JP2846499B2 - 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 light-sensitive material, and more particularly to a silver halide photographic material having a high spectral sensitivity to a helium-neon laser light source and having an improved residual color after processing. It relates to a silver photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, scanning and exposure of silver halide photographic materials with a laser beam to record images has become popular. Typical devices include a scanner that decomposes continuous-tone photographs, etc., a facsimile to output image information that has been transmitted, and an output device for computer typesetting that is used to output character manuscripts in the printing field. It is. As a laser light source used for such a device, there are an ion laser such as argon and a gas laser such as helium-neon, and an argon laser light source has been mainly used so far. However, since this light source is large and expensive, a dot generator type scanner using a compact and inexpensive helium-neon laser light source has recently been developed by various companies.

[0003] The photosensitive material used in the scanner is required to have various characteristics. That is, with a helium-neon laser light source (632.8 nm), 10 ⁻³ to 10 ^−7.
It has high spectral sensitivity to so-called high-illuminance short-time exposure (called flash exposure) in the order of seconds,
Characteristics such as high resolution are required. Various methods have been employed to obtain this high-sensitivity, high-contrast silver halide photographic light-sensitive material. However, problems such as residual color due to dye contamination and an increase in fog occur, and these methods are still insufficient. However, a new technique for obtaining a high-sensitivity silver halide photographic material is required.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material having high sensitivity to a helium-neon laser light source and having less residual color and fog due to dye contamination. is there.

[0005]

SUMMARY OF THE INVENTION The object of the present invention is as follows.
Having at least one silver halide photographic emulsion layer spectrally sensitized with a sensitizing dye represented by the formula (1), and wherein said silver halide photographic emulsion layer and / or another hydrophilic colloid layer are At least one of the compounds represented by Chemical formula 9 or Chemical formula 10
A silver halide photographic light-sensitive material characterized by containing

[0006]

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Wherein Z and Z ₁ are each a 5-membered ring and 6
Represents the group of atoms necessary to form a membered nitrogen-containing heterocycle. Examples of the heterocycle include a thiazoline ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, a selenazole ring, a benzoselenazole ring, a naphthoselenazole ring, an oxazole ring, a benzoxazole ring, a naphthoxazole ring, an imidazole ring, and a benzimidazole ring. Represents a group of non-metallic atoms necessary for forming a nitrogen-containing heterocyclic ring such as a halogen atom (eg, a chlorine atom, a bromine atom, etc.), an alkyl group (eg, a methyl group, an ethyl group) Group, n-propyl group, n-butyl group, t-butyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, n-propyloxy group, etc.), hydroxy group, aryl group, etc. Is also good. R ₁ and R ₂ may be the same or different and each represents an alkyl group (eg, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, etc.) or a substituted alkyl group (eg, β- Hydroxyethyl group, γ-hydroxypropyl group, β-acetoxyethyl group, γ-acetoxypropyl group, β-methoxyethyl group, γ-methoxypropyl group, carboxymethyl group, β-carboxyethyl group, γ-carboxypropyl group, δ-carboxybutyl group, ω-carboxypentyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, β-methoxycarbonylethyl group, γ-methoxycarbonylpropyl group, δ-methoxycarbonylbutyl group, β-sulfoethyl group, γ- Sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, benzyl , Phenethyl group,
p-carboxybenzyl group, p-sulfophenethyl group and the like, and alkenyl group (for example, allyl and the like). R
₃ represents an alkyl group, a substituted 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 represent a methine group, and may have a substituent;
For example,

[0008]

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R ₄ represents an ethyl group, a methyl group, an ethoxy group, or an aryl group (for example, a phenyl group, a p-chlorophenyl group, a p-methylphenyl group, etc.). X represents an anion (eg, chloride ion, bromine ion, iodine ion, perchlorate ion, benzenesulfonate ion, p-
Toluenesulfonate, methylsulfate, ethylsulfate, etc.). n represents 0 or 1, and in the case of an internal salt, n = 0. ]

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[0013]

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Wherein R ²¹ is an alkyl or alkenyl group having 4 to 16 (more preferably 5 to 12) carbon atoms;
R ³¹ is an alkyl group or alkenyl group having 5 to 17 carbon atoms (more preferably an integer of 5 to 11), and R ³² and R ³³ may be the same or different and may be an alkyl group having 4 or less carbon atoms, or a hydroxyalkyl group. (For example, β-hydroxyethyl group, γ-hydroxypropyl group, etc.), and the total carbon number of R ³² and R ³³ represents 5 or less. R ⁴¹ and R ⁴² may be the same or different and each is an alkyl or alkenyl group having 4 to 12 carbon atoms, and the total number of carbon atoms of R ⁴¹ and R ⁴² is 18 or less (more preferably, the total carbon number of R ⁴¹ and R ⁴² Number 10-1
4 ) wherein R ⁵¹ is an alkyl or alkenyl group having 5 to 17 carbon atoms (more preferably 13 or less carbon atoms)
And R ⁵² represents an alkyl group having 1 to 3 carbon atoms. p is 1
Represents an integer of 1 to 11 (more preferably an integer of 1 to 8), and q represents 2, 3 or 4. r is an integer of 2 to 8 (more preferably an integer of 2 to 5), s is 0 or 1, t is 1,
Represents 2 or 3. u represents 2, 3 or 4;
²¹ , M ⁴¹ and M ⁵¹ may be the same or different and represent a hydrogen atom or an alkali metal atom (eg, Na, K). ]

Next, specific examples of the sensitizing dye represented by Chemical formula 6 used in the present invention will be shown. However, the compounds used in the present invention are not limited to these.

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Next, specific examples of the compounds represented by the formulas (7), (8), (9) and (10) are shown.

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[0065]

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The sensitizing dye represented by Chemical formula 6 used in the present invention can be synthesized by referring to US Pat. No. 2,656,351. The sensitizing dye of formula (I) is generally added to the emulsion before the emulsion is coated on a suitable support, but may be added during chemical ripening or during the formation of silver halide grains. The compounds represented by the general formulas 7, 8, 9 and 10 used in the present invention are known compounds, for example, JP-B-44-8401,
U.S. Pat. Nos. 2,739,891, 3,502,473
No. 3,026,202, JP-A-48-43924
Nos. 46-79185 and 50-46133, and Ryohei Oda et al., "Synthesis of Surfactant and Its Application" (Maki Shoten, 1964). W. Perry, "Surface Active Agents" (Interscience, 1958); P. The compound can be synthesized by referring to, for example, Encyclopedia of Active Ages, Vol. 2 (Chemical Publish, 1964) by Sisley.

The compounds represented by the formulas (7), (8), (9) and (10) can be added at any time during the preparation of the silver halide photographic emulsion. After aging, it is preferable to wait until it is applied. More preferably, the compounds represented by Chemical Formula 7, Chemical Formula 8, Chemical Formula 9, and Chemical Formula 10 are preferably added before the addition of the sensitizing dye represented by Chemical Formula 6. Further, the addition amount is 1 × 10 ⁻⁷ to 1 × 10 ⁻³ mol / mol Ag, and preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻⁴ mol / mol Ag in sensitizing dyeing 6.
In Compounds 7 to 10, 1 × 10 ^-6 to 1 × 10 ^-1 mol /
It is mol Ag, preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻² mol / mol Ag.

The silver halide emulsion used in the present invention can be prepared by various known methods. The silver halide emulsion used in the present invention may be prepared by using a so-called single jet method or a mixing method called a double jet method, but it is preferable to use a monodisperse emulsion prepared using the latter method. Is good. Further, the crystal habit of the silver halide crystal used in the present invention may be any of cubic, octahedral, tetradecahedral, and tabular crystals, and the grain size is not particularly limited, but is preferably 0.1 μm.
Those having an average particle size of about 2.0 μm are preferred.

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, and Sulfur-containing compounds described in 2,440,206, 3,187,458, 3,415,649, and 3,501,313 can be used. Along with sulfur sensitization, US Pat. Nos. 2,448,060 and 2,540,086
Nos. 2,556,245 and 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 chloroaurate 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, benzotriazole and benzimidazole, various development accelerators such as antifoggants and polyalkylene oxides, thioether compounds and quaternary ammonium salt compounds are used. Can be used.

The hydrophilic colloid used in the present invention includes proteins such as gelatin, colloidal albumin and casein, cellulose derivatives such as carboxymethylcellulose, sugar derivatives such as agar, sodium alginate and starch, polyvinyl alcohol and polyacrylamide. Can be used alone or in a mixture at an appropriate ratio.

The support used in the present invention may be a film usually used for a photographic material such as a cellulose acetate film, a polyethylene terephthalate film or the like, a baryta or a paper coated or laminated with polyethylene, polypropylene or the like. Any may be used.

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 for controlling the properties of the material. Hereinafter, the present invention will be described specifically with reference to examples.

[0074]

EXAMPLE A cubic monodispersed silver iodobromide emulsion having an average particle diameter of 0.25 μm was prepared by the pAg controlled double jet method. The content of silver iodide is 1.5 mol%,
The distribution was averaged over the entire particle. This emulsion was subjected to sulfur-gold sensitization by a conventional method, and 1-phenyl-5-mercaptotetrazole was added thereto.
After adding 1.8 × 10 ⁻³ mol / mol Ag to
Sensitizing dyeing 6 or 61 as a comparison
^-5 mol / mol Ag was added. Thereafter, an emulsion obtained by adding a betaine-type fluorinated surfactant and formalin as a hardening agent was coated on a polyethylene terephthalate film base prepared by subbing so that silver was 3.8 g / m ² .

[0075]

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Each sample obtained in this way was
Wedge exposure was performed with a neon laser beam, development processing was performed, and sensitivity, fog, and residual color were evaluated. The results are shown in Table 1. The sensitivity value was determined as the exposure amount necessary to obtain a transmission density of 3.2.
It is shown as a relative value when 0. For the residual color, the hue of the unexposed portion was visually evaluated. "5" is best, "1"
Indicates the worst quality.

[0077]

[Table 1]

As is clear from Table 1, the sample of the present invention
It can be seen that sensitivity, fog, and residual color all show good performance.

[0079]

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

Claims (1)

(57) [Claims] A silver halide photographic emulsion layer spectrally sensitized with a sensitizing dye represented by the following formula (1):
And the silver halide photographic emulsion layer and / or another hydrophilic colloid layer contains at least one of the compounds represented by the chemical formulas (2), (3), (4) and (5). Photosensitive material. Embedded image [In the formula, Z and Z ₁ each represent an atom group necessary to form 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 and each represents an alkyl group, a substituted alkyl group, or an alkenyl group. R ₃ represents an alkyl group, a substituted alkyl group, an alkenyl group or an aryl group. L, L ₁ and L ₂ each represent a substituted or unsubstituted methine group. X
Represents an anion. n represents 0 or 1, and in the case of an internal salt, n = 0. ] Embedded image Embedded image Embedded image [Wherein R ²¹ represents an alkyl group or alkenyl group having 4 to 16 carbon atoms, R ³¹ and R ⁵¹ represent an alkyl group or alkenyl group having 5 to 17 carbon atoms, and R ³² and R ^{33 each} have 4 or less carbon atoms. An alkyl group or a hydroxyalkyl group, R ³² and R
The total carbon number of ³³ is 5 or less. R ^41, R ⁴² is an alkyl or alkenyl group having 4 to 12 carbon atoms, R ⁴¹
A total number of carbon atoms of R ⁴² represents 18 or less. R ⁵² represents an alkyl group having 1 to 3 carbon atoms. p is an integer of 1 to 11,
q represents 2, 3 or 4; r is an integer of 2 to 8;
Represents 0 or 1, t represents 1, 2 or 3, u represents 2,
Represents 3 or 4. M ²¹ , M ⁴¹ and M ⁵¹ represent a hydrogen atom or an alkali metal atom. ]