 13 for comparison with the sensitizing dye of the present invention. / GAg was added. These emulsions at 40 ° C
The spectral sensitizing effect was stabilized for 45 minutes in the above bath.
Then, after adding a predetermined amount of a stabilizer, a surfactant and a hardener, it was coated on a polyethylene-laminated paper support, dried, and left at 35 ° C. overnight. Then, it was cut into an appropriate size and used as a test sample. Each sample thus obtained was wedge-exposed according to the ISO method, and D-7
2 developer (developing solution of Eastman Kodak Co., USA) was developed at 20 ° C. for 90 seconds, stopped and fixed, washed with water, and dried to obtain strips having a predetermined black and white image. The density was measured using a MACHBETH-TD504 densitometer manufactured by Macbeth Corporation in the United States to evaluate sensitivity, fog and residual color. The reference point of the optical density for which the sensitivity was determined was the point of [fog + 0.70]. The white light sensitivity was set to 100 for the non-added sample to which no sensitizing dye was administered, and the red sensitivity was the Ratten Gelatin Filter No. 29, and the relative value when the sensitivity value of Comparative Sensitizing Dye 13 is set to 100. The residual color was evaluated by visually evaluating the hue of the unexposed area. "5" represents the best quality and "1" represents the worst quality. The results are shown in Table 1.

[0029]

[Chemical 11]

[0030]

[Chemical 12]

[0031]

[Chemical 13]

[0032]

[Table 1]

As is clear from Table 1, the sensitizing dyes of the present invention are superior to the comparative sensitizing dyes in terms of sensitivity, fog and residual color.

[0034]

By using the sensitizing dye 1 of the present invention, it is possible to obtain a silver halide photographic light-sensitive material having high sensitivity and less residual color or fog due to dye contamination.

Claims (1)

[Claims] 1. A spectral sensitizing dye for photography represented by the following chemical formula 1. [Chemical 1] [In the formula, Z ¹ and Z ² each represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle. R ¹ and R ² are
Each independently represents a substituted or unsubstituted alkyl group or alkenyl group, and R ³ , R ⁴ , R ⁵ , and R ⁶ each independently represent a substituted or unsubstituted alkyl group, alkenyl group, or aryl group. L ¹ , L ² , L ³ , L ⁴ , L
^5's each independently represent a substituted or unsubstituted methine group. m and n each independently represent an integer of 0 or 1, but they never become 0 at the same time. X represents a counter ion. ]