JPH09160160A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a superior spectrally sensitizing dye high in sensitivity, especially, in a red wavelength region and small in residual dye stains after development processing by incorporating at least one kind of specified spectrally sensitizing dye. SOLUTION: The silver halide photographic sensitive material contains at least one of the spectrally sensitizing dyes represented by formulae I and II in which each of Z1 -Z9 is an atomic group necessary to form a 5- or 6-membered N-containing hetero ring, such as an oxazoline ring or the like in the case of Z1 , Z4 , and Z5 , and a thiazolidine ring or the like in the case of Z2 , Z3 , Z6 -Z9 ; each of R1 , R3 , and R4 is an optionally substituted alkyl group; each of R2 and R5 is a group represented by formula III: -L4 -S-R6 , here, L4 is a divalent bonding group and R6 is an alkyl group: each of L1 -L3 is an optionally substituted methine group unit comprising 1 C or 3 C X is a counter-ion; and (n) is an integer necessary to neutralize an intramolecular charge.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, 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 Silver halide photographic light-sensitive materials are required to have high sensitivity in different specific wavelength ranges depending on the purpose of use. As one of the manufacturing techniques for such a silver halide photographic light-sensitive material, various types of sensitizing dyes are added to a silver halide photographic emulsion, and in a wavelength region longer than the intrinsic light-sensitive wavelength region of the silver halide, It is generally well known that 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 photosensitive 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.

In order to satisfy the above requirements, various types of cyanine dyes and merocyanine dyes have been proposed. Especially, He-Ne laser, red L
For sensitizing dyes for red light sources such as D and red LED, US Pat. Nos. 4,965,183 and 5,116,7
The dyes described in No. 22 and the like have been proposed, and one of the features thereof is that they have little residual color contamination after development processing.

[0005] However, even these sensitizing dyes do not completely satisfy the above requirements, and further improvement is required.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide an excellent spectral sensitizing dye which satisfies the above-mentioned requirements, has a high sensitivity especially in the red region, and has little residual color contamination after development processing. It is to be.

[0007]

The object of the present invention has been achieved by the spectral sensitizing dyes represented by Chemical Formulas 1 and 2 above.

The sensitizing dye of the present invention will be specifically described below. In the formulas 1 and 2, Z _{1 to} Z ₉ are each 5
Alternatively, it represents an atomic group necessary for forming a 6-membered nitrogen-containing heterocycle. Specific examples of the nitrogen-containing heterocycle formed by Z ₁ , Z ₄ , and Z ₅ (indicated by the name of the starting tertiary base for convenience) include, for example, oxazoline ring, oxazole ring, benzoxazole ring, naphthoxazole ring, Thiazoline ring,
Thiazole ring, thiazine ring, benzothiazole ring, naphthothiazole ring, benzoselenazole ring, naphthoselenazole ring, quinoline ring, benzoquinoline ring, indolenine ring, benzoindolenine ring, benzimidazole ring,
There are naphthoimidazole rings and the like. Further, carbon atoms of these heterocycles include 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 groups (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. Among these, those having 12 or less carbon atoms including a substituent are preferred.

Specific examples of the nitrogen-containing heterocycle formed by Z ₂ , Z ₃ and Z _{6 to} Z ₉ include, for example, an oxazolidine ring, a thiazolidine ring, an imidazolidine ring and the like, and nitrogen substitution of these heterocycles. Examples of groups are alkyl groups (eg methyl, ethyl, n-propyl, i-propyl,
n-butyl, n-amyl, 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, allyl, propargyl group, etc.), aryl group (eg, phenyl, methoxyphenyl group, etc.), heterocyclic group (eg, 2- Pyridyl, 2-thiazolyl, 4-tetrahydropyranyl group, etc.) and the like. Among these, those having 12 or less carbon atoms including a substituent are preferred.

R ₁ , R ₃ and R ₄ represent a substituted or unsubstituted alkyl group (for example, as described in the examples of the nitrogen substituents of Z ₂ , Z ₃ , Z _{6 to} Z ₉ ). R ₂ and R ₅ represent a group represented by Chemical formula 3. In the formula of Chemical formula 3, R ₆ represents a substituted or unsubstituted alkyl group. Of these, preferred is a lower alkyl group having 4 or less carbon atoms. L ₄ represents a divalent linking group. Of these, preferred is an alkylene group having 4 or less carbon atoms.

L _{1 to} L ₃ each represent a substituted or unsubstituted methine group unit having 1 or 3 carbon atoms.
Examples of those substituents are alkyl groups (eg Z ₂ ,
Z ₃ , Z _{6 to} Z ₉ as described in the examples of nitrogen substituents), an aryl group (for example, as described in the examples of nitrogen substituents of Z ₂ , Z ₃ , Z _{6 to} Z ₉ ), alkoxy A group (eg, methoxy,
Ethoxy group) etc. X is a counter ion (for example, anion such as chlorine, bromine, iodine, perchloric acid, benzenesulfonic acid, p-toluenesulfonic acid, methylsulfate or ethylsulfate ion, cation such as triethylammonium, pyridinium, sodium or potassium). Represent n represents an integer necessary to neutralize the charge. Further, in order to impart good residual color characteristics to these dyes, it is preferable to have at least two water-solubilizing groups in the molecule of Chemical formula 1 and at least one water-solubilizing group in the molecule of Chemical formula 2. A preferable example of the water-solubilizing group is pK.
a group having a dissociative proton having an a value of less than 12 (for example, phenolic hydroxyl group, sulfonamide group, etc.), free carboxylic acid and sulfonic acid or salts thereof (for example, triethylammonium, pyridinium, sodium,
Examples thereof include salts such as potassium) and lower alkyl esters (such as methyl ester and ethyl ester).

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

[0013]

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[0014]

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[0015]

[Chemical 6]

[0016]

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[0017]

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Next, among the dyes of the present invention, typical synthesis examples will be described.

Synthesis of S1 In a mixed solution of 35 g of 3-ethyl-2-methylbenzothiazolium p-toluenesulfonate and 100 ml of pyridine, 14 g of 3-methylthiopropionyl chloride was added dropwise under ice-water cooling and stirring for 10 minutes. did. Then, the bath temperature was raised and the mixture was stirred at 70 ° C. for 30 minutes. Next, the solvent was distilled off, and 150 ml of 1N hydrochloric acid was added to the residue. The precipitated solid was collected by filtration, washed with water and hydrous ethanol (water / ethanol = 2/3) in that order, and dried to obtain 20 g of a ketone derivative: intermediate A. Melting point: 174 to 177.5 ° C

15 g of intermediate A, 11 g of Lawesson's reagent and 100 ml of benzene were mixed and heated under reflux for 30 minutes. Then the solvent was distilled off, and the residue was 100 ml of ethanol.
Was added and stirred at room temperature for 1 hour. Then, the precipitated crystals were collected by filtration, washed with ethanol and dried to obtain 10.2 g of thioketone derivative: intermediate B. Melting point: 99-101.
5 ℃

Intermediate B 3.0 g, dimethyl sulfate 1.3
g, and sulfolane 3 ml, and mixed at a bath temperature of 90 ° C. for 30
Heated for minutes. Then 1.9 g of Rhodanine-3-acetic acid,
20 m of ethanol was added, and 4.2 ml of triethylamine was further added with heating under reflux. After heating under reflux for 20 minutes, an ethanol solution of potassium acetate (1.5 g / 15
ml) was added, and the mixture was allowed to cool, and the precipitated crystals were collected by filtration. Then, wash with ethanol and diisopropyl ether in that order and dry,
2.6 g of merocyanine dye A: intermediate C was obtained. Melting point: 192 ° C-decomposition λmax (methanol) 532 nm

0.49 g of intermediate C, 0.37 g of methyl p-toluenesulfonate and 2 ml of m-cresol were mixed and heated and stirred at a bath temperature of 50 ° C. for 75 minutes. Next, 0.35 g of 2-methyl-3- (2-carboxyethyl) benzothiazolium iodide and 10 m of ethanol were added, and 0.4 ml of triethylamine was further added with stirring at a bath temperature of 50 ° C. After stirring for 20 minutes at the same temperature, ethanol solution of potassium acetate (0.3 g / 5 ml) was added, and the precipitated crystals were collected by filtration. The crude dye crystals thus obtained were treated with 20 m of ethanol.
It was dispersed in 1 l, heated under reflux for 20 minutes, and then filtered again. Subsequently, ethanol and diisopropyl ether were washed in this order and dried to obtain 0.15 g of S1. Melting point 202 ° C-decomposition λmax (methanol) 604.5 nm

Synthesis of S15 0.49 g of the intermediate C, 0.37 g of methyl p-toluenesulfonate and 2 ml of m-cresol were mixed, and the bath temperature was 50.
The mixture was heated and stirred at 75 ° C for 75 minutes. Next, add 0.19 g of rhodanine-3-acetic acid and 10 m of ethanol, and further add a bath temperature of 5
0.4 ml of triethylamine was added with stirring at 0 ° C. 2
After stirring for 0 minutes at the same temperature, a potassium acetate ethanol solution (0.3 g / 5 ml) was added, and the precipitated crystals were collected by filtration. The crude dye crystals thus obtained were dissolved by heating in 20 ml of methanol, and 0.5 ml of 2N hydrochloric acid was added therein. The precipitated crystals were collected by filtration, washed with methanol, water, methanol and diisopropyl ether in this order and dried to give 0.11 g of S15.
I got Melting point 210 ° C-decomposition λmax (methanol) 583 nm

In order to use the above chemical formulas 1 and 2 of the present invention in a silver halide emulsion, methanol, ethanol, acetone, cellosolve, pyridine, dimethylacetamide and dimethylformamide, which are water-soluble and can be optionally mixed with water. It can be added to the silver halide emulsion as a solution of an organic solvent such as the above alone or as a mixed solvent, or can be dispersed and added to the silver halide emulsion as a solid fine particle dispersion. When these compounds are added to the silver halide emulsion, they may be added at any time during the emulsion production process, but generally they are preferably added after the physical ripening and before the coating after the completion of the chemical ripening. The addition amount varies depending on the type of compound or the type of silver halide emulsion, but is usually 5 × 10 ⁻⁶ to 2 × 1 per mol of silver halide.
A range of 0 ^-1 mol is preferred.

The dyes represented by Chemical Formulas 1 and 2 used in the present invention may be used alone or in combination of two or more kinds. Further, it may be used in combination with a sensitizing dye other than the present invention.

The silver halide emulsion used in the present invention is not particularly limited, and silver chlorobromide, silver chloroiodobromide, silver iodobromide, silver bromide and the like can be used. When silver or silver iodobromide is used, the content of silver iodide is preferably 5 mol% or less.

The form, crystal habit, size distribution, etc. of the silver halide grains used in the present invention are not particularly limited, but those having an average grain size of 0.7 micron or less, particularly 0.5 micron or less are preferable. It is preferable that 90% or more of all particles have a particle diameter within the range of ± 10% of the average particle diameter. The preparation method of silver halide emulsion is forward mixing, reverse mixing,
Any known method such as simultaneous mixing may be used.

The emulsion that has been physically ripened is preferably coated with necessary additives after desalting, but the desalting treatment can be omitted.

The silver halide emulsion used in the present invention is:
It can be chemically aged by a known method. Examples of the sulfur sensitizer include thiosulfate, thiourea, allylisothiocyanate, cystine and rhodanine, and US Pat. Nos. 1,574,944 and 2,278,947.
No. 2,410,689, No. 2,440,20
No. 6, No. 3,187,458, No. 3,415,6
Sulfur-containing compounds as described in No. 49, No. 3,501,313, etc. can be used. In addition to sulfur sensitization, U.S. Pat. Nos. 2,448,060 and 2,
540,086, 2,556,245, 2,566,263 described in combination with a sensitizing method using a salt of a noble metal such as platinum, palladium, iridium, rhodium, ruthenium. Can be used. Further, a sensitizing method using various gold compounds such as potassium chloroaurate and auric chloride and palladium compounds such as palladium chloride can be used in combination.

The light-sensitive material of the present invention may be provided with an overcoat layer, an intermediate layer, a backcoat layer, an undercoat layer and other hydrophilic colloid layers in addition to the light-sensitive emulsion. Furthermore, a matting agent may be contained in these layers.

As the binder or protective colloid that can be used in the emulsion layer, overcoat layer, intermediate layer, backcoat layer and the like of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic substances are used. Sex colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives, polyvinyl alcohol. , A partial acetal of polyvinyl alcohol, poly-N-vinylpyrrolidone,
It is possible to use various synthetic polymer substances such as single or copolymers of polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and the like. As the gelatin, other than lime-processed gelatin, acid-processed gelatin or acid-processed gelatin as described in Bull.Soc.Sci.Phot.Japan, No.16, P30 (1966) may be used. A hydrolyzate or an enzymatic hydrolyzate thereof can also be used.

The photographic emulsion used in the present invention includes, for example, known stabilizers such as mercaptotetrazoles, mercaptotriazoles, benzotriazoles and benzimidazoles, antifoggants, polyalkylene oxides, thioether compounds and quaternary compounds. Various development accelerators such as ammonium salt compounds can be contained. Further, an amine compound, a hydrazine compound, a quaternary onium salt compound, a carbinol compound, or the like may be contained as a compound that promotes a high contrast. Examples of these nucleation accelerators include U.S. Pat. Nos. 4,975,354 and 5,126,227.
JP-A-62-250439 and 63-12404.
No. 5, and those described in JP-A-2-97939.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chrome alum etc.), aldehydes (formaldehyde, glyoxal etc.), N-methylol compounds, dioxane derivatives (2,3-dihydroxydioxane etc.), active vinyl compounds, active halogen compounds (2,4-dichloro-). 6-hydroxy-s-triazine and the like) can be used alone or in combination.

Further, the photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material produced by using the present invention may be coated with a coating aid,
A surfactant may be included for various purposes such as antistatic, improvement of slipperiness, emulsion dispersion, prevention of adhesion and improvement of photographic characteristics (for example, development acceleration, hardening, sensitization). For example, saponins (steroids), alkylene oxide derivatives (polyethylene glycol, polyethylene glycol alkyl ethers, etc.), glycidol derivatives (alkenyl succinic acid polyglyceride, etc.), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Anionic interface containing carboxylic groups such as ionic surfactants, alkyl carboxylates, alkyl sulfates, alkyl phosphates, etc., and acidic groups such as sulfo, phospho, sulfate, phosphate, etc. Activators, amino acids, aminoalkyl sulfonic acids, amphoteric surfactants such as aminoalkyl sulfates or phosphoric acid esters, aliphatic or aromatic quaternary ammonium salts, pyridinium,
Cationic surfactants such as heterocyclic quaternary ammonium salts such as imidazolium can be used.

The photographic light-sensitive material used in the present invention may contain a water-insoluble or sparingly soluble synthetic polymer decomposition product in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Monomer components such as vinyl acetate, acrylonitrile, olefin, styrene, etc., or a combination thereof with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, styrene sulfonic acid, etc. The polymer can be used.

For the photographic light-sensitive material used in the present invention, any support known in the art can be used. Examples of the support include glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta-coated paper, polyolefin (eg, polyethylene, polypropylene, etc.) laminated paper, polystyrene film, polycarbonate film, metal plate such as aluminum, and the like. These supports may be subjected to corona treatment by a known method, and if necessary, may be subjected to an undercoating treatment by a known method.

In the present invention, a system may be adopted in which a developing agent is incorporated in the light-sensitive material and the processing is carried out with an alkaline activator solution. (JP-A-57-129433,
57-129434, 57-129435, 5
7-129436, U.S. Pat. No. 4,323,643, etc.). The treatment temperature is usually selected from 18 ° C to 50 ° C, but may be lower than 18 ° C or higher than 50 ° C.

[0038]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples.

Example 1 A silver chloride emulsion prepared by a conventional method for producing a silver halide photographic emulsion was added with a sensitizing dye of the present invention and a comparative sensitizing dye.
1.2 ml / g Ag of 75 mmol / l DMF solution was added. These emulsions were aged in a bath at 40 ° C. for 45 minutes to stabilize the spectral sensitization effect. Thereafter, predetermined amounts of a stabilizer, a surfactant, and a hardener were added, and then the mixture was applied to a polyethylene-laminated paper support, dried, and aged at 35 ° C. overnight. Then, it was cut into an appropriate size to obtain a test sample. Each sample thus obtained was wedge-exposed based on the ISO method, developed with D-72 developing solution (developing solution of Eastman Kodak Company, USA) at 20 ° C. for 90 seconds, stopped and fixed, and After washing with water and drying, strips having a predetermined black and white image were obtained. This is MACHBETH-TD5 manufactured by Macbeth Corporation of the United States.
The density was measured using a 04 densitometer to evaluate sensitivity, fog and residual color. The reference point of the optical density at which the sensitivity was determined was [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. manufactured by Eastman Kodak Company. 29, the relative value when the sensitivity value of the comparative sensitizing dye CS3 is set to 100 in Table 1, and the sensitivity value of the comparative sensitizing dye CS6 is 1 in Table 2
The values are shown as relative values when 00 is set. For the residual color, the hue of the unexposed portion was visually evaluated. "5" is the best,
"1" represents the worst quality. The results are shown in Tables 1 and 2.

[0040]

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[0041]

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[0042]

[Table 1]

[0043]

[Table 2]

As is clear from Tables 1 and 2, the sensitizing dyes of the present invention have less residual color after treatment than the sensitizing dyes for comparison, and also in terms of sensitivity and balance with fog. It can be seen that it shows superiority.

[0045]

By using the sensitizing dye of the present invention,
It is possible to obtain a highly sensitive silver halide photographic light-sensitive material with little residual color due to dye contamination.

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one spectral sensitizing dye represented by the following chemical formula 1 or chemical formula 2. Embedded image Embedded image [Wherein Z ₁ to Z ₉ represents an atomic group necessary for forming a 5 or 6-membered nitrogen-containing heterocyclic ring. R ₁ , R ₃ and R ₄ represent a substituted or unsubstituted alkyl group. R ₂ and R ₅ represent a group represented by Chemical formula 3. L _{1 to} L ₃ each represent a substituted or unsubstituted methine group unit having 1 or 3 carbon atoms. X represents a counter ion. n represents an integer necessary to neutralize the charge. ] [In the formula, R ₆ represents a substituted or unsubstituted alkyl group. L ₄ represents a divalent linking group. ]