JPH0279833A - Direct positive silver halide photographic sensitive material and method for processing thereof - Google Patents

Abstract

PURPOSE:To improve the quality of the subject material by specifying the weight ratio of silver to gelatin per unit area of a photographic constituting layer on the side of an emulsion layer contd. in the photosensitive material. CONSTITUTION:The photosensitive material has the weight ratio (Ag/gelatin) of the silver to the gelatin per unit area of >=1.0, preferably 1.5-3.0 in the photographic constituting layer on the side of the emulsion layer which contains silver halide particles previously fogged by a reducible fogging agent, and a water-soluble gold compd. and is mounted on a substrate. The total processing time of the photosensitive material is 20-60sec. When the wt. ratio of the silver to the gelatin is <1.0, namely when the amount of the gelatin is large against that of the silver, the troubles about faulty fixing and a deep residual color generate, and the good quality of the photosensitive material, without deteriorating the optical density of the material, is obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a direct positive silver halide photographic light-sensitive material,
More specifically, the present invention relates to a photographic material suitable for ultra-rapid processing and a processing method thereof.

[Background of the invention]

In recent years, direct positive silver halide photographic materials to which fog has been imparted have been moving toward higher sensitivity. In order to achieve high sensitivity, it is necessary to obtain sufficient development activity with as little fog as possible. For this purpose, a method of imparting fog in the presence of a reducing fogging agent and a water-soluble gold compound is advantageously used.

An example of such a fogging method is U.S. Pat.
1.305, 3,501.306, 3,501
, No. 307, etc.

On the other hand, another widely used technique for increasing the sensitivity of fogged direct positive silver halide photographic materials is to use an organic desensitizer adsorbed on the surface of silver halide grains as an electron acceptor. . Examples of the desensitizing agent include U.S. Pat. Nos. 2,930.694 and 3,431.11.
No. 1, No. 3,492.123, No. 3,501.31O
There are compounds described in No. 3,567.456, No. 3,582.343, etc. In recent years, the consumption of silver halide photographic materials has continued to increase. For this reason, the number of sheets of silver halide photographic light-sensitive materials to be developed has increased, and there is a demand for speeding up the development process, that is, increasing the amount of grain deposited within the same amount of time.

The above trend can also be seen in the printing plate making field.

In other words, as the immediacy and number of times information is rapidly increasing, it has become necessary to perform printing plate-making work in a short delivery time and in larger quantities. In order to meet such demands of the printing plate making industry, it is necessary to promote the simplification of the printing process and to process printing plate making films more quickly.

When trying to meet the above-mentioned demands, it is not possible to achieve the objective simply by shortening the number of sheets of direct-positive photosensitive material to be processed. That is, if the processing time is shortened, the developed density will decrease, the image will become softer, and the residual color will become stronger.

[Purpose of the invention]

In order to solve the above-mentioned problems, the purpose of the present invention is to provide a silver halide photographic material and a processing method thereof, which have good quality with high contrast, little residual color, and little loss of density even when ultra-rapid processing is performed. It is to provide.

[Structure of the invention]

The above object of the present invention is to provide a direct positive silver halide photographic light-sensitive material having an emulsion layer containing silver halide grains prefogged on a support using a reducing fogging agent and a water-soluble gold compound. The weight ratio of the amount of silver to the amount of gelatin per unit area in the photographic constituent layer on the side with the emulsion layer (
Ag/gelatin) is 1.0 or more, and the above-mentioned direct-positive silver halide photographic light-sensitive material is processed for a total processing time of 20
This is achieved by a method for processing a direct positive silver halide photographic light-sensitive material, which is characterized by processing in 60 seconds.

The details of the present invention will be explained below.

The amount of gelatin in the embodiment of the present invention refers to the total amount of gelatin in one or more layers on the side of the support that includes the photosensitive silver halide emulsion layer, and is limited to the amount of gelatin in the silver halide emulsion layer. It's not something you can do. In addition, when a plurality of layers are coated on the same side of the support, the amount of silver is defined based on the total amount of silver in each layer.

In the present invention, the ratio between the amount of silver and the amount of gelatin must satisfy the following formula.

Ag/gelatin≧1.0 Unit y/m” In the above formula, if it is less than 1.0, that is, if the amount of gelatin is large compared to the amount of silver, it may cause problems such as poor fixing or strong residual color.The above ratio is preferably 1.5 or more and 3.0 or less.

In this specification, ultra-quick processing means that the leading edge of the film is inserted into an automatic developing machine, passes through a developing tank, a transition area, a fixing tank, a transition area, a washing tank, a transition area, and a drying area. [In other words, the total length of the processing line (+a) is the line conveyance speed (m/
Refers to processing in which the quotient (sea, )) divided by see, ) is less than 60 seconds. The reason why the time for the transition part should be included here is that it is well known in the industry that even in the transition part, the liquid from the previous process is swollen in the gelatin film, so it is virtually impossible to This is because it can be considered that the processing process is progressing.

In the present invention, general formulas (1) and (n) are used.

At least one of the compounds represented by (I[[) , [:IV) and (V)] is contained, and these are advantageously used as organic desensitizers. These compounds are
It is superior in that it provides high sensitivity and low residual color.

General formula (I) General formula (II) General formula (I[I) General formula CIV) General formula [v] (However, general formula CI), (n), (I[), (IV) and [■] , R, , R, and R3I are hydrogen atoms,
Represents a halogen atom, alkyl group, alkoxy group, aryloxy group, or nitro group, R2゜R3,R,,R,
,,R,3,R,,,R32+ R,,,R,,.

R44 and R54 represent an unsubstituted or substituted alkyl group, alkenyl group, aryl group, or aralkyl group, R,, R,, R, s, R2,, R,.

R, , R, , R, , R, 11 and Rsa are hydrogen atoms, halogen atoms, alkyl groups, aryl groups, thienyl groups, alkoxy groups, hydroxy groups, cyano groups, alkylsulfonyl groups, alkoxycarbonyl groups, represents a phenylsulfonyl group, trifluoromethyl group, trifluoromethylsulfonyl group, or nitro group, R41 represents an aryl group, R6□ represents an alkyl group, R8+ represents an unsubstituted or substituted alkyl group, Xθ represents an anion, and n represents l or 2. However, when the compound forms an inner salt, n is l. ) The photosensitive material of the present invention has general formulas CI) and (II).

It is sufficient that at least one compound arbitrarily selected from the group consisting of compounds represented by CI[[), (IV] and [v] is contained, and one compound represented by any one general formula is sufficient. Alternatively, two or more types of compounds represented by two or more general formulas may be contained, and in the case of two or more types, the combination thereof is arbitrary.

As a method for synthesizing the organic desensitizer of the present invention, general formula (I)
, Cm) and (III) are disclosed in, for example, U.S. Pat. Nos. 3,567.456 and 3,582.343;
The method described in 3.598.596 etc., the general formula (
The compound represented by IV) is disclosed in U.S. Patent No. 3,539.349.
The method described in U.S. Patent Nos. 3,431.111 and 3,492,12
There is a method described in No. 3, etc.

Next, the general formula CI), (I[), (I[[)
, (IV) and (V), the following CI-1) to Cl-9), [:I[-1]
~(n-3).

(III-1) ~ [:I[l-6), (IV-1
), (IV-2).

(V-1) to (V-3), but the present invention is not limited to these specific compounds CI-2) [-3) (Pts represents a para-toluenesulfonic acid group. Same below) Cl-4) CI-6) NO8 NHCOCR5 (n-1) (n-2) NO5 (If-3) NHCOCH.

(III-1) CIII-2) C, H.

N.L.I.

CIII-3) (III-4) CI[[-5] [:llll-6) (■-1) CH.

(IV-2) 2H1 (V-1) (V-2) (V-3) C,H.

These organic desensitizers are preferably dissolved in a suitable solvent and added in an amount of 10@-4 to lo@-2 mol per mol of silver halide to the desalted silver halide. Further, the above organic desensitizers may be used alone or in combination of two or more.

The photographic layer in the present invention is a general term for a photosensitive layer and a non-photosensitive layer. Specifically, the photosensitive layer is a direct positive silver halide photographic emulsion layer, a direct positive silver halide emulsion layer which has been fogged in the presence of a reduced fogging agent and a water-soluble gold compound, and the like. Specifically, the non-photosensitive layer is a base layer, an intermediate layer, a protective layer, etc.

Examples of reducing fogging agents used to impart fog in the present invention include formalin, hydrazine, polyamines (such as triethylenetetramine, tetraethylenepene, tamine, etc.), thiourea dioxide, tetrahydroxymethylphosphonium chloride, amineporan, These include boron hydride compounds, stannous chloride, etc., and it is generally preferable to use them in an amount of 10-7 to lo-3 mol per mol of silver halide. Incidentally, these reducing fogging agents may be used alone or in combination of two or more.

Further, water-soluble gold compounds include, for example, potassium chloroaurate, chloroauric acid, potassium gold cyanide, potassium gold thiocyanate, sodium gold thiomaleate, gold thioglycose, etc., and generally have a concentration of lo-6 per mole of silver halide.
It is used in a range of from lo-4 mol to lo-4 mol.

The silver halide emulsion used in the present invention may have any grain size, crystal habit, silver halide composition, etc., but those useful as light-sensitive materials have a grain size of about 0.1 to about 1 μm. It is preferable in terms of sharpness and sharpness, and in silver iodobromide, the silver iodide content is preferably 5 mol% or less, and more preferably 3 mol% or less.
Those within the mol% range have a small development inhibition property and are excellent in practical use. These silver halide emulsions are prepared by various methods. For example, a method of containing a Group 8 soluble total complex salt as described in U.S. Pat. Ammoniacal emulsion preparation method as described in U.S. Pat.
, 501°305, a method for preparing a heterodisperse emulsion as described in JP-A-49-43627, and US Pat. No. 3,501.
306, U.S. Patent No. 3,367.785, British Patent No. 1,
No. 229.868, No. 1,186,718, etc., and the internal latent image type emulsion preparation method described in U.S. Patent No. 2,592.250. The following methods can be applied.

Other photographic additives may also be used in the direct positive silver halide photographic emulsion used in the present invention. Stabilizers may include, for example, triazoles, azaindenes, quaternary benzothiazolium compounds, mercapto compounds, or water-soluble inorganic salts such as cadmium, cobalt, nickel, manganese, gold, thallium, zinc, and the like. Hardening agents include formalin, glyoxal, aldehydes such as mucochloric acid, s-triazines, epoxies,
Aziridines, vinyl sulfonic acid, etc., coating aids such as saponin, sodium polyalkylene sulfonate, polyethylene glycol lariul or oleyl monoether, amylated alkyl taurine, fluorine-containing compounds, etc., and sensitizers such as polyester Alkylene oxide and its derivatives may also be included. Furthermore, it is also possible to contain a color coupler. In addition, a preservative, an antistatic agent, a developer, etc. can also be contained as necessary.

Supports used in the present invention include supports such as paper, glass, cellulose acetate, cellulose nitrate, polyester, polyamide, polystyrene, and polypropylene, or, for example, a combination of paper and polyolefin (e.g., polyethylene, polypropylene, etc.). A bonded body of two or more substrates, such as a laminate, is used.

As the developer according to the present invention, one having a composition commonly used can be used. Examples of developing agents include hydroquinone, alkylhydroquinone (e.g. methylhydroquinone, dimethylhydroquinone, t-butylhydroquinone), catechol, pyrazole, chlorohydroquinone, dichlorohydroquinone, methoxyhydroquinone, ethoxyhydroquinone, aminophenol developing agent (e.g. N-methyl-p・Aminophenol, 2
．． 4-diaminophenol), ascorbic acid developing agent, N-methyl-p-aminophenol sulfate, pyrazolones (e.g. 4-aminopyrazolone), 3-pyrazolidone developing agent (e.g. l-phenyl-3-pyrazolidone, l-phenyl- 4,4-dimethyl-3-pyrazolidone, 1-7enyl-5-methyl-3-pyrazolidone,
1-7enyl-4-methyl-3-pyrazolidone, 1.5
-diphenyl-3-pyrazolidone, 1-p-tolyl-3
-pyrazolidone, t-p-hydroxyphenyl-4,4
-dimethyl-3-pyrazolidone) and the like can be used alone or in combination. In particular, combinations of hydroquinone and 3-pyrazolidones or hydroquinone and aminophenols are suitable for the rapid treatment of the present invention.

In addition, the developer of the present invention may include preservatives such as sulfites, bisulfites, and hydroxylamines; alkaline agents such as hydroxides, carbonates, and phosphates; and pi adjusters such as acetic acid. agents; solubilizing agents such as polyethylene glycols; sensitizers such as quaternary ammonium salts; methanol, diethylene glycol, jetanolamine, dimethylformamide,
Organic solvents such as dimethylsulf7oxide: Development accelerators; Surfactants: Defoaming agents; Color toning agents; Viscosifiers such as carboxymethyl cellulose and hydroxyethyl cellulose; Hardeners such as gel taraldehyde; Silver sludge inhibitor: thioether, Silver halide solvents such as thioamide, thiocyanate, and thiosulfate; antifoggants such as potassium bromide and benzotriazole; and various additions such as chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, and phosphonocarboxylic acid. agent may be included.

As the fixer used in the present invention, those having compositions commonly used can be used. Sodium thiosulfate, ammonium thiosulfate, sodium thiocyanate, ammonium thiocyanate as a fixing agent, thiourea as a silver halide solvent, amine derivatives, etc., as well as sodium sulfite, ammonium sulfite, sodium bisulfite, potassium metabisulfite, etc. Sulfites; borates such as boric acid, borax, and sodium metaborate; organic carboxylic acids such as acetate, citric acid, tartaric acid, and malic acid; inorganic acids such as sulfuric acid and hydrochloric acid; ethylenediamine, jutanolamine, triethanolamine, etc. amines; water-soluble aluminum salts such as potassium light bread, ammonium light bread, aluminum sulfate, aluminum chloride; organic compounds such as methanol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polyoxyethylene glycol, acetone; Iodides such as potassium iodide and sodium iodide, and other additives can be included as necessary.

〔Example〕

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

Example l Preparation of emulsion coating solution In a 1% aqueous gelatin solution IQ at 65°C, 220 mQ of a 3% aqueous silver nitrate solution and 220 mQ of an aqueous solution containing 98 mol% potassium bromide and 2 mol% potassium iodide based on the silver nitrate were added.
12 were added simultaneously and over 30 minutes while controlling the addition rate to increase over time. Subsequently, 280 mQ of a 40% silver nitrate aqueous solution and 280 mQ of an aqueous solution containing 98 mol% potassium bromide and 2 mol% potassium iodide relative to the silver nitrate were added simultaneously and the addition rate was controlled so as to increase over time. The mixture was added over a period of 100 minutes. During the above process, pi is kept at about 2 with nitric acid, and pAg is kept at about 7.5 with potassium bromide.
I kept it. After completing the above steps, adjust the pH using sodium carbonate aqueous solution.
was adjusted to about 5.5, water-soluble salts were removed by a conventional flocculation method, and 15 g of gelatin was added to finish.

As a result, a silver iodobromide emulsion having an average grain size of 0.27 μm, containing 2 mol % silver iodide, and consisting of highly monodisperse and regular cubic grains was obtained.

The above emulsion was adjusted to pH-6.8 with a sodium carbonate aqueous solution, and at pAg-6.8, 0.12 mg of thiourea dioxide was added per mole of silver halide, and the mixture was heated at 70°C.
Aged for 0 min, then 0.50 min/mol silver halide.
+ng of chloroauric acid was added and aged at 70° C. for 60 minutes to cause reduction fog and metal fog.

By adding potassium bromide to the fogged emulsion, the pA
g = 9.2, and then 600 mg of the above-mentioned Cl-4), [r-7) or (:I[-11] per mole of silver halide was added as an organic desensitizer, and citric acid was added. The pH was adjusted to 5.3 using

Next, add 0.2g/diethylene glycol as a wetting agent.
m”, 40 mg of sodium 1-decyl-2-(3-isopentyl)succinate-2-sulfonate as a coating aid.
/m', 60 mg/m2 of styrene-maleic anhydride copolymer as a thickener, and 16 mg of formalin as a hardening agent per 1 g of gelatin to prepare a direct positive silver halide emulsion coating solution.

Preparation of coating solution for protective layer Add pure IH water to 1 kg of gelatin, and after swelling, add 40'0
30 g of a polymer of methyl methacrylate (average particle size: 0.27 μm) as a matting agent was dispersed in gelatin and finished to 20Q to obtain a protective layer coating solution.

Preparation of coating sample The emulsion coating solution prepared above and the coating solution for the protective layer were simultaneously multilayer coated onto a subbed polyethylene terephthalate support having a thickness of 100 μI to obtain an Ag/gelatin ratio of 0.95 to 3. Sample No. 15 was prepared by adjusting the flow rate of the coating solution for the protective layer so that the flow rate was 0.0.Formalin hardener was added to the coating solution for the protective layer during simultaneous multilayer coating.

These samples were exposed to light using a tungsten light source using a glass wedge. This sample was processed at line speed 2000.
The treatment was carried out using GR-27 (manufactured by Konica) improved in mm/win according to the following recipe.

Developer prescription (composition A) Pure water (ion exchange water) 150mf
f Ethylenediaminetetraacetic acid disodium salt 2g diethylene glycol 509 Potassium sulfite (55% W/V aqueous solution) 100ml Potassium carbonate 509 Hydroquinone 1595-Methylbenzotriazole 2001191-Phenyl-5-
Mercaptotetrazole 30119 Potassium hydroxide
Potassium bromide amount to make I)H of working solution 1O09
4.5g (composition) Pure water (ion-exchanged water) 3mg diethylene glycol 509 ethylenediaminetetraacetic acid disodium salt 25IIIg acetic acid (9
0% aqueous solution) 9.3+aff2
-Sodium mercapto-penzimidazole-5-sulfonate 50+11
91-phenyl-3-pyrazolidone 50
When using a 0 mg developer, the above compositions A and B were dissolved in 500 m of water (2) in this order and finished to 1 Q before use.

Fixer formulation (composition A) Ammonium thiosulfate (72.5% W/V aqueous solution) 230m
n Sodium sulfite 9.5g Sodium acetate trihydrate 15.99 Boric acid 6.7g Sodium citrate dihydrate 2g Acetic acid (90% W
/W aqueous solution) 8.1a12 (composition) Pure water (ion exchange water) 17m12
Sulfuric acid (50% W/W aqueous solution) 5.8
9 Aluminum sulfate (Aa, O, converted content 8.1% W/W (7) aqueous solution)
When using a 26.5 g fixer, it was dissolved in 500 mQ of water in the order of the above composition A1 and finished to 1Q.

The pH of this fixer was about 4.3.

[Rapid development processing conditions]

(Process) (Temperature) (Time) (Tank capacity)
Development 35℃ 10 seconds
20Q fixing 35°0 15 seconds 20I2 water washing 18℃
10 seconds 15Q drying
40°C 10 seconds 20Q Each process time includes the so-called wading conveyance time to the next process.

Dry to Dry time, 45 seconds For the developed sample subjected to wedge exposure, draw a photographic characteristic curve, calculate the relative value of the sensitivity at optical density 2.5 using sample No. 1 as a reference, and calculate the gamma as Optical density 1.0 to 2
．． The jan# value of the straight line section up to 5 is shown.

Next, using xenon light, a set of photographs was taken with a camera for printing plates, and the quality of the formed mesh (dot quality) was evaluated. The dot quality is so-called 50, where the halftone area and the clear area are equal.
Regarding the % dots, the state of fringe (blur) occurring around the halftone dots was visually judged and evaluated on a 5-point scale with 5 being the smallest fringe.

That is, 5 is excellent and 1 is extremely bad. 5
If the 0% dot quality is below 3, this is generally unacceptable.

Furthermore, for the exposed samples, five films were stacked one on top of the other, and the remaining color of the film was visually evaluated in five stages. 5 is colorless, l is strong residual color. Generally, residual color below 3 is considered to be a major drawback.

In addition, the maximum density was measured for the unexposed sample.

These results are shown in Table 1.

As is clear from the results in Table 1, when the ratio of the amount of silver to the amount of gelatin per unit area is 1 or more, it is clear that the dots have high contrast, little residual color, and good dot quality.

Moreover, when the above ratio is 3 or more, scratches and pressure deteriorate.

4 insects.

Table 1 [Effects of the invention] According to the present invention, even when ultra-quick processing is performed, images with high contrast and
It has been possible to provide a silver halide photographic material having good quality with little residual color and little decrease in density, and a method for geographically disposing the same.

Claims (2)

[Claims] (1) A direct positive silver halide photographic light-sensitive material having, on a support, an emulsion layer containing silver halide grains prefogged with a reducing fogging agent and a water-soluble gold compound. A silver halide photographic material for direct positive use, characterized in that the weight ratio of the amount of silver to the amount of gelatin per unit area (Ag/gelatin) in the side photographic constituent layer is 1.0 or more. (2) A method for processing a direct-positive silver halide photographic light-sensitive material, which comprises processing the direct-positive silver halide photographic light-sensitive material according to claim 1 in a total processing time of 20 to 60 seconds.