JPH01309046A - Silver halide photographic sensitive material with improved preservable property of coating solution - Google Patents

Abstract

PURPOSE:To improve the photosensitivity of the title material in from a red color region to an infra-red region, and to lessen the characteristic change of the photosensitive material at the time of preserving the coating solution by incorporating a specified compd. in the silver halide contd. in a silver halide emulsion layer, and then aging the obtd. emulsion layer, and by composing the silver halide emulsion layer of silver chloroiodobromide contg. a prescribed amount of silver chloride. CONSTITUTION:The compd. shown by formula I is incorporated in the silver halide contd. in the silver halide emulsion layer, and then the obtd. emulsion layer is aged. The silver halide contd. in the silver halide emulsion layer is composed of the silver chloroiodobromide contg. 50mol% of the silver chloride. In the formula, R1-R3 are each hydrogen atom or a substituting group, X<-> is an anion. The tetrazolium compd. shown by formula I is incorporated in the photosensitive material in an amount of about >=1mg and up to 10g, preferably about >=10mg and up to about 2g per 1mol of the silver halide. Thus, the sensitivity of the photosensitive material in from the red color region to the infra-red region and the contrast of said material are improved, and the characteristic change of the photosensitive material at the time of preserving the coating solution, is lessened.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a highly sensitive silver halide photographic material that develops photosensitivity in the red region or infrared region, and more specifically relates to changes in performance during storage of a coating solution. The present invention relates to the above-mentioned silver halide photographic light-sensitive material having a small amount of carbon.

[Background of the invention]

Recently, it has become common to use scanners in the plate-making process of photo printing, and they are widely used for color separation, layout, etc. of color manuscripts. Although lasers, especially Ar lasers, are often used as light sources for scanners, the use of helium-neon laser-1 infrared semiconductor lasers, which emit long wavelength light, has become widespread due to its stability as a light source, cost, and other considerations.

In addition, in the plate-making process, a so-called hatching process is necessary to convert the gradation of the original image, which has continuous gradations, into the area of halftone dots. It is common practice to directly obtain halftone images. Therefore, the photosensitive materials used in such scanners are required to be silver halide photographic materials that have high photosensitivity in the long wavelength range and extremely high contrast suitable for forming halftone dots. A photosensitive material suitable for forming halftone dots, for example, has silver halide grains with an average grain size of about 0.
Halogenated silver chlorobromide or silver chloroiodobromide emulsion with fine grains of 5 μm or less, narrow particle size distribution, uniform grain shape, and high silver chloride content, for example, 50 mol% or more. Silver photosensitive materials with low sulfite ion concentration,
So-called lithographic photosensitive materials are used that are developed with an alkaline developer containing only hydroquinone as a developing agent, but such developers have poor shelf life and are susceptible to auto-oxidation, so plate makers are constantly checking the quality. In order to obtain a high net negative or positive image, it is necessary to manage the developer to keep the activity of the developer constant, which decreases over time or with use, and the complexity of the operation can be avoided. do not have.

As one of the methods to solve these problems,
No. 67419 discloses a silver halide photographic material containing a tetrazolium compound. Although this photographic light-sensitive material can form extremely high-contrast images, it is also greatly affected by the additives used in combination, such as sensitizing dyes.
In particular, there have been many problems with photographic materials that have high photosensitivity in the long wavelength range and are suitable for scanners using the helium-neon laser 1 or infrared semiconductor laser as a light source. In particular, such photosensitive materials containing tetrazolium compounds sensitized to long wavelengths have problems such as decreased sensitivity, which is thought to be due to inhibition of dye adsorption by the tetrazolium compounds, and large changes in performance during storage of coating solutions. Coating solution storage refers to storing the coating solution for each photographic layer prepared for coating onto a support during the production of photographic light-sensitive materials in a solution state from the end of preparation to the end of coating. Store at a temperature of 30°C to 40°C for several hours. As a method for improving this decrease in sensitivity and changes in performance during storage of the coating solution, there is a method using supersensitizers as described in, for example, JP-A-59-191032 and JP-A-59-192242. However, when the above-mentioned supersensitizer is added to a photographic emulsion layer containing a tetrazolium compound, there is a drawback that the high contrast effect of the tetrazolium compound is impaired.

[Purpose of the invention]

An object of the present invention is to provide a silver halide photographic material that has high photosensitivity in the red or infrared region, has high contrast, and exhibits little change in performance during storage of a coating solution.

[Structure of the invention]

The above object is to provide a halogenated photographic material having at least one photosensitive silver halide emulsion layer on a support, in which silver halide in the silver halide emulsion layer is formed by the following general formula [I] during chemical ripening. A halogen which is aged by containing at least one of the compounds shown above, and wherein the silver halide contained in the silver halide emulsion layer is silver chloroiodobromide containing at least 50 mol% of silver chloride. This can be achieved using silver oxide photographic materials.

44 also represents the general formula [I] [wherein R,, R2 and R5 each represent a hydrogen atom or a substituent, and XO represents an anion. ] The present invention will be described in detail below.

First, in the above general formula [I], preferable examples of the substituents represented by R1 to R3 include alkyl groups (e.g. methyl,
ethyl, cyclopropyl, propyl, isopropyl, cyclobutyl, butyl, isobutyl, pentyl, cyclohexyl, etc.), amino group, acylamino group (e.g. acetylamino), hydroxyl group, alkoxy group (e.g. methoxy, ethoxy, propoxy, butoxy, pentoxy, etc.) , acyloxy group (e.g. acetyloxy), halogen atom (e.g. fluorine, chlorine, bromine, etc.), carbamoyl group, acylthio group (e.g. acetylthio), alkoxycarbonyl group (e.g. ethoxycarbonyl), carboxyl group, acyl group (e.g. acetyl) , a cyano group, a nitro group, a mercapto group, a sulfoxy group, and an aminosulfoxy group.

Examples of the anion represented by Xθ include halogen ions such as chloride ion, bromide ion, and iodide ion, acid groups of inorganic acids such as nitric acid, sulfuric acid, and perchloric acid, and acid groups of organic acids such as sulfonic acid and carboxylic acid. , anionic activators, specifically lower alkylbenzenesulfonic acid anions such as p-toluenesulfonic acid anions, higher alkylbenzenesulfonic acid anions such as p-dodecylbenzenesulfonic acid anions, and higher alkyl sulfates such as lauryl sulfate anions. anion, boric acid anion such as tetraphenylporone, dialkyl sulfosuccinate anion such as di-2-ethylhexyl sulfosuccinate anion, polyether alcohol sulfate ester anion such as cetyl polyethenoxy sulfate anion, and high concentration anion such as stearate anion. Examples include polymers with acid groups attached, such as aliphatic anions and polyacrylic acid anions.

Specific examples of the compounds represented by the general formula [1] used in the present invention are listed in Table 1 below. It can be easily synthesized according to the method described in Reviews, Vol. 55, pp. 335-483.

The tetrazolium compound represented by the general formula [j] used in the present invention is about 10 g or more per mole of silver halide contained in the silver halide photographic material of the present invention.
up to about 10 mg to 2 g, preferably about 10 mg or more.

The tetrazolium compound used in the present invention is described, for example, in Chemical Reviews.
) Vol. 55, pp. 335-483.

The tetrazolium compound represented by the general formula (1) of the present invention is used in an amount of about 1 mg or more to 10 g, preferably about 10 mg or more to 2 g per mol of silver halide contained in the silver halide photographic light-sensitive material of the present invention. It is preferable to use the range up to .

The tetrazolium compounds represented by the general formula CI) used in the present invention may be used alone or in combination of two or more in an appropriate ratio. Furthermore, the tetrazolium compound of the present invention and the tetrazolium compound outside the present invention may be used in combination in an appropriate ratio.

In the present invention, particularly favorable results can be obtained when an anion that binds to the tetrazolium compound of the present invention and lowers the hydrophilicity of the tetrazolium compound of the present invention is used in combination. Examples of such anions include acid groups of inorganic acids such as perchloric acid, acid groups of organic acids such as sulfonic acids and carboxylic acids, anionic activators, and specifically lower alkylbenzene sulfones such as p-toluenesulfonic acid anions. acid anion,
Dialkyl sulfosuccinate anions such as p-dodecylbenzenesulfonate anions, alkylnaphthalenesulfonate anions, lauryl sulfate anions, tetraphiniylporones, di-2-ethylhexylsulfosuccinate anions, cetyl polyetheno Examples include polyether alcohol sulfate anions such as xisulfate anions, stearate anions, and polyacrylate anions.

Such anions may be added to the hydrophilic colloid layer after being premixed with the tetrazolium compound of the present invention, or may be added alone to the silver halide emulsion layer containing or not containing the tetrazolium of the present invention or to the hydrophilic colloid layer. Can be added to the colloid layer.

The silver halide used in the silver halide photographic light-sensitive material of the present invention is silver chlorobromide or silver chloroiodobromide, and contains at least 50 mol % of silver chloride. The average grain size of the silver halide grains is 0. It is preferably 1O to 0.40 μm, and preferably has a narrow particle size distribution with a particle size variation coefficient of 15% or less.

When preparing the silver halide emulsion used in the present invention, a rhodium salt can be added to control the sensitivity or gradation. It is generally preferable to add the rhodium salt at the time of grain formation, but it may also be added at the time of chemical ripening or at the time of preparing the emulsion coating solution.

Furthermore, when using a rhodium salt, other inorganic compounds such as an iridium salt, a platinum salt, a thallium salt, a cobalt salt, a gold salt, etc. may be used in combination. Iridium salts are often used for the purpose of imparting high-luminance properties at 1O-8 mol-1 per mol silver.
It can be preferably used up to a 0-' mole range.

Various additives can be used in the photosensitive material of the present invention depending on the purpose. These additives are, in more detail,
Research Disclosure Volume 176 1tem17
643 (December 1978) and Volume 187 Ite
m18716 (November 1979), and the relevant parts are summarized in the table below.

Furthermore, there are no particular limitations on the exposure and development conditions for the photosensitive material of the present invention, and for example, see the description in Research Disclosure Vol. 176, pages 28-30.
D17643 RD187161, chemical sensitizer
Page 23 Page 648 Right column 2, Sensitivity enhancer
Same as above 3, Spectral sensitizer, supersensitizer Pages 23-24 Page 648 right column - Page 649 right column Additive types RD17643 RD187164,
Brighteners page 24 5, antifoggants and stabilizers pages 24-25 page 649 right column 7, anti-stain agents page 25 right column 650 left to right column 8,
Dye image stabilizer page 25 9, hardener
Page 26, page 651 left column IO, binder page 26 same as above 11, plasticizer, lubricant page 27 page 650 right column 12,
Coating aid, surface page 26-27 Same as supernatant agent 13, anti-static agent page 27 same
Moreover, as a matting agent, for example, British Patent No. 1, 22
1.980, U.S. Patent No. 2.992.101, U.S. Patent No. 2.956.884, French Patent No. 1.396.544
Compounds described in Japanese Patent Publication No. 48-43125, etc., especially silica gel having a particle size of 0.5 to 20 μI,
．． Examples include polymers of polymethyl methacrylate having a particle size of 5 to 20 μm.

Examples of the support used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plate,
Representative examples include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, polycarbonate films, and polystyrene films. These supports are appropriately selected depending on the intended use of the silver halide photographic material.

The silver halide photographic material containing the compound of the general formula [1] of the present invention has the general formula [1] represented by the following general formula [1].
I[] [In the formula, R4 represents a 5- or 6-position nitro group, and R3 represents a hydrogen atom or a C1 to C, lower alkyl group. M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a cation such as an ammonium ion. ] Specific compounds represented by the general formula [ri] include 5-nitroindazole, 6-nitroindazole, etc., but the present invention is not limited thereto in any way.

The compound represented by the general formula [1[] can be developed by dissolving it in an organic solvent such as diethylene glycol, triethylene glycol, ethanol, jetanolamine, and triethanolamine, an alkali such as sodium hydroxide, and an acid such as acetic acid. It may be added to the liquid or may be added as is.

The compound represented by the general formula [+11] is about 1 per 11 developer solution.
Preferably, the concentration ranges from about 50 mg to 300 mg, more preferably from about 50 mg to 300 mg.

After exposure, the silver halide photographic material according to the present invention can be developed by various commonly used methods.

The black and white developer contains hydroxybenzenes, l-phenyl-
It is an alkaline solution containing a developing agent such as 3-pyrazolidones, aminophenols, and aminobenzenes, and may also contain other alkali metal salts such as sulfites, carbonates, bisulfites, bromides, and iodides.

Any sensitizing dye may be used in the present invention, but it is preferable that the dye has a maximum spectral sensitivity in the red or infrared region. Furthermore, in terms of storage stability of coating solutions for photographic emulsion layers containing tetrazolium compounds, the general formula [11[-
a], [111-b], and [112-C] are preferably used. Particularly, in the case of a sensitizing dye having a maximum spectral sensitivity in the infrared region, that is, in a wavelength region longer than 700 nm, the improvement in the storage stability of the coating solution is remarkable.

General formula [I[I-a] [However, Y and Y2 are each a benzothiazole ring,
Represents a group of nonmetallic atoms necessary to form a benzoselenazole ring, naphthothiazole ring, naphthoselenazole ring, or quinoline ring, and these heterocycles are lower alkyl groups,
It may be substituted with an alkoxy group, a hydroxyl group, an aryl group, an alkoxycarbonyl group, or a halogen atom. R,, R711 each represent a lower alkyl group, an alkyl group having a sulfo group, or an alkyl group having a carboxyl group. R6 represents a methyl group, an ethyl group, or a propyl group. X represents an anion. nr, R2 is
Represents O or l. m represents l or 0, and when it is an inner salt, m = 0. [However, Y, , Y, □, Y2□ and Y2□ are each 5- or 6-membered Represents a nonmetallic atom group necessary to complete a nitrogen-containing heterocycle, such as a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoxazole ring, a quinoline ring, a 3,3-dialkylindolenine ring,
Examples include a benzothiazole ring and a pyridine ring.

These heterocycles include lower alkyl groups, alkoxy groups, hydroxyl groups, aryl groups, alkoxycarbonyl groups,
It may be substituted with a halogen atom.

R, □, R, , R, and R22 each represent a lower alkyl group, an alkyl group having a sulfo group, or an alkyl group having a carboxyl group.

R,,,R,,,R,,,R2,,R,,,R,, and R26 are hydrogen atoms, substituted or unsubstituted alkyl groups,
or represents an unsubstituted alkyl group (the alkyl moiety has 1 to 18 carbon atoms, preferably 1 to 4 carbon atoms) or an aryl group, and Wl and W2 are connected to each other to form a 5- or 6-membered nitrogen-containing heterocycle. It can also be formed.

Further, R13 and R15 and R23 and R25 can be connected to each other to form a 5-membered ring or a 6-membered ring.

X11 and X21 represent anions. n1□n, □+
nz+ and n2□ represent 0 or l. +1111
and m3i represents 1 or O, and when it is 0, it represents an inner salt. ] Next, specific examples of sensitizing dyes used in the present invention will be shown, but the present invention is not limited to these dyes.

1[1-2 (CHz)zsOxH(CH2)3SO301I-4 1l-5 CH, CH.

II[-6 (CH2)3SO3e I[1-8 C285C21(5I0 C2H6C3H? I 0 III -10 ll-12 c, Is C!Is
ll-13 ■-14 III -15 I[[-16 C,)1. 1″″ 1[1-17 C,H.

ll-18 C,H.

I [I -19 2US ■-20 C2H,02H6 ! 0 1I-21 The sensitizing dye used in the present invention is preferably l rag to 2 g per mole of silver halide, more preferably 5B-
It is contained in a silver halide photographic emulsion in an amount of 1 g.

The sensitizing dye used in the present invention can be directly dispersed into the emulsion and can be added at any time during chemical ripening. They can also be first dissolved in a suitable solvent, such as evaporative methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and then added to the emulsion in the form of a solution.

The sensitizing dyes used in the present invention may be used alone or in combination of two or more. Furthermore, sensitizing dyes other than those of the present invention may be used in combination.

The sensitizing dye used in the present invention is disclosed in U.S. Patent No. 2503.
776, British Patent No. 742112, French Patent No. 20
By referring to the specifications of No. 65662 and Japanese Patent Publication No. 40-2346, art technicians can easily synthesize the images.

〔Example〕

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present description is not limited thereto.

Example 1 (Preparation of emulsion) Solution A Water
9.7Q Sodium Chloride
20g gelatin 105
g solution B solution
3.8Q Sodium Chloride
365g gelatin 94g
Potassium bromide 450g Hexachloroiridate potassium salt 0. n1% aqueous solution 28a+(2
0.01% aqueous solution of potassium hexabromorodate salt 1.0m+2 solution C water
3.8Q silver nitrate 1
, 700g40'C! In the solution A kept at a temperature of
The above solution B and solution C were simultaneously added functionally over 60 minutes while maintaining the pH at 3, I) Ag at 7.7, and further 1
After stirring for 0 minutes, add 6 pu of sodium carbonate aqueous solution.
．． 0, 20% magnesium sulfate aqueous solution 212 and 5% polynaphthalene sulfonic acid aqueous solution 2.5! The emulsion was flocculated at 40'O, decanted and washed with water to remove excess aqueous salt. Next, 3.7a of water is added to disperse it, and 0.9Q of a 20% aqueous magnesium sulfate solution is added again to remove the excess salt in the aqueous solution. Add 3.7Q of water and 141g of gelatin to it and disperse for 55°030 minutes. As a result, particles containing 35 mol % of silver bromide, 65 mol % of silver chloride, and an average monodispersity of 0.25 μm are obtained.

Next, 140 fflff of a 1% citric acid aqueous solution and 57 m4 of a 5% potassium bromide aqueous solution were added, followed by 120 mff and a 0.2% aqueous solution of sodium thiosulfate.
After adding 80 mQ of chloroauric acid aqueous solution and aging at 60°C for 70 minutes, I-1, llll-6, II
[-1L lll-18 and (a) (bXc) were added in the amounts shown in Table-1, and after 5 minutes, I-3 or l-11 was added as the compound of general formula [I] in the amounts shown in Table-1. After another 5 minutes, 10 g of 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene as a stabilizer and 1600 m of a 20% gelatin aqueous solution were added to the emulsion.
12 was added to stop the ripening, and the pH and pAg were adjusted. Thereafter, 30 g of hydroquinone as an antifoggant, 10 g of sodium p-dodecylbenzenesulfonate as a spreading agent, and 120 g of ethyl acrylate polymer latex were added, and styrene was added as a thickener.
20g of maleic anhydride copolymer was added, l-hydroxy-3,5-cyclos-triazine sodium salt and formalin were added as hardeners just before coating, and the above emulsion was coated with a banking layer and undercoated. The coating was placed on a prepared polyethylene terephthalate support so that the silver content was 4.2 g/m'', and as a protective film, 10 g of potassium bromide was added to an aqueous solution of 500 g of gelatin, and 15 g of the following compound (e) was added as a spreading agent. Furthermore, 20g of amorphous silica with an average particle size of 3.5μ was added and dispersed, and 1.1g of gelatin was added.
The emulsion layer and the protective layer were coated at the same time in such a manner that the thickness of the compound I-3 of the general formula [I]
Or, add l-11 to the rubber roll with the spreading agent added as shown in Table 1, and otherwise follow the same method as above (e) In addition, in order to evaluate the storage stability of the emulsion layer coating solution, the emulsion layer coating solution before adding the hardener was stored at 40°C with stirring for 12 hours, and the coating solution was also stored for 1 hour. We investigated changes in sensitivity to

Sensitivity evaluation was performed by passing the obtained sample through an optical wedge and a Kodak Latchin filter under a xenon light source for 10
-' second exposure I;. In addition, samples 1 to 6 have Wratten No.
9+ Samples 7-12 are Ratten NO, 88A, Samples 13-
For No. 24, Ratten No. 4 was used, respectively. Subsequently, processing was carried out using a developing solution and a fixing solution having the following formulation in a rapid processing automatic processing machine for a total processing time of 90 seconds.

Development processing conditions (process) (temperature) (time) Development 28℃ 30 seconds fixing 28℃ approx. 20
Wash with water for 2 seconds and dry at room temperature for about 20 seconds
Dry 45°0 20
Second developer composition (composition A) Pure water (ion-exchanged water) 150 ha Ethylenediaminetetraacetic acid disodium salt 2g diethylene glycol 50g potassium sulfite (55% w/v aqueous solution) 100m2 Potassium carbonate 50g hydroquinone
15 g 5-methylbenzotriazole 200 haze a 1-phenyl-5-mercaptotetrazole 30 g Potassium hydroxide pH of working solution
Potassium bromide amount to make 1O14
4.5g (composition) Pure water (ion-exchanged water) 3mg diethylene glycol 50g ethylenediaminetetraacetic acid disodium salt 25g Acetic acid (90% aqueous solution) 0.3+aQ5-nitroindazole 110mg 1-phenyl-3
- Pyrazolidone 500mg When using a developer, dissolve in 500ml of water in the order of the above composition A1 composition,
It was finished to lQ and used.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 40
mff Sodium sulfite 17g Sodium acetate trihydrate 6.5g Boric acid
6g sodium citrate
Dihydrate 2g acetic acid (90% vx/v aqueous solution)
13.6m12 (composition) Pure water (ion exchange water) 17m12
Sulfuric acid (50% w/w aqueous solution) 4.7g
Aluminum sulfate (Afl, O, aqueous solution with a converted content of 8.1% w/w)
When using a 26.5 g fixer, it was dissolved in 500 ml of water in the order of the above compositions A1 and 1Q.

The po of this fixer was about 4.3.

Photographic characteristic curves were drawn for the developed samples and sensitivity and gamma were measured. Sensitivity was determined from the reciprocal of the exposure amount required to form an optical density of 2.5, and gamma was determined from the linear portion from 0.5 to 4.0 in density.

The change in sensitivity due to storage of the coating solution was evaluated by the rate of change in sensitivity after 8 hours of storage when the sensitivity after 1 hour of storage was taken as 100. The changes in gamma were also compared after 1 hour and 8 hours, and the results are shown in Table 1.

As can be seen from Table 1, although it is possible to increase the contrast by adding the tetrazolium compound represented by the general formula [I], it is found that the stagnation storage stability is poor.

On the other hand, samples 3, 6.9, and 12 show little change in sensitivity during storage of the coating solution and little deterioration in gamma. Moreover, from Samples 13 to 24, it can be seen that the storage stability of coating solutions of emulsions spectrally sensitized in the green or blue region is hardly affected by the tetrazolium compound.

〔Effect of the invention〕

According to the present invention, it has high photosensitivity in the red region or infrared region,
It was possible to provide a silver halide photographic material with little change in performance during storage of the coating solution.

Claims (1)

[Scope of Claims] In a halogenated photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, the silver halide in the silver halide emulsion layer forms a compound of the following general formula [I] during chemical ripening. ], and the silver halide contained in the silver halide emulsion layer is silver chloroiodobromide containing at least 50 mol% of silver chloride. A silver halide photographic light-sensitive material. General formula [I] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1, R_2 and R_3 each represent a hydrogen atom or a substituent, and X^■ represents an anion. ]