JP2838580B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material having high sensitivity in the red or infrared region and little residual color, and more particularly to photographic performance over time. The present invention relates to a red-sensitive silver halide photographic material having little deterioration and little change in performance during storage of a coating solution.

[Background of the Invention]

A so-called scanner method in which an original figure is scanned as one of the exposure methods of a photographic photosensitive material, and exposure is performed on a silver halide photographic photosensitive material based on the image signal to form a negative image or a positive image corresponding to the image of the original figure. Is known. 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 can provide high output, but the equipment is large, expensive, requires a modulator, and uses visible light, which limits safelighting of photosensitive materials and is inferior in handling. There is such a problem.

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]

Accordingly, an object of the present invention is to provide a silver halide photographic material having a high spectral sensitivity in the red or 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].

 In the formula, A represents a phosphorus atom or a nitrogen atom. R₁, R_Two,
R_ThreeAnd R_FourRepresents a substituted or unsubstituted alkyl group,
Represents a reel group or an aralkyl group;₁, R_Two, R_ThreeAnd R_Four
At least one of which is an electron-withdrawing substitution component.
Is an aryl group or an aralkyl group. X Is
Represents an acid anion.

 Hereinafter, the present invention will be described in detail.

In the general formula [I], the optionally substituted alkyl group represented by R ₁ , R ₂ , R ₃ and R ₄ is preferably a lower alkyl group having 1 to 8 carbon atoms (for example, a methyl group, An ethyl group, an iso-propyl group, an n-butyl group, an octyl group, and the like. Examples of the substituent of the alkyl group include a hydroxy group, a sulfonic acid group, a carboxylic acid group, an amino group, and a halogeno group. .

Examples of the aryl group which may have a substituent represented by R ₁ , R ₂ , R ₃ and R ₄ include, for example, a phenyl group and naphthyl, and a phenyl group is preferable. As a substituent for the aryl group, an alkyl group (preferably having 1 to 8 carbon atoms)
A lower alkyl group), an alkoxycarbonyl group, an alkylsulfonyl group, an alkylcarbonyl group (the alkyl group portion of these groups preferably has 1 to 8 carbon atoms), a nitro group, a cyano group, a halogen atom, -N (C ₂ H ₅ ) ₂ HCl and the like.

Examples of the electron-withdrawing substituent of the aryl or aralkyl group of R ₁ , R ₂ , R ₃ and R ₄ include a nitro group, a cyano group, a halogeno group, a carbonyl group, a carboxyl group, a carboxyl group, a sulfonyl group and a quaternary amino group. Groups and the like are typical examples.

 X Examples of the anion represented by
Ion, bromide ion, iodide ion, cyanide ion
, Hypochlorite ion, p-toluenesulfonic acid ion
Benzenesulfonate ion, hydroxide ion, etc.
I can do it.

The compound represented by the general formula [I] can be easily synthesized by the method described in JP-B-50-40665.

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

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 of addition varies depending 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 in an emulsion layer, 10 ^-6 to 10 ^-2 mol per mol of silver halide is used. , More preferably in the range of 10 ^-5 to 10 ^-3 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.

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 It can also form a 5- or 6-membered nitrogen-containing heterocycle.

 Also, R₁₃And R_FifteenAnd R_{twenty three}And R_{twenty five}Is connected to each other and has 5 members
A ring or a 6-membered ring can be formed. X₁₁ And X
_{twenty one} Represents an anion. n₁₁, n₁₂, n_{twenty one}And n_{twenty two}Is 0 or
Represents 1.

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 2 g, more preferably from 5 mg to 1 g, 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 50/50 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. The addition amount is preferably in the range of 10 ^-9 to 10 ^-6 mol per mol of silver.

When using a rhodium salt, other inorganic compounds such as iridium salt, platinum salt, thallium salt, cobalt salt,
A gold salt or the like may be used in combination. Iridium salts are often used in an amount of 10 ^-8 mol / mol silver for the purpose of imparting high illuminance characteristics.
It can be preferably used up to the range of 10 ^-6 mol.

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.

The exposure and development conditions of the light-sensitive material of the present invention are not particularly limited. For example, the description of Research Disclosure, Vol. 176, pp. 28-30 can be referred to.

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, typical examples include a polyester film such as polyethylene terephthalate, a polyamide film, a polypropylene film, a polycarbonate film, and a polystyrene film. These supports are appropriately selected depending on the purpose of 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].

In the formula, R ₁₁ represents a nitro group at the 5- or 6-position, and 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 preferably contained in a concentration of about 1 mg to 1,000 mg, more preferably about 50 mg to 300 mg per developer.

After exposure, the silver halide photographic light-sensitive material according to the present invention can be subjected to development processing by various methods generally used.

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 255 and flocculate the emulsion at 40 ° C., decant and remove excess aqueous salt to 1/10 volume. Then, 3.7 parts of water was added thereto to disperse the mixture, and 0.9% of a 20% aqueous solution of magnesium sulfate was added again to remove excess salts of the aqueous solution. This was repeated twice. Then add 3.7 g of water and 141 g of gelatin,
Disperse at 5 ° C for 30 minutes. This gives 35 mol% of silver bromide,
Grains having a silver chloride content of 65 mol%, an average particle size of 0.25 μm and a monodispersity of 9 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 as a stabilizer in the above emulsion, 20% of gelatin
After stopping the ripening by adding 1600 ml of an aqueous solution, I-3, I-6, I-8, I-1 were obtained as compounds of the general formula [I] or [II].
6, II-2, II-4, II-10, II-16 and II-20 were added in the amounts shown in Table 1, and after adjusting the pH and pAg, 30 g of hydroquinone was further spread as an antifoggant. 10 g of sodium p-dodecylbenzenesulfonate as an 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. -Dichloro-S-triazine sodium salt and formalin are added just before coating,
The emulsion was such that the silver 4.2 g / m ² has a backing layer and the subbing processed polyethylene terephthalate support on, as a protective film, potassium bromide was 10g added to an aqueous solution of gelatin 500 g, spreading 15 g of the following compound (a) was added as an agent, and 20 g of amorphous silica having an average particle size of 3.5 μm was further added and dispersed. The emulsion layer and the protective layer were simultaneously coated so that the gelatin became 1.1 g / m ^2. , Sample Nos. 1 to 18 were prepared. In addition, Sample Nos. 19 and 20 to which Comparative Compounds A and B were added instead of the compound of the general formula [I] were also prepared.

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 was stored by stirring at 40 ° C. for 8 hours, and an emulsion coating solution also stored for 1 hour was prepared.

Storage property over time The obtained sample was divided into 3 minutes, and one part of it was used as it was as a fresh sample on the same day.

Humidity control: A portion 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.

No humidity control: Partly sealed at 23 ° C and 48% relative humidity with a moisture-proof material laminated with polyvinyl acetate at 55 ° C and 50% relative humidity.
% In a constant temperature room 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 Normal temperature Approx. 20 seconds Dry 45 ° C 20 seconds Developing solution composition (Composition A) 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 100
It was expressed by the rate of change in sensitivity of the sample that had been stagnated for 8 hours. The residual color was evaluated by visual evaluation of the following five steps after developing the unexposed sample.

5: No residual color.

4: There is very slight residual color.

3: A level with many residual colors that is not practical.

2: Very residual color contamination is unusable.

1: Remarkable residual color (blue) 結果 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 (1) significantly reduces the photographic performance degradation during storage over time, stabilizes the stagnation of the coating solution, and provides a photosensitive material with little residual color.

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

In addition to such effects of the present invention, the stagnation of the emulsion coating solution was stabilized, and the emulsion coating solution had characteristics of less residual color contamination after the development processing.

Continuation of the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) G03C 1/34 G03C 1/10-1/26

Claims (1)

(57) [Claims] 1. A silver halide having at least one layer on a support
In a silver halide photographic light-sensitive material having an emulsion layer,
Are emulsion layers cationic di- and tricarbocyanine dyes?
Spectral sensitization by at least one selected from the group consisting of
And at least one compound represented by the following general formula (I)
Silver halide photographic feeling characterized by containing one
Light material.[In the formula, A represents a phosphorus atom or a nitrogen atom. R₁, R_Two,
R_ThreeAnd R_FourRepresents a substituted or unsubstituted alkyl group,
Represents a reel group or an aralkyl group;₁, R_Two, R_ThreeAnd R_Four
At least one of which is an electron-withdrawing substitution component.
Is an aryl group or an aralkyl group. X Is
Represents an acid anion. ]