JP3343827B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly to a laser and an LED in the red-sensitive region.
The present invention relates to a silver halide photographic material having a high spectral sensitivity to a light source, and having improved fog and residual color after processing.

[0002]

2. Description of the Related Art With the development of rapid information transmission systems in recent years, silver halide photographic light-sensitive materials are increasingly required to have high sensitivity. For example, there are a photocomposition system for immediately displaying information output from an electronic computer as characters or graphics by a cathode ray tube, and a press facsimile system for quickly sending a newspaper manuscript to a remote place.

The characteristics required for a silver halide photographic material for such applications include a cathode ray tube (CRT), a laser such as helium-neon gas, and a light emitting diode (L).
A light source such as ED) has high sensitivity to so-called high illuminance short-time exposure (called flash exposure) of 10 ^-4 seconds or less, and further requires characteristics such as high contrast and high resolution. In order to obtain a high-sensitivity, high-contrast silver halide photographic light-sensitive material, various methods have been adopted.
Problems such as residual color and increase in fog due to dye contamination have occurred, and these are not yet satisfactory, and a new technique for obtaining a high-sensitivity silver halide photographic material is required.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to have high sensitivity to a red-sensitive laser and an LED light source,
It is another object of the present invention to provide a silver halide photographic light-sensitive material having less residual color and fog due to dye contamination.

[0005]

An object of the present invention is to provide at least one silver halide photographic emulsion layer spectrally sensitized with a sensitizing dye represented by the formula (3), And / or in another hydrophilic colloid layer, a silver halide photographic light-sensitive material characterized by containing a polymer represented by the following formula (5).

[0006]

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(Wherein Z and Z ₁ each represent an atom group necessary to form a 5- or 6-membered nitrogen-containing heterocyclic ring. Examples of the heterocyclic ring include a thiazoline ring, a thiazole ring and a benzothiazole. A non-metallic atomic group necessary to form a nitrogen-containing heterocycle such as a ring, a naphthothiazole ring, a selenazole ring, a benzoselenazole ring, a naphthoselenazole ring, an oxazole ring, an imidazole ring, a benzimidazole ring or a quinoline ring. The carbon atom of the heterocyclic ring includes a halogen atom (for example, chlorine atom, bromine atom, etc.), an alkyl group (for example, methyl group, ethyl group, n-
Substituents such as a propyl group, an n-butyl group, a t-butyl group and the like, an alkoxy group (for example, a methoxy group, an ethoxy group, an n-propyloxy group and the like), a hydroxy group and an aryl group may be attached.

R ₁ and R ₂ may be the same or different and each represents an alkyl group (eg, a methyl group, an ethyl group, an n-
Propyl, isopropyl, n-butyl, 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 group, δ-methoxycarbonylbutyl group, β-sulfoethyl group, γ-sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, vinylmethyl group, benzyl group, phenethyl group, p-carboxybenzyl group, p —Sulfophenethyl group, etc.) and alkenyl group (eg, allyl, etc.).

R ₃ represents an alkyl group, an alkenyl group or an aryl group (for example, a phenyl group, a tolyl group, a methoxyphenyl group, a chlorophenyl group, a naphthyl group, etc.) as described above for R ₁ and R ₂ . L,
L ₁ and L ₂ each represent a methine group and may have a substituent, for example, a compound of the formula ( ₄₎ , wherein R ₄ is an ethyl group, a methyl group, an ethoxy group, an aryl group (for example, a phenyl group, p
-Chlorophenyl group, p-methylphenyl group, etc.). X represents an anion (eg, chloride ion, bromine ion, iodine ion, perchloric acid, benzenesulfonate,
p-toluenesulfonate, methyl sulfate, ethyl sulfate, etc.). n ₁ and n ₂ each represent 1 or 2. m represents 0 or 1, and in the case of an inner salt, m = 0.

[0010]

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[0011]

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Wherein A represents a monomer unit derived from an ethylenically unsaturated dicarboxylic acid or dicarboxylate copolymerizable with an ethylenically unsaturated monomer. M represents a hydrogen atom or a monovalent metal atom. X and y represent the molar percentage of each component, x takes a value of 20 to 100, and y takes a value of 0 to 80.)

Next, specific examples of the compound used in the present invention will be illustrated. However, the compound used in the present invention is not limited to these.

Specific examples of the sensitizing dye represented by Chemical formula 3.

[0015]

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[0016]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0024]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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The compound represented by Chemical formula 3 used in the present invention can be synthesized by referring to US Pat. No. 2,656,351.

The sensitizing dye of formula (3) may be added to the silver halide photographic emulsion at any time during the emulsion process. The amount of addition varies depending on the type of sensitizing dye or the type of silver halide photographic emulsion, but is usually 0.01 g to 10 g, more preferably 0.1 g to 1 g, per 1 kg of silver nitrate.

Specific examples of the acid polymer represented by Chemical Formula 5.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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Examples of the synthesis of these acid polymers are described in JP-A-62-220947.

The addition amount of these acid polymers is 10 mg to 1 g per 1 m ² , more preferably 10 mg to 50 g.
0 mg. These acid polymers can be added to the silver halide emulsion layer or another hydrophilic colloid layer.

The silver halide emulsion used in the present invention is:
Chemical sensitization can be performed by a known method. Examples of the sulfur sensitizer include thiosulfate, thiourea, allylisothiocyanate, cystine, rhodanine, and U.S. Patent Nos. 1,574,944, 2,278,947, 2,410,689, Sulfur-containing compounds as described in JP-A Nos. 2,440,206, 3,187,458, and 3,501,313 can be used. No. 2,448,060 with sulfur sensitization.
No. 2,540,086, 2,556,245
No. 2,566,263 can be used in combination with a sensitization method using a salt of a noble metal such as platinum palladium, iridium, rhodium or ruthenium. Further, a sensitization method using various gold compounds such as potassium chlorolate and auric trichloride and a palladium compound such as palladium chloride can be used in combination.

In the present invention, known stabilizers such as mercaptotetrazole, mercaptotriazole and benzimidazole, various development accelerators such as antifoggants and polyalkylene oxides, thioether compounds and quaternary ammonium salt compounds are used. Can be. Examples of the hydrophilic colloid used in the present invention include gelatin, colloidal albumin, proteins such as casein, cellulose derivatives such as carboxymethylcellulose, sugar derivatives such as agar, sodium alginate and starch, and synthetic polymers such as polyvinyl alcohol and polyacrylamide. Can be used alone or in a mixture at an appropriate ratio.

As the support used in the present invention, there may be used those usually used for photographic light-sensitive materials such as films such as cellulose acetate film and polyethylene terephthalate film, and paper such as baryta or paper coated or laminated with polyethylene or polypropylene. Any is fine.

The light-sensitive material of the present invention may further contain various compounds such as a hardener, a surfactant, an antistatic agent, a plasticizer and a matting agent in order to control the properties of the material. Hereinafter, the present invention will be described specifically with reference to examples.

[0047]

【Example】

Example 1 A cubic monodispersed silver iodobromide emulsion having an average particle diameter of 0.40 μm was prepared by a pAg control double jet method. The content of silver iodide was set at 1.0 mol% so that the silver iodide was distributed evenly throughout the grains.

This emulsion was adjusted to pH 6.0, sulfur-gold sensitized by a conventional method, and a stabilizer was added. Then, a sensitizing dye shown in Table 1 was added in an amount of 0.7 g / m ² (3 0.0 g /
m ² ) was added. Thereafter, sodium sulfonate bis (2-ethylhexyl) ester sodium salt was added as a surfactant, and a 15 mg / m ² oil-soluble fluorescent whitening agent was further added to di (2-ethylhexyl) phthalate ester and ethyl acetate. This solution was added to an aqueous gelatin solution containing sodium 2-sulfonate-succinate bis (2-ethylhexyl) ester sodium salt and emulsified and dispersed. Silver was added to an RC paper obtained by adding an acid polymer of 50 mg / m ² and formalin as a hardening agent to an undercoated emulsion paper.
Coating was performed so as to be 5 g / m ² . Each sample thus obtained was exposed and developed to evaluate the sensitivity, fog and hue. The results are shown in Table 1.

For exposure, a xenon lamp was used.
10 ⁻⁵ through an interference filter having a transmission peak at m
Exposure in seconds. Further, the sensitivity value was determined as an exposure amount necessary to obtain a reflection density of 0.75. The relative values when the sensitivity value of one sample was set to 100 are shown. The hue was evaluated on a 5-point scale, with 5 being good, 1 being bad, and 3 or more being usable.

(Comparison of sensitizing dye)

[0051]

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[0053]

[Table 1]

As is clear from Table 1, the sample of the present invention has high sensitivity, low fog and good hue.

[0055]

According to the present invention, it is possible to obtain a silver halide photographic material having high sensitivity to a light source in the red-sensitive region and having less residual color and fog due to dye contamination.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁷ , DB name) G03C 1/22 G03C 1/053

Claims (1)

(57) [Claims] 1. A support having at least one silver halide emulsion layer on a support, wherein said halide emulsion is spectrally sensitized with a sensitizing dye represented by the following formula 1, and said emulsion layer and / or Wherein the hydrophilic colloid layer contains a polymer represented by the following formula (2). Embedded image (In the formula, Z and Z ₁ each represent an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocyclic ring usually used in cyanine dyes. R ₁ and R ₂ may be the same or different. R ₃ represents an alkyl group, an alkenyl group or an aryl group, L, L ₁ and L ₂ each represent a substituted or unsubstituted methine group, and X represents an anion. N ₁ and n ₂ each represent 1 or 2. m represents 0 or 1, and in the case of an intramolecular salt, m = 0.) (In the formula, A represents a monomer unit derived from an ethylenically unsaturated dicarboxylic acid or a dicarboxylic acid salt copolymerizable with an ethylenically unsaturated monomer. M represents a hydrogen atom or a monovalent metal atom. , Y represents the molar percentage of each component, x takes a value of 20 to 100, and y takes a value of 0 to 80.)