JP2890055B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material having a spectral sensitivity in the infrared region. The present invention relates to a silver halide photographic light-sensitive material having little change in performance during storage.

BACKGROUND OF THE INVENTION One of the methods of exposing a photographic light-sensitive material is to scan the cause, perform exposure on a silver halide photographic light-sensitive material based on the image signal, and form a negative image or a positive image corresponding to the image of the cause. There is known an image forming method by a so-called scanner method for forming. There are various types of recording apparatuses that use a scanner-type image forming method, and a glow lamp, a xenon lamp, a mercury lamp, a tungsten lamp, a light-emitting diode, and the like have been conventionally used as a recording light source of these scanner-type recording apparatuses. However, each of these light sources has a practical problem that the output is weak and the life is short. In order to solve these problems, there is a scanner that uses a coherent laser light source such as a helium-neon laser, an argon laser, and a helium-cadmium laser as a light source of a scanner system. These light outputs can be obtained, but the equipment is large, expensive,
There is a problem that a modulator is required, and safe light of a photosensitive material is limited due to the use of visible light.

In contrast, semiconductor lasers are small, inexpensive, easy to modulate, and have a longer life than the above lasers. In addition, since light is emitted in the infrared region, a bright safelight can be used, which has an advantage that handling workability is improved.

However, since there is no photosensitive material having high photosensitivity in the infrared region and excellent storage stability, there has been no photosensitive material capable of fully utilizing the characteristics of the semiconductor laser having excellent performance as described above.

In general, the sensitivity of an infrared-sensitized photosensitive material is unstable, and storage requires special consideration such as refrigeration or freezing.

[Object of the invention]

An object of the present invention is to provide a silver halide photographic light-sensitive material having a high spectral sensitivity in the infrared region and having no deterioration in photographic performance during storage over time.

[Configuration of the invention]

As a result of intensive studies, the present inventors have found that the above-mentioned object is achieved as follows, and have accomplished the present invention.

That is, in a silver halide photographic material having at least one silver halide emulsion layer on a support, the emulsion layer is formed by at least one selected from the group consisting of cationic di- and tricarbocyanine dyes. Spectrally sensitized,
It is achieved by a silver halide photographic material containing at least one compound represented by the following general formula [I].

General formula [I] Wherein R ₂ , R ₃ , R ₄ are each a hydrogen atom, a halogen atom,
Represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a cyano group, a sulfo group, or a carboxy group.
R ₂ and R ₃ , R ₂ and R _4, and R ₃ and R ₄ may form a ring with each other. R ₁ is a hydrogen atom, an alkyl group, an aryl group, an amino group or an —OR ₅ group (where R ₅ is an alkyl group, an aryl group,
Represents a saturated carbocyclic residue. ). m represents an integer of 0 to 3, and n represents an integer of 1 to 3. Hereinafter, the present invention will be described in detail.

In the general formula [I], R ₂ , R ₃ and R ₄ may be the same or different, and each represents a hydrogen atom, a halogen atom (eg, a chlorine atom or a bromine atom), an alkyl group (preferably a carbon atom). An aryl group (preferably a phenyl group), an alkoxy group (preferably a lower alkoxy group such as a methoxy group, an ethoxy group, a propoxy group, etc.), an aryloxy group (such as a phenoxy group, etc.), cyano Represents a group, a sulfo group, or a carboxyl group.

R ₂ and R ₃ , R ₂ and R _4, and R ₃ and R ₄ may be connected to each other to form a ring (preferably a benzo-condensed ring). R ₁ is a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably a phenyl group), an amino group (which may have a substituent, and an alkyl group, aryl group, and a saturated carbocyclic residue.), or -OR ₅ group (wherein R ₅ represents the alkyl group (preferably having 1 to 8 carbon atoms), an aryl group (preferably phenyl group), Represents a saturated carbocyclic residue (for example, represents a cyclohexyl group). m represents an integer of 0 to 3, and n represents an integer of 1 to 3.

Further, the alkyl group and the aryl group may further have a substituent, for example, a hydroxy group,
Alkoxy, aryloxy, halogen, alkoxycarbonyl, cyano, amino, acylamino, sulfonylamino, sulfamoyl, nitro, carbamoyl, alkylthio, arylthio, sulfonyl, sulfinyl, sulfo And a carboxyl group.

The amount of the hydroxyaldoxime compound of the general formula [I] used in the present invention is 1 mg to 5 g per mole of halogen.
The particularly preferred addition amount is in the range of 10 mg to 5 g.

Hereinafter, specific examples of the compound represented by the general formula [I] include the following compounds, but are not limited thereto.

In order to incorporate the compound represented by the general formula [I] into the constituent elements of the silver halide photographic light-sensitive material, the compound is dissolved in water or an organic solvent such as methanol or ethanol that is arbitrarily miscible with water, What is necessary is just to make it contain in a component.
The amount added depends on the type of silver halide, the type of constituent elements to be contained, the type of compound used, and the like. In general, when added to an emulsion layer, it is added per mole of silver halide.
It can be added in the range of 10 ^-7 to 10 ^-3 mol, more preferably 10 ^-6 to 10 ^-4 mol.

Next, as the cationic di- or tricarbocyanine infrared sensitizing dye used in the present invention, the following general formula [II-
Compounds represented by a) and [II-b] are preferred.

General formula [II-a] General formula [II-b] In the formula, Y ₁₁ , Y ₁₂ , Y ₂₁ and Y ₂₂ each represent a non-metallic atomic group necessary for completing a 5- or 6-membered nitrogen-containing heterocyclic ring, for example, a benzothiazole ring, a naphthothiazole ring,
Benzoselenazole ring, naphthoselenazole ring, benzoxazole ring, naphthoxazole ring, quinoline ring,
Examples include a 3,3-dialkylindolenin ring, a benzimidazole nucleus, and a pyridine ring.

These heterocycles are a lower alkyl group, an alkoxy group,
It may be substituted with a hydroxyl group, an aryl group, an alkoxycarbonyl group, or a halogen atom.

R ₁₁ , R ₁₂ , R ₂₁ and R ₂₂ each represent a substituted or unsubstituted alkyl group, aryl group or aralkyl group.

R ₁₃ , R ₁₄ , R ₁₅ , R ₂₃ , R ₂₄ , R ₂₅ and R ₂₆ are each a hydrogen atom, a substituted or unsubstituted alkyl group, an alkoxy group,
Phenyl group, benzyl group, Represents Here, W ₁ and W ₂ each represent a substituted or unsubstituted alkyl group (having 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms in the alkyl portion) and an aryl group, and W ₁ and W ₂ are linked to each other. To form a 5- or 6-membered nitrogen-containing heterocycle.

R ₁₃ and R ₁₅ and R ₂₃ and R ₂₅ can be linked to each other to form a 5- or 6-membered ring. X ₁₁ and X ₂₁
Represents an anion. n ₁₁ , n ₁₂ , n ₂₁ and n ₂₂ are 0 or 1
Represents

Next, specific examples of the sensitizing dye used in the present invention (hereinafter, referred to as the sensitizing dye of the present invention) are shown, but the present invention is not limited thereto. In addition, II-1 to 13 are compounds represented by the general formula [II-b], and II-14 to 21 are compounds represented by the general formula [II-a].

The sensitizing dye of the present invention is contained in a silver halide photographic emulsion in an amount of preferably from 1 mg to 1 g, more preferably from 5 mg to 500 mg, per mol of silver halide.

The sensitizing dye of the present invention can be directly dispersed in an emulsion. These can be first dissolved in a suitable solvent, for example, methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution.

The sensitizing dyes of the present invention may be used alone or in combination of two or more. Further, sensitizing dyes other than the present invention can be used in combination. When a sensitizing dye is used in combination, it is preferable that the total content is the above content.

The sensitizing dyes of the present invention are described in U.S. Patent No. 2503776, British Patent No. 742112, French Patent No. 2065662, Japanese Patent Publication No. 40-2346.
Can be easily synthesized with reference to the reference numbers.

The silver halide used in the silver halide photographic light-sensitive material of the present invention is not particularly limited, but silver chloride or silver chlorobromide is preferred. The composition of silver chlorobromide is AgCl / AgBr = 100/0
~ 2/98, but preferably AgCl / AgBr = 100
/ 0 to 5/50 molar ratio. The average grain size of the silver halide grains is preferably from 0.10 μm to 0.40 μm, and the coefficient of variation represented by (standard deviation of grain size) / (average grain size) × 100 has a narrow grain size distribution of 15% or less. Is more preferred.

When preparing the silver halide emulsion used in the present invention, a rhodium salt can be added to control the sensitivity or gradation. In general, the rhodium salt is preferably added at the time of grain formation, but may be added at the time of chemical ripening or at the time of preparing an emulsion coating solution.

When using a rhodium salt, other inorganic compounds such as iridium salt, platinum salt, thallium salt, cobalt salt,
You may use gold salt etc. together. Iridium salts are often used for the purpose of imparting high illuminance characteristics to 10 ^-8 mol to 10 ^-6 mol per mol of silver.
It can be preferably used up to the molar range.

Various additives can be used in the light-sensitive material of the present invention depending on the purpose. These additives are described in more detail in Research Disclosure, Vol. 176, Item 17643.
(December 1978) and Volume 187, Item 18716 (November 1979)
The relevant locations are summarized in the table below.

There are no particular restrictions on the conditions of exposure and development of the light-sensitive material of the present invention, and for example, the description of Research Disclosure, Vol. 176, pp. 28-30 can be referred to.

Additive RD-17643 RD-18716 Page Classification Page Classification Chemical sensitizer 23 III 648-Upper right sensitizing dye 23 IV 648 Right-649 Left Development accelerator 29 XXI 648-Upper right Antifoggant 24 VI 649-Lower right Stabilizer 〃 〃 Color stain inhibitor 25 VII 650 left-right Image stabilizer 25 VII UV absorber 25-26 VIII 649 right-650 left Filter dye 〃 白 Whitening agent 24 V Curing agent 26 X 651 right Coating aid 26-27 XI 650 right surfactant 26 to 27 XI 650 right plasticizer 27 XII 〃 sliding agent 〃 static inhibitor 27 XII マ ッ ト matting agent 28 IX 650 right binder 26 IX 651 As the support used in the present invention, for example, baryta paper,
Polyethylene coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate,
For example, a polyester film such as polyethylene terephthalate, a polyamide film, a polypropylene film, a polycarbonate film, a polystyrene film and the like are typically included. These supports are
Each is appropriately selected according to the intended use of the silver halide photographic light-sensitive material.

The silver halide photographic material containing the compound represented by the general formula [I] is preferably developed in the presence of the compound represented by the following general formula [III].

General formula (III) [Wherein, R ₁₁ represents a nitro group at the 5- or 6-position, R ₁₂ represents a hydrogen atom or a C ₁ -C ₅ lower alkyl group. M represents a cation such as a hydrogen atom, an alkali metal atom, an alkaline earth metal atom or an ammonium ion. As a specific compound represented by the general formula [III], 5-
Examples include nitroindazole and 6-nitroindazole, but the present invention is not limited thereto.

The compound represented by the general formula [III] is dissolved in an organic solvent such as diethylene glycol, triethylene glycol, ethanol, diethanolamine and triethanolamine, an alkali such as sodium hydroxide and an acid such as acetic acid, and added to a developer. Or it may be added as it is.

The compound represented by the general formula [III] is used in an amount of about 1 per developer.
mg to 1,000 mg is preferred, more preferably about 50 mg to 3 mg
It is contained in a concentration range of 00 mg.

The silver halide photographic light-sensitive material according to the present invention can be subjected to development processing by various methods usually used after exposure.

The black-and-white developer is an alkaline solution containing a developing agent such as hydroxybenzenes, 1-phenyl-3-pyrazolidones, aminophenols and aminobenzenes, and other sulfites, carbonates and bisulfites of alkali metal salts. , Bromide and iodide.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited by these.

Example 1 (Preparation of emulsion) Solution A water 9.7 sodium chloride 20 g gelatin 105 g solution B water 3.8 sodium chloride 365 g gelatin 94 g potassium bromide 450 g 0.01% aqueous solution of potassium hexachloroiridate 28 ml 0.01% aqueous solution of potassium hexabromorhodate 1.0 ml Solution C Water 3.8 Silver nitrate 1,700 g To the above solution A kept at 40 ° C, while keeping pH 3 and pAg 7.7, simultaneously add the above solution B and solution C functionally over 60 minutes, and further stir for 10 minutes. After that, the pH was adjusted to 6.0 with an aqueous sodium carbonate solution, and a 20% aqueous magnesium sulfate solution 2 and a 5% aqueous solution of polynaphthalenesulfonic acid were used.
Add 2.55, flocculate the emulsion at 40 ° C, decant and wash with water to remove excess aqueous salts. Then add water of 3.7 and disperse it again
0.9% of a 0% aqueous solution of magnesium sulfate is added in the same manner to remove excess salts of the aqueous solution. Then, 3.7 g of water and 141 g of gelatin are added and dispersed at 55 ° C. for 30 minutes. As a result, grains having a silver bromide content of 35 mol% and a silver chloride content of 65 mol% and an average monodispersity of 9 of 0.25 μm are obtained.

Next, 140 ml of an aqueous solution of 1% citric acid and 57 ml of an aqueous solution of 5% of potassium bromide were added.
% Aqueous solution and 120 ml of a 0.2% aqueous solution of chloroauric acid were added thereto, followed by aging at 60 ° C. for 80 minutes.

10 g of 4-hydroxy-6-methyl-1.3.3a, 7-tetrazaindene and 20 parts of gelatin
% Aqueous solution to stop ripening, adding the compounds shown in Table 1 as compounds of general formulas [I] and [II], adjusting pH and pAg, and further adding 30 g of hydroquinone as an antifoggant. Then, 10 g of sodium p-dodecylbenzenesulfonate as a spreading agent, 20 g of a styrene-maleic anhydride polymer as a thickener, and 120 g of a polymer latex of ethyl acrylate were added, and 1-hydroxy-3.5 as a hardening agent was added. - addition of dichloro -s- triazine sodium salt and formalin immediately before coating, and so that the silver 4.2 g / m ² in the emulsion has a backing layer and subbing processed polyethylene terephthalate support on further protection As a film, 10 g of potassium bromide was added to an aqueous solution of 500 g of gelatin, and the following compound (a) was used as a spreading agent.
Is added, and amorphous silica having an average particle size of 3.5μ is further added.
The emulsion layer and the protective layer were simultaneously coated so that 20 g of the emulsion layer was added and dispersed so that the gelatin became 1.1 g / m ² .

(A) The storage stability of the emulsion coating solution of the obtained sample and the storage stability with time of the photosensitive material were evaluated by the following methods.

Coating solution preservability In the state where the hardener added immediately before the coating is not added
An emulsion coating solution stored with stirring at 40 ° C. for 8 hours and an emulsion coating solution also stored for 1 hour were prepared, and the change in sensitivity between the two was examined.

Storage stability with time The obtained sample was divided into 2 minutes, and a part of the sample was used as it was as a fresh sample on the same day.

A part was put in a polyethylene bag, further wrapped in a paper bag, and then heat-treated in a constant temperature room at 55 ° C. and a relative humidity of 50% for 72 hours.

The obtained sample was exposed for ^10-5 seconds with a xenon light source through an optical wedge and Kodak Wratten Filter No. 88A. Subsequently, processing was carried out using a developing solution and a fixing solution having the following formulation in an automatic developing machine for rapid processing for a total processing time of 90 seconds.

Developing conditions (Process) (Temperature) (Time) Current image 28 ° C 30 seconds Fixed 28 ° C Approx. 20 seconds Rinse room temperature Approx. 20 seconds Drying 45 ° C 20 seconds Developing solution composition (Composition A) Pure water (ion exchange water) 150 ml disodium salt of ethylenediaminetetraacetic acid 2 g diethylene glycol 50 g potassium sulfite (55% w / v aqueous solution) 100 ml potassium carbonate 50 g hydroquinone 15 g 5-methylbenzotriazole 200 ml 1-phenyl-5-mercaptotetrazole 30 mg potassium hydroxide Amount to make 10.4 Potassium bromide 4.5 g (Composition B) Pure water (ion-exchanged water) 3 mg Diethylene glycol 50 g Ethylenediaminetetraacetic acid disodium salt 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-phenyl-3-pyrazolidone When using a 500 mg developing solution, the above composition A and composition B were dissolved in 500 ml of water in this order, and finished to 1 for use.

Fixer formulation (Composition A) Ammonium thiosulfate (72.5% w / v aqueous solution) 240ml Sodium sulfite 17g sodium acetate trihydrate 6.5g boric acid 6g sodium citrate dihydrate 2g acetic acid (90% w / w aqueous solution) 13.6ml (Composition B) Pure water (ion-exchanged water) 17 ml Sulfuric acid (50% w / w aqueous solution) 4.7 g Aluminum sulfate (aqueous solution whose content in terms of Al ₂ O ₃ is 8.1% w / w) 26.5 g 500 ml of water when using the fixing solution The above composition A and composition B were melted in this order and finished to 1 for use.

 The pH of the fixing solution was about 4.3.

A photographic characteristic curve was written for the developed sample, and the sensitivity was measured.

The sensitivities in the table were obtained from the reciprocal of the exposure amount required to obtain a density of 1.0, and were expressed as relative sensitivities when the sample on the same day as Sample No. 1 was set to 100.

In addition, the storage stability of the coating solution was 10 hours after the sample sensitivity.
It was expressed as the rate of change in sensitivity of the sample stagnated for 8 hours when it was set to 0.

 The results obtained are shown in Table 1 below.

As is clear from Table 1, the general formula [I] according to the present invention
It can be seen that the addition of the compound of the formula (1) significantly reduces photographic performance degradation during storage over time and provides a photosensitive material in which the stagnation storage stability of the coating solution is stabilized.

〔The invention's effect〕

According to the present invention, a silver halide photographic light-sensitive material having high spectral sensitivity in a red region or an infrared region and having no deterioration in photographic performance during storage with time is obtained.

Further, in addition to such effects of the present invention, the emulsion coating solution had a property that the storage stagnation property was stabilized.

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support, wherein said emulsion layer is at least one selected from the group consisting of cationic di- and tricarbocyanine dyes. A silver halide photographic material which is spectrally sensitized by one and contains at least one compound represented by the following general formula [I]. General formula [I] Wherein R ₂ , R ₃ , R ₄ are each a hydrogen atom, a halogen atom,
Represents an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a cyano group, a sulfo group, or a carboxy group.
R ₂ and R ₃ , R ₂ and R _4, and R ₃ and R ₄ may form a ring with each other. R ₁ represents a hydrogen atom, an alkyl group, an aryl group, an amino group, or an —OR ₅ group (where R ₅ represents an alkyl group, an aryl group, or a saturated carbocyclic residue). m represents an integer of 0 to 3, and n represents an integer of 1 to 3. ]