JP2597432B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

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BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spectrally sensitized silver halide, and more particularly to a system having a maximum spectral sensitivity in a red light region and including a step of exposing mainly with a He-Ne laser beam. The present invention relates to a silver halide light-sensitive material which is used, has high sensitivity, has low fog, has good footing, and has excellent suitability for fatigue liquid.

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2. Description of the Related Art Silver halide photographic materials are required to have sensitivities at different specific wavelengths depending on the purpose. As one of the techniques for producing such a light-sensitive material, it is generally well known that certain sensitizing dyes are added to silver halide to effectively increase sensitivity at a specific wavelength.

Further, with the rapid development of optoelectronics in recent years, a light source such as laser light or LED light has begun to be used as a light source for outputting digitized image information instead of a conventional incandescent light bulb or the like. Above all, He-Ne laser light, ruby laser, and red LED light, which are already in the practical range, have emission wavelengths in the range of 600 to 700 nm, and photosensitive materials for recording these red lights are widely used.

As one of such techniques for producing a light-sensitive material, a certain sensitizing dye is added to a silver halide photographic emulsion, and a specific sensitizing dye is added to a specific wavelength in a wavelength range longer than the intrinsic wavelength range of the silver halide. It is generally well known to effectively increase the sensitivity in the wavelength range.

Although many sensitizing dyes have been proposed, triheterocyclic dyes described in JP-B-49-13331, JP-A-50-62425, British Patent No. 1471701, and the like ( It is known that triheterocyclic dyes) are very effective in increasing such red light sensitivity. However, while these sensitizing dyes increase the red light sensitivity of silver halide photographic emulsions, they cause an increase in fog and a worsening of the toe portion of the photographic characteristic curve. In particular, since this shortage greatly affects the image quality of the photosensitive material, it is important for a photosensitive material used mainly in a system including a step of exposing using a He-Ne laser beam.

For the purpose of suppressing such fog, an antifoggant is generally used. However, when a silver halide photographic emulsion sensitized red with a triheterocyclic dye is used in combination with a fog inhibitor containing a mercapto group, the sensitivity is reduced. And the photographic sensitivity is greatly reduced when processed with a tired developer. With regard to the processing with the fatigued developer, there is no problem as long as an appropriate replenishment of the developer is performed according to the processing amount of the photosensitive material. However, the management of the processing liquid is very complicated, and even the processing liquid which is tired. It is important to say that stable properties are obtained.

However, by performing sensitization with a triheterocyclic dye, a photographic material having sufficient sensitivity to such red light, low fog density, good cut-out, and excellent suitability for fatigue liquid can be obtained. The fact was that there was nothing satisfactory.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a light-sensitive material having high sensitivity in the red wavelength region, low fog, good cut-out, and excellent fatigue solution suitability.

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According to the present invention, there is provided at least one photosensitive silver halide emulsion layer on a photographic support,
And in the non-photosensitive layer on the same side as the emulsion layer on a support a silver halide light-sensitive material having at least one layer comprises at least one sensitizing dye represented by at least one layer of one said emulsion layer, The layer containing the sensitizing dye of the formula (1) is substantially free of the compound of the formula (2), and the layer containing the sensitizing dye of the formula (1) contains at least one compound of the formula (3). and it was effectively achieved by containing at least one said non-photosensitive layer at least one layer of second compound represented by the.

In Chemical Formula 1, Z and Z ₁ each represent an atom group necessary for forming a 5-membered and / or 6-membered nitrogen-containing heterocyclic ring usually used in cyanine dyes. As the heterocyclic nucleus, for example, thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, 2-quinoline nucleus, A 4-quinoline nucleus, a 2-pyridine nucleus, a 4-pyridine nucleus, a 3,3-dialkylindolenine nucleus, a benzimidazole nucleus, etc., wherein the carbon atom of the heterocyclic ring is a halogen atom, an alkyl group, an alkoxyl group, And a substituent such as a monoaryl group.

R and R ₁ are each a saturated or unsaturated aliphatic group, for example, a lower alkyl group (eg, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, etc.), a substituted alkyl group (preferably an alkyl radical). Having 5 or less carbon atoms), for example, those having a substituent such as a hydroxy group, an acetoxy group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, a sulfo group, a vinyl group or a monoaryl group.

Q and Q ₁ (combination) represent an atom group necessary for forming a 4-thiazolidinone, 5-thiazolidinone or 4-imidazolidinone nucleus.

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Further, L ₁ and R, and L ₃ and R ₁ may be linked by a methylene chain to form a nitrogen-containing heterocyclic ring.

M and n represent 0 or 1.

X represents an anion such as a chloride ion, a bromide ion, an iodide ion, a P-toluenesulfonate ion and the like.

P represents 0 or 1, and when it is an inner salt, P
= 0.

In the chemical formula 2, Z ₂ represents a nonmetallic atom group necessary for forming a 5-membered ring and / or a 6-membered heterocyclic ring. M represents a hydrogen atom, an alkali metal atom, an ammonium group or an organic amine residue.

Wherein Y and Z ₃ each independently represent any of methine, substituted methine, and a nitrogen atom;
Q ₂ represents a group of atoms necessary to form a 5- or 6-membered hetero ring, and these rings may be further condensed. M
₁ represents a hydrogen atom or a cation.

The addition amount of the sensitizing dye of the formula (1) used in the present invention ranges from 5 mg to 500 mg per mol of silver halide, and the optimum amount for obtaining the effect can be arbitrarily selected. These sensitizing dyes may be used alone or in combination.

The sensitizing dye can be added to these silver halide emulsions as a solution of a single or mixed solvent such as methanol, ethanol, isopropanol, pyridine, dimethylformamide and water.
Further, it can be added to the emulsion by using ultrasonic dispersion. Further, U.S. Pat.
Nos. 5195, 3469987 and 364928
No. 6, No. 3485634, No. 3342605,
And the method described in Japanese Patent No. 2912343 can also be used.

These sensitizing dyes can be added to a silver halide photographic emulsion at any time during the emulsion production process.

Next, specific examples of the sensitizing dye used in the present invention will be listed, but the sensitizing dye used in the present invention is not limited thereto.

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The sensitizing dye used in the present invention is Francis. M. By Hammer (Frances.M.Hamer) The Cyanine Dyes and Related Compounds, John Wiley and Sands Limited
Sons Ltd) (1964), German Patent No. 97194
No. 1, can be readily synthesized in relation technician if such a reference the first 1013167 GoAkira Saisho.

Next, specific examples of the compound used in the present invention represented by Chemical formula 2 are listed, but the compounds used in the present invention are not limited thereto.

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The compound of formula 2 used in the present invention may be added at any time before coating.

Further, for the non-photosensitive layer, 0.1 to 30
mg / m ^2, preferably from 0.5 to 10 mg / m ^2.

For the addition, the solution is added as a solution of a suitable solvent, for example, a single or mixed solvent of methanol, ethanol, isopropanol, pyridine, dimethylformamide, water and the like.

Next, specific examples of the compound used in the present invention represented by Chemical formula 3 are listed, but the compounds used in the present invention are not limited thereto.

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The compound of formula (3) used in the present invention may be added at any time before coating.

The amount of addition is 0.1 to 50 m.
g / m ² , preferably 0.5 to 30 mg / m ² .

For the addition, it is added as a solution of a suitable solvent, for example, a single or mixed solvent such as methanol, ethanol, isopropanol, pyridine, dimethylformamide and water.

The silver halide photographic emulsion used in the present invention can be prepared by various known methods.

The silver halide grains in the photographic emulsion may have regular crystals such as cubic, octahedral, tetradecahedral, and rhombohedral, and irregular grains such as spherical and tabular. Those having a crystal system or those having a composite form of these crystal forms may be used. Further, it may be composed of a mixture of particles of various crystal forms.

The silver halide grains may have different phases between the inside and the surface, or may consist of a uniform phase.

Further, for example, a composite silver halide crystal in which an oxide crystal such as PbO is combined with a silver halide crystal such as silver chloride, and a silver halide crystal which is epitaxially grown (for example, Silver chloride, silver iodobromide, silver iodide, etc. are epitaxially grown on silver bromide.).

The aspect ratio is 3 or more, preferably 5
To 20 tabular silver halide grains can also be used. For more details, see U.S. Pat.
39520, JP-A-59-99433, "Research Disclosure" Vol. 22534 (1
Jan. 983).

Further, the grain size distribution of the silver halide grains used in the present invention is arbitrary, but may be monodispersed. Here, the monodisperse is a dispersion system in which 95% of the particles fall within ± 60%, preferably 40%, of the number average particle size. Here, the number average particle size is
It is the number average diameter of the projected area diameter of the silver halide grains.

The photographic emulsion used in the present invention is a photographic emulsion prepared by GFDuffin.
Emulsion chemistry (Photographic EmulsionC
hemistry, The Focal Pres
s) (1966), VLZelikman et al, Making and Coating Photographic Emulsion (Making and Coating)
Coating Photo-graphic Emulsion), The Focal
The adjustment can be performed using a method described in, for example, the Press (The Focal Press) (1964). That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halide may be any one of a one-sided mixing method, a double-sided mixing method, and a combination thereof. Good.

As one type of the double jet method, a method of keeping pAg constant in a liquid phase in which silver halide is formed, that is, a controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a nearly uniform grain size can be obtained.

Further, two or more kinds of silver halide emulsions formed separately may be mixed.

In the course of silver halide grain formation or physical ripening, cadmium salts, zinc salts, lead salts, thallium salts,
An iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, or the like may coexist.

As a method for removing the soluble salts from the emulsion after the formation of the precipitate or after the formation of the physical solution, a noodle method for gelling gelatin, an inorganic salt, an anionic surfactant, an anionic polymer or a modified gelatin is used. A precipitation method (a flocculation method) or the like is used.

The silver halide emulsion can be chemically sensitized by a known method. Examples of the sulfur sensitizer include thiosulfate, thiourea, allylisothiocyanate, cystine, rhodanine, and US Pat.
No. 278947, No. 2410689, No. 244020
No. 6, No. 3187458, No. 3415649, No. 3
Sulfur-containing compounds such as those described in JP-A-501313 and the like can be used. Also, US Pat.
No. 2,597,915, and 2399083 can be subjected to gold sensitization with a gold compound.
U.S. Patent Nos. 2448060 and 2540036
No. 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. And these sensitization methods can be used in combination instead of single.

In the present invention, a polyalkylene oxide,
Various development accelerators such as thioether compounds and quaternary ammonium salt compounds can be used.

The silver halide photographic emulsion used in the present invention may optionally contain other sensitizing dyes such as cyanine,
Merocyanines may be used in combination for spectral sensitization, and may further contain additives such as stabilizers, surfactants, and hardeners by known methods.

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

In the light-sensitive material of the present invention, all those usually used as supports for photographic light-sensitive materials are used. Examples thereof include a cellulose nitrate film, a cellulose acetate film, a cellulose acetate butylate film, a cellulose acetate propionate film, a polystyrene film, a polyethylene terephthalate film, a polycarbonate film, a laminate thereof, and paper. Substrates such as paper coated or laminated with baryta or α-olefin polymers, especially polymers of α-olefins having 1 to 10 carbon atoms such as polyethylene and polypropylene, are also suitable.

[0134]

EXAMPLES The present invention will be specifically described below with reference to examples, but it is needless to say that the present invention is not limited by these descriptions.

Example 1 A silver iodobromide emulsion having an average grain size of 0.3 μm of silver halide crystal grains produced by a conventional method for producing a silver halide photographic emulsion was subjected to a second ripening by a sulfur-gold sensitization method. After that,
Of sensitizing dye of 25 mg per mol of silver halide,
After adding the compounds of formulas 2 and 3 as shown in Table 1,
A stabilizer, a coating aid and a hardener were added to obtain a coated emulsion.

Further, after adding the compound of the formula (2) to the 5% aqueous gelatin solution as shown in Table 1, a coating aid and a hardening agent were added to obtain an overcoating solution.

The coated emulsion and the overcoat solution were applied to a 100 μm thick photographic polyethylene-coated paper and the coated emulsion layer was 1.8 g / m ^{2 of} silver and 1.5 g of gelatin after drying of the overlayer. / M ² by a wire bar coating method and dried to obtain a sample.

This sample was exposed using a sensitometer having a light source having a color temperature of 5400 ° K. The light source was provided with an interference filter transmitting 633 nm light. Subsequently, each sample was prepared by using a developer MRA-CD231 manufactured by Mitsubishi Paper Mills Co., Ltd.
Developed at 8 ° C for 20 seconds, stopped, fixer MR manufactured by Mitsubishi Paper Mills, Ltd.
Using A-CF601, fixing and further washing with water were performed to obtain strips having a predetermined black and white image.

The density of the sample was measured using a MACBETH TD-504 densitometer manufactured by Macbeth Corporation of the United States to obtain red light sensitivity. The optical density reference points for which the sensitivities were determined were all points at a density of 0.75. After the unexposed sample was developed at 38 ° C. for 60 seconds, it was processed in the same manner and the fog density was measured. Further, in order to check the development progress, the same processing is performed with the development time set to 32 ° C. for 20 seconds, and the sensitivity difference ΔS from the case of the development processing at 38 ° C. for 20 seconds is determined.

The results are shown in Table 1. Sensitivity is 38 ° C 20
This is a value obtained when the developing process is performed for a second, and is indicated by a relative sensitivity when the sample 1 is set to 100. The addition amounts of Chemical formulas ² and 3 are the additive amounts (mg) per 1 m ² . 38 ° C
The cut of the foot portion of the photographic characteristic curve after the development processing for 20 seconds was evaluated in five levels. 1 is the best, 5 is the worst, and 3 or more is a level that has a clear adverse effect on image quality and poses a practical problem.

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As is evident from Table 1, it can be seen that the present invention has high sensitivity, low fog, good footing, and good development progress.

Example 2 A sample was prepared in the same manner as in Example 1 except that the sensitizing dye and the compounds represented by Chemical Formulas 2 and 3 were as shown in Table 2.
Chemical formula 89 was used as a comparative dye. The addition amount of the sensitizing dye is the amount (mg) per mol of silver halide, and the addition amount of the chemical formula ² is the addition amount (mg) per 1 m ² .

This sample was treated with a color temperature of 54 in the same manner as in Example 1.
Using a sensitometer with a light source of 00K, the light source was 633n
m, and exposure was performed with an interference filter that transmits light of m. Subsequently, each sample was used as a developer MRA-CD manufactured by Mitsubishi Paper Mills, Ltd.
Developed at 38 ° C. for 20 seconds using 231 and stopped, fixed using MRA-CF601, a fixing solution manufactured by Mitsubishi Paper Mills, and further washed with water to obtain strips having a predetermined black and white image. In order to examine the developer, the developer was developed with a new solution and the sample 1 was treated with 5 m ^{2 /} L of the developer.
The same treatment was carried out using a developing solution which was developed and was fatigued.

The results are shown in Table 2.

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As described above, it can be seen that the product of the present invention has high sensitivity, and both the fatigue solution and the new solution have good breaking and little fog.

[0149]

According to the present invention, in the silver halide light-sensitive material used in a system having a maximum spectral sensitivity in a red light region and mainly including a step of exposing with a He-Ne laser beam, a sensitivity in a red wavelength region. A photosensitive material having high development, low fog, and excellent development progress is obtained.

 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-1-13539 (JP, A) JP-A-1-144041 (JP, A) JP-A-62-215272 (JP, A) JP-A-4- 299335 (JP, A) JP-B-49-13331 (JP, B2) JP-B-52-25331 (JP, B2) US Patent 4,910,129 (US, A)

Claims (1)

(57) [Claims] [Claim 1 further comprising at least one layer of light-sensitive silver halide emulsion layer on a photographic support and the silver halide photosensitive having at least one layer of non-photosensitive layer on the same side as the emulsion layer on a support in the material, into at least one layer of the emulsion layer 1
Wherein at least one sensitizing dye represented by the formula (1) is contained, and the layer containing the sensitizing dye of the formula (1) is substantially free of the compound represented by the formula (2). Is 3
With a compound containing at least one silver halide photographic material characterized by containing at least one compound represented by at least one layer of 2 of the non-photosensitive layer. Embedded image In Chemical Formula ₁ , Z and Z ₁ each represent an atom group necessary to form a 5-membered and / or 6-membered nitrogen-containing heterocyclic ring usually used in cyanine dyes. R and R ₁ each represent a saturated or unsaturated aliphatic group. Q and Q ₁ (combination) represent the atoms required to form a 4-thiazolidinone, 5-thiazolidinone, or 4-imidazolidinone nucleus. R ₂ | L ₁ , L ₂ and L ₃ represent a methine group or a substituted methine group (= C—R ₂ represents an optionally substituted lower alkyl group or an aryl group). Further, L ₁ and R, and L ₃ and R ₁ may each be bonded by a methylene chain to form a nitrogen-containing heterocyclic ring. m and n represent 0 or 1. X represents an anion such as a chloride ion, a bromide ion, an iodide ion, and a P-toluenesulfonic acid ion. P represents 0 or 1, and in the case of an inner salt, P = 0. Embedded image In Chemical Formula 2, Z ₂ represents a nonmetallic atom group necessary for forming a 5-membered ring and / or a 6-membered heterocyclic ring. M represents a hydrogen atom, an alkali metal atom, an ammonium group or an organic amine residue. Embedded image In Chemical Formula 3, Y and Z ₃ each independently represent a methine, substituted methine, or nitrogen atom, Q ₂ represents an atom group necessary for forming a 5- or 6-membered heterocyclic ring,
These rings may be further fused. M ₁ represents a hydrogen atom or a cation.