JPH0420954A - Image forming method - Google Patents

Abstract

PURPOSE:To prevent the production of sludges in a development processing solution and to attain the high sensitivity and high density by applying the supply of a developer incorporating a hydroquinone group on the exposed surface of a photosensitive material. CONSTITUTION:A silver halide photosensitive material 4 incorporating at least one nucleating agent is transported in the direction of the arrow A with the rotation of carrier rollers 1-3, and when the silver halide photosensitive material 4 is transported, the developer consisting of the hydroquinone is supplied from the supply openings 6a-8a at the supplying nozzles 6-8. The developer flows in the direction of a pair of carrier rollers 1-3 and both surfaces of the silver halide photosensitive material 4 are applied. A fresh developer from the respective supplying nozzles 6-8 is supplied on the silver halide photosensitive material 4, falls from the carrier roller 1 in the upper stage downwards, further falls from the carrier roll 2 in the middle stage downwards, then falls from the carrier roll 3 and is dumped and the developer is disposable.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a method for forming an image by developing a silver halide photographic light-sensitive material. The present invention relates to an image forming method for a silver halide photographic material that prevents the occurrence of .

[Background of the invention]

Traditionally, halogen silver photosensitive materials have been processed in automatic processing machines. For example, after exposure, a photosensitive material is transported into a developer stored in a developer tank by a roller transport mechanism. Images are obtained by immersion for a predetermined period of time.

Problems with such conventional methods include that the active ingredients in the developer stored in the developer tank deteriorate due to fatigue during the running process, and that the developer becomes inert due to air oxidation of the developing agent over time. For example,

Under these circumstances, the applicant has filed, for example, Japanese Patent Application No. 1-1956.
No. 41, No. 1-195644, No. 1-189847, No. 1-175997, etc. disclose that images are created by supplying and coating a developer onto the exposed surface of a photosensitive material without immersing the photosensitive material in a developer. I suggested a way to get it.

According to the processing method, development with a tired developer is avoided,
The advantage is that high-quality images can always be obtained stably.
.

However, when a silver halide photographic light-sensitive material is developed outside the solution using a developer supply coating method, the development mla'1aI
f raw TIEaIllfpJ/+C power-*1 Hime*t4
se-婉1+! A phenomenon appeared in which muddy precipitates (called sludge) were generated in the I-fu' treatment solution. or,
This sludge also adhered to the photosensitive material during the running process, causing serious damage to images, and urgent improvements were needed.

A considerable amount of this sludge is generated even with conventional processing methods, and countermeasures include, for example, making the silver salt less soluble or increasing the hardness of the photosensitive material to prevent its elution. In addition, techniques are generally known in which a metal chelating agent is added to a developer to chelate the eluate.

However, in the developer supply coating method according to the present invention, these conventional techniques result in a significant deterioration in developability, and further investigation is desired.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a developer supplying development system that:
An object of the present invention is to provide a method for forming an image on a silver halide photographic material that does not generate sludge, has high density, and has high sensitivity. Other objectives will become apparent from the description below.

[Structure of the invention]

It was discovered that the above object of the present invention can be easily achieved by the following image forming method, and the present invention has been completed.

That is, in the photosensitive layer and/or other hydrophilic colloid layer,
In a method of forming an image by developing a silver halide photographic light-sensitive material containing at least one nucleating agent after imagewise exposure, the processing method includes supplying a developer containing hydroquinones, This is achieved by a method for forming an image on a silver halide photographic material, which is characterized by coating the exposed surface of the material.

The present invention will be explained in detail below.

In the developer supply method of the present invention, the amount of developer supplied and coated on the surface of the photosensitive material may be arbitrary, but from the viewpoint of economy and obtaining the desired effect of the present invention, it is preferably 70 to 300 m<
2/m2, more preferably 100-200
m2/m2.

In the present invention, a method for developing a photosensitive material after exposure without immersion will be specifically described below.

The image forming method of the present invention involves supplying a developer containing hydroquinones to the exposed surface of a silver halide photographic light-sensitive material containing a nucleating agent in a coated manner without immersing the light-sensitive material in the solution. The image is then developed. Specifically, examples include a roller transfer method, a day-lag method, a processing device having a plurality of guide means having slits holding a developer in the film transport direction, and a curtain coating method.

In the case of a low viscosity treatment liquid, it may be applied by spraying under pressure. The treatment liquid may be supplied not only once, but also several times.

It is preferable to supply the liquid to both sides of the silver halide photographic light-sensitive material while transporting the light-sensitive material.Transportation may be carried out horizontally or vertically, but it takes up less space for the equipment to transport the material vertically. It is preferable that it can be made smaller.

The developer according to the present invention uses hydroquinone, chlorohydroquinone, and methylquinone as hydroquinones. The amount used may range from 1 to 20 g/M. In addition, the developer includes a 3-pyrazolidone developing agent, a dialdehyde hardener, or an indazole-based, benzimidazole-based, benzotriazole-based, or mercaptothiazole-based developer as described in JP-A-63-10158. Anti-capri agents selected from the following may also be used, as well as chelating agents, buffers, alkaline agents, solubilizing agents, PL (adjusting agents, development accelerators, surfactants, etc.), if necessary.

In the present invention, when transporting the photosensitive material using the exposure method, a step of heating the photosensitive material may be included. As the heating heater, a far infrared heater is preferable.

Next, the present invention will be explained in detail based on the accompanying drawings.

FIG. 1 shows a developing device to which an example of the protrusion of the present invention is applied. In this developing device, a pair of transport rollers 1, 2.
3 are vertically stacked in three stages, and the silver halide photographic material 4 is fed in the direction of the exposure mark A and subjected to development processing.

The upper, middle, and lower stages are each constructed in the same way, and above the pair of conveyance rollers 1 to 3 are provided with a pair of supply nozzles 6, 7, and 8, respectively, and the supply ports 6a to 6 of the supply nozzles 6 to 8 8a faces toward the contact surfaces of the conveyance rollers 1 to 3, and is arranged so as to face the roller surfaces.

The silver halide photographic light-sensitive material 4 is transported in the direction of arrow A by the drive of the transport rollers l to 3, and when the silver halide photographic material 4 is transported, it is developed from the supply ports 6a to 8a of the supply nozzles 6 to 8. liquid is supplied. This developer flows toward the contact surfaces of the pair of transport rollers 1 to 3, and is applied to both sides of the silver halide photographic material 4.

A new developer is supplied from each supply nozzle 6 to 8 to the silver halide photographic light-sensitive material 4, falls downward from the upper conveyance roller I, further downwards from the middle conveyance roller 2, and then continues to the conveyance roller. 3 falls and is discarded, and the developer is now disposable.

In addition, a tray is arranged below the transport rollers 1 to 3 so that the developer falls onto the tray, and piping is connected to the tray so that a pump can circulate the developer in the tray to the supply nozzle. You can also do this.

In this case, the developing solution does not undergo development fatigue due to processing, and since the circulating developing solution has a small contact area with the atmosphere, there is little fatigue over time due to carbon dioxide absorption, and reuse is possible.

The nucleating agent referred to in the present invention has the effect of increasing the maximum density and activating the development when developing a silver halide emulsion, and also suppresses the generation of silver sludge that dissolves into the developer. It is something.

As a compound having such an effect, a nucleating agent compound for directly obtaining a positive image by subjecting an internal temperature type silver halide emulsion to surface development processing can be preferably used.

In the present invention, examples of compounds useful for improving developability and preventing silver sludge include compounds represented by the following general formula CI) or [■].

General formula (1) In the formula, Zl represents a group necessary to form a 5- to 6-membered heterocycle, and Z forms a 4- to 12-membered non-aromatic hydrocarbon ring or non-aromatic heterocycle. represents the group necessary for P represents a nitrogen atom or a carbon atom, and R represents an aliphatic group.

However, R and 2. ．． 2. At least one of the substituents to
One shall contain an alkynyl group.

Furthermore, R and 2. ．． At least one of 22 may be substituted with a group having a group that promotes adsorption to silver halide. X- is an anion, and n represents the number necessary to balance the charges.

Preferred examples of the heterocyclic bone nucleus completed with ZI include quinolinium, benzimidazolium, pyridinium, acridinium, phenanthridinium, naphtopyridinium and inquinolinium nuclei. More preferred are quinolinium, naphtopyridinium, and benzimidazolium nuclei, and most preferred is quinolinium.

The ring nucleus formed by z2 is preferably a carbon atom, particularly cyclopentane, cyclohexane, cyclohebutane, cyclohexene, indane, tetrahydrobilane, tetrahydrothiophene and the like.

The aliphatic group R is preferably an unsubstituted alkyl group having 1 to 18 carbon atoms or a substituted alkyl group having 1 to 18 carbon atoms in the alkyl moiety.

R is preferably an alkynyl group, and most preferably a propargyl group.

Among the compounds represented by the general formula CI), examples of the group having a group that promotes adsorption to silver halide include a thioamide group, an azole group, and a heterocyclic mercapto group.

General formula CI+) R,R.

R1 represents an aliphatic group, an aromatic group, or a heterocyclic group, and R2 represents a hydrogen atom, an alkyl group, an aralkyl group, an aryl group, an alkoxy group, an alkoxyalkyl group, an aryloxy group, or an amino group.

X represents a carbonyl group, a sulfonyl group, a sulfonyl group, a phosphoryl group, or an iminomethylene group.

R1 and R4 each represent a hydrogen atom, or one of them represents a hydrogen atom, and the other represents any one of an alkylsulfonyl group, an arylsulfonyl group, or an acyl group. Furthermore, R1+ Rt,
A substituent having a group that promotes adsorption to silver halide may be introduced into one of Rs and R4.

R is preferably an aromatic group, an aromatic heterocycle or an aryl-substituted methyl group, and more preferably an aryl group.

When X is a carbonyl group, R2 is preferably a hydrogen atom, an alkyl group, an alkoxy group, an alkyl group, or an aryl group.

Hydrogen atoms are similarly preferred as Rs and Rh. Incidentally, examples of the adsorption-promoting group to silver halide include those having the same meaning as in general formula (I).

Next, specific examples of compounds represented by the general formulas CI) and (I[) used in the present invention will be shown, but the present invention is not limited thereto.

Cl(, C=CH CH2CHCN CB, C=CH ■ ■ ■ CH, C=CH ■ ■ CH, C=CH ■ H C8, C=CH ■ CH, C Mi CH ■ CI(2fjcH ■ CH.

■ CH2CE: CH ■ ■ ■ ■ ζ ■ H2C CH CH2CECH F12C CH ■ song ■ ■ ■ C1l, C=CH ・CFjSO,- CH2C: CH CH,C-CH ■ ■ ■ ■ CH ■ CH.

■ ■ ■ ■ ■ ■ ■ ■ ■ R song C,H.

■ ■ ■ ■ so, cHx ■ ■ ■ ■ CH, CH2SH The above compounds are known compounds, for example, Research Disclosure No. 15162 (1976, 11
) and same No. 23516 (1983, 11), same No.
o, 22534 (1983°1), same No. 2321
3 (1983, 8).

The above-mentioned nucleating agent used in the present invention is added and contained in the photosensitive layer and/or other hydrophilic colloid layer constituting the silver halide photographic light-sensitive material.

The photosensitive layer is a silver halide emulsion layer, preferably a highly sensitive silver iodobromide emulsion layer.

Further, other hydrophilic colloid layers include, for example, a protective layer, an intermediate layer, an undercoat layer, etc. adjacent to the above-mentioned silver halide emulsion layer.
Examples include a filter layer, an antihalation layer, an ultraviolet absorbing layer, an antistatic layer, etc., and preferably a protective layer exhibits the effects of the present invention well.

The nucleating agent may be added to one or both of the photosensitive layer and the hydrophilic colloid layer.

In order to incorporate the nucleating agent of the general formula CI) and [■] into the constituent layers of a photographic light-sensitive material, water or alcohols (eg, methanol, ethanol), esters (eg, ethyl acetate), ketones (eg, It is dissolved in a hydrophilic solvent such as acetone and added to the colloid solution.

When added to the silver halide emulsion of the photosensitive layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added to the coating solution after chemical ripening.

The amount added is not uniform depending on the type of compound, but is in the range of 1X10-' mol to 5X102 mol per mol of silver halide, more preferably 1X10-' mol-2X 1
0-2 mol is sufficient.

When added to the hydrophilic colloid layer, I
mol-5X10-''mol/l112, more preferably IX10-'mol2X10-3mol/m2.

The emulsion used in the silver halide photographic light-sensitive material of the present invention may be any silver halide such as silver iodobromide, silver iodochloride, silver iodochlorobromide, etc., but it is said that particularly high sensitivity can be obtained. From this point of view, silver iodobromide is preferred.

Silver halide grains in photographic emulsions are cubic, octahedral, 1
Whether it is a completely isotropic crystal like a tetrahedron, a polyhedral crystal like a sphere, a twin crystal with planar defects, or a mixture or composite of these. good.

The grain size of these silver halide grains may range from fine grains of 0.1 μm or less to large grains of up to 20 μm.

The emulsion used in the silver halide photographic material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No. 47643 (December 1978), pages 22-23, 1.
ionPreparation and types
) and (RD) No. 18716 (November 1979), page 648.

The emulsion of the silver halide photographic light-sensitive material according to the present invention is described, for example, in "The theory o" by T. H. James.
f thephotographic process
``4th edition, published by Macmillan (1977) 3
Method described on pages 8-104, G, F, Dauf fi
“Photograph emulsion chemistry” by n.
"emulsion Chemistry", Foca
Published by l press (1966), P, G l
afk i d e s s y r s i g i s s s y s s y s s y s s y s s y s s y s s y s s y s s y s s
l”: himio 04physique photo
grahique” Paul Monte1 (1
967), V. L. Zelikman et al. “Manufacturing and Coating of Photographic Emulsions” “MakiB and coatin”
g photography mulsion” F
It is prepared by the method described in Ocal Press (1964).

That is, solution conditions such as neutral method, acidic method, ammonia method, etc.
It can be produced using particle preparation conditions such as bed heating method, back mixing method, double jet method, Chondral double jet method, conversion method, core/fel method, and combination methods thereof.

A preferred embodiment of the present invention is a monodispersed emulsion in which silver iodide is localized inside the grains.

The term "monodispersed emulsion" as used herein means at least 9 particles in number or weight when the average particle diameter is measured by a conventional method, for example.
5% of the grains are silver halide grains within 140%, preferably within 130% of the average grain size.

The grain size distribution of silver halide has a narrow distribution.
There may be one.

The crystal structure of silver halide may have different silver halide compositions inside and outside.

The emulsion as a preferred embodiment of the present invention is a core/shell type monodisperse emulsion having a clear two-layer structure consisting of a high iodine core portion and a low iodine shell layer.

The silver iodide content of the high iodide portion of the present invention is 20 to 40 mol%, particularly preferably 20 to 30 mol%.

Methods for producing such monodispersed emulsions are known, for example, J. Ph.
ot, Sic, pp. 12.242-251 (1963)
, JP-A-48-36890, JP-A-52-16364,
No. 55-142329, No. 58-49938, British Patent No. 1,413,748, U.S. Patent No. 3,574,628
No. 3,655.394.

As the above-mentioned monodisperse emulsion, an emulsion in which grains are grown by using seed crystals and supplying silver ions and halide ions using the seed crystals as growth nuclei is particularly preferred.

Incidentally, methods for obtaining the core/shell emulsion include, for example, British Patent No. 1,027.146 and US Patent No. 3,505.06.
No. 8, No. 4,444.877, JP-A-60-1433
This is detailed in publications such as No. 1.

The silver halide emulsion used in the present invention may be tabular grains having an aspect ratio of 5 or more.

The advantages of such tabular grains include improved spectral sensitization efficiency and improved image graininess and sharpness, as described in British Patent No. 2. No. 12.157, U.S. Pat. No. 4,439
, No. 520, No. 4,433.048, No. 4,414.
It can be prepared by the method described in publications such as No. 310 and No. 4,434.226.

The above-mentioned emulsion may be either a surface latent image type emulsion that forms a latent image on the grain surface or an internal latent image type that forms a latent image inside the grain. Good too. These emulsions may use cadmium salts, lead salts, zinc salts, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex salts thereof, iron salts or complex salts thereof, etc. at the stage of physical ripening or grain preparation.

The emulsion was subjected to the Tardel water washing method to remove soluble salts, 7
A water washing method such as 0-Kyureshimin sedimentation method or ultrafiltration method may be used. Preferred water washing methods include, for example, the method using an aromatic hydrocarbon aldehyde resin containing a sulfo group as described in Japanese Patent Publication No. 35-16086, or the method described in Japanese Patent Publication No. 1982-1608.
Examples of agglomerated polymer agents described in No. 158644 G 3 and G
A particularly preferable desalting method is a method using a method such as No. 8.

Various photographic additives can be used in the emulsion according to the present invention in the steps before and after physical ripening or chemical ripening.

Examples of known additives include compounds described in Research Disclosure+ No. 17643 (December 1978) and No. 18716 (November 1979). Compound types and descriptions shown in these two research disclosures Additives Chemical sensitizers Sensitizers Dye development accelerators Antifoggants Stabilizers Color stain inhibitors Image stabilizers Ultraviolet absorbers Filters Dyes Brighteners Hardeners Coating agent coating aid Surfactant Plasticizer Slip agent Static inhibitor Matting agent Binder RD-17643 Page Classification 23 I[1 23mV 29 II+ 24 Vl)/ // 25 ■ 25 ■ 25 ~26 ■ 〃 〃 24 V 26 Right-650 Left 651 Left 650 Right 650 Right 650 Right 651 Left Supports that can be used for the photosensitive material according to the present invention include, for example, the above-mentioned RD-17643, page 28 and RD
-18716, page 647, left column, 17" 25).

Suitable supports include plastifilm and 7-layer film, and the surface of these supports may be coated with an undercoat layer or subjected to corona discharge, ultraviolet irradiation, etc. to improve the contact of the coating layer. l/). Then, the emulsion according to the present invention can be coated on one or both sides of the support thus treated.

The present invention is applicable to all silver halide photographic materials, but is particularly suitable for high-sensitivity black-and-white photographic materials.

When applying the present invention to medical X-ray radiography,
For example, a fluorescent intensifying screen whose main component is a phosphor that generates near-ultraviolet light or visible light when exposed to penetrating radiation is used. It is desirable to expose this material in close contact with both surfaces of a light-sensitive material prepared by coating both surfaces with the emulsion of the present invention.

The penetrating radiation herein refers to high-energy electromagnetic waves, and means X-rays and gamma rays.

Further, the fluorescent intensifying screen refers to, for example, an intensifying screen whose fluorescent component is mainly calcium tungstate, or a fluorescent intensifying screen whose main component is a rare earth compound activated with terbium.

〔Example〕

Next, the present invention will be specifically explained with reference to Examples.

Note that the present invention is not limited to these examples.

Example 1 (Preparation of seed crystals) The following solutions were prepared.

A liquid water
23Q Potassium Bromide 4.1
ggelatin 0.2kgB liquid water
5.2a Potassium bromide 130g
Potassium iodide 3.6g gelatin
110g0.2N sulfuric acid 7
7 m QC liquid water
6Q potassium bromide 1.90
kg potassium iodide 54g gelatin 150g D liquid water
5.4Q silver nitrate 190gE
liquid water
6.412 Silver nitrate 2.8
Solution A was placed in a 2 kg reaction vessel and kept at 60°C, and the other solutions were added at 59°C. At this time, liquid D and liquid D were added over 30 minutes using a controlled double jet method.
Thereafter, liquid C and liquid E were added over 105 minutes using a controlled double jet method. Stirring is 800rp+
I went with a. The flow rate increases in proportion to the total surface area of the silver halide grains as the grains grow, so that new growth nuclei are not generated when the additive solution flows in, and so-called Ostwald ripening occurs, resulting in a change in grain size distribution. It was added at a flow rate that did not spread. When adding silver ion solution and halide ion solution, pAg was 8.3 using potassium bromide solution.
The pH was adjusted to 2.0±0.1 using sulfuric acid. The resulting emulsion had a silver iodide content of 2 mol % and a grain size of 0.
30μm, σ/γ-0,11, and (111) plane is 5
%, and the others were cubic-shaped tetradecahedral monodisperse particles with slightly rounded corners, consisting of (100) planes.

After growing the seed crystals, adjust the pH to 6.0 using sodium carbonate solution.
After adjusting the temperature to 0 ± 0.3, the temperature was lowered to 40°C, and desalination was performed by coagulation using a naphthalene sulfonic acid formalin STM aqueous solution and a magnesium sulfate solution, and gelatin was further added. pAg -8,50, pH
= 5.85 seed crystal emulsion (A) was obtained in an amount of 16.9 kg.

The obtained seed crystals were cooled and stored in a cool dark place.

Next, particles were grown using the seed crystal (A) in the following manner.

First, the following solutions were prepared. All amounts are per mole of silver halide.

J solution (reaction mother liquor) Gelatin 10g Concentrated ammonia water 28mQ Glacial acetic acid 3m12 Water To finish to 600mQ, liquid potassium bromide 5g Potassium iodide 3g Gelatin 0.8g Water 110+off4: To finish L liquid potassium bromide 90g Gelatin 2.0g Water to 240mQ Finishing M liquid (
0.75N) AgNOs 9.9gNH4OH7
-OraQ Water 110mffJ: Finishing N
Liquid AgN0. 130gNH4
OH100+o(2 Water 0 liquid potassium bromide to finish to 240mQ 94g Water P liquid to finish to 165m12 AgNOs 9, 9gNHaOH7,
011 (1 water) Solution J to be finished to 110W+Q was kept warm at 40°C and stirred at 800 rpm+o with a stirrer.The pH of Solution J was adjusted to 9.90 using acetic acid, and seed crystals (A) were added to this solution for 6 hours. .2 g/1 mole of Ag At this time, I) Ag was kept constant at 7.30. Furthermore, after adjusting the po-8,83 and pAg-9,0 using a potassium bromide solution and acetic acid over 10 minutes, the N solution and L solution were simultaneously added over 30 minutes.

At this time, the inflow velocity ratio at the start of addition and at the end of addition is 1:l
O, and the flow rate increased with time. Furthermore, the pH was lowered from 8.83 to 8.00 in proportion to the amount of inflow. Further, when the L solution and the N solution were added in a total amount of 273, the O solution was additionally injected and added at a constant rate over 8 minutes. At this time, pAg rose from 9.0 to 11.0 and t
two.

Next, 300 mg of 1 mol of AgX was added to the spectral sensitizing dye ① described later, and the mixture was stirred for 30 seconds. Add acetic acid to adjust the pH to 6.0.
Adjusted to. Next, excess salt was removed from this suspension by a desalting method as shown below to obtain an emulsion. 40% suspension
Naphthalene sulfonic acid formaldehyde resin (5 g/AgX 1 moQ), Mg5O while kept at °C.

(8g/AgX 1mo(1) was added, stirred for 5 minutes, and left to stand still.

Next, drain the supernatant and add AgX l mo12;
The liquid volume was set to 00cc. After that, 40℃ pure water - (1,
81/AgX 1mof2) Add and stir for 59 minutes. Next, Mg5Oa (20g/AgX1 mo(
1) was added, stirred in the same manner as above, allowed to stand, and the supernatant liquid was removed to perform desalting. Next, post-gelatin was added to re-disperse the AgX aggregates, and the mixture was stirred at 55°C for 20 minutes to obtain emulsion Em-1.6 The resulting emulsion had an average grain size of 0.
．． The grains were monodisperse grains with a diameter of 60 μm and a silver iodide content of approximately 2 mol %.

Next, the obtained particles were chemically sensitized. That is, 50m
g/AgX l moQ of ammonium thiocyanate and 6 mgl AgX 1 moff of ammonium thiocyanate and 3
Add 5 mg/AgX l gaon of hypo, 55
Gold-sulfur sensitization was performed at °C.

Then 1.5 g/AgX l moQ of 4-hydroxy-6-methyl-1,3,3a,7-titrazaindene was added, then 150 mg/AgX l moQ
(1) Spectral sensitizing dyes ■ and ■ listed below in KI
00 mg, 5 mg/AgX I IIIo (l) was added to perform spectral sensitization.

Sensitizing dye■ Sensitizing dye■ Next, the emulsion layer coating solution and the protective layer coating solution containing the obtained emulsion are applied to both sides of the subbed polyester film support from the support side to the emulsion layer and the protective layer coating solution. Two layers were simultaneously coated in this order and then dried to produce a silver halogenide photographic film.

To the emulsion layer, the following additives were added to AgX l mo (2), and an exemplary nucleating agent according to the present invention was added as shown in Table 1.

T-butylcatechol 400mg
PolyvinylpyrrolidonrojW: 10,000)
1.0g trimethylolpropane 1
0g diethylene glycol 5g nitrophenylphosphonium chloride 50mg1.3
-Dihydroxybenzene-4-ammonium sulfonate 4g Sodium 2-mercaptobenzimidazole-5 sulfonate
15+mg 1-phenyl-5-mercaptotetrazole 1mg 1.1-dimethylol-1 bromine Nitromethane 0mg Styrene maleic anhydride copolymer 7.5g In addition, the following compounds were added to the protective layer per 1g of gelatin.

C,F, ,0iCH,CH20hCH,CH20H2
+ag C3F17SO3 ll1g 0□CH, CI, OhiH Polymethyl methacrylate with average particle size 5μm 7rng
Colloidal silica (average particle size 0.01μ+n)
70mg (CH2=C)I-3O2CH2+0
As a 70 mg subtraction liquid, glycidyl methacrylate 50vt%, methyl methacrylate 1Qvt
%, butyl methacrylate 40wt%
An aqueous copolymer solution was used by diluting the copolymer consisting of the following to a concentration of 10% by volume.

The following tests were conducted on the obtained samples.

[Sensitometry]

Using the standard light B described in the "New Edition, Lighting Data Book" as a light source, the film was exposed to light with an exposure time of 0.1 seconds and 3.2 C■S without a filter so that the same amount of light was applied to both sides of the film.

Next, processing was performed for 90 seconds at a temperature of 35°C using developer XD-5R and fixer χF-3R (both manufactured by Konica Corp.) using the development method according to the present invention described above to determine the sensitivity of each sample. I asked for it. For sensitivity, calculate the reciprocal of the amount of light required for the blackening density to increase by 1.0, and set the sensitivity of the comparative sample to 100.
It is expressed as relative sensitivity.

In addition, γ indicates the slope of the straight line part of the characteristic curve, and DIIlax
is the highest concentration value.

[Sludge generation rate]

The obtained samples were each cut into 50 large-sized pieces and exposed to light so that the density was about 1.0.

The 50 exposed samples were subjected to continuous running processing using the same processing solution and processing machine as used for sensitometry, and the state of the sludge generated in the developer IQ was visually evaluated in the following five grades.

1: No total heat is generated 2: Very few occurrences 3: Slight occurrence (within practical tolerance) 4: Frequently occurs (outside practical tolerance) 5: Very frequent occurrence The results obtained are shown in Table 1 below.

As is clear from the table, it can be seen that the samples according to the present invention suppress the generation of sludge and have excellent photographic performance.

Example 2 Liquid A Potassium bromide Potassium iodide HO (CH2) is (CHz)zs (CHz)zOH Gelatin Water g 0.3g O, 1g 5g Q Liquid B Silver nitrate 8.3g Water 45m<1 Liquid Potassium bromide C 6.2g potassium iodide 0.4g water
Solution A was placed in a 45 m 12 reaction vessel and kept at 45°C, and solutions B and C were added in 60 seconds by the double jet method. After the addition, the temperature was raised to 53°C. Over the next 60 minutes, 150 g of silver nitrate was added at an accelerated flow rate. (The flow rate at the end of addition is 5
During the addition of silver nitrate, a mixed solution of potassium bromide and potassium iodide was added using a controlled double jet method to maintain pBr at 1.8.

When 110 g of silver nitrate was added, 1(0(CHx)zs(CFIx)zs(CHx)*O
5 g of H was added, and after the silver nitrate addition was completed, 0.5 g of potassium iodide was added.

After washing the obtained emulsion with water in the same manner as in Example 1, gelatin was added to adjust the pAg to 8.0 and the pH to 6.5, and the emulsion was redispersed.

Next, the spectral sensitizing dye (2) was added at 560 g/AgX 1
mol was added, and then chemical ripening was performed at 56° C. for 20 minutes according to the method of Example 1. The resulting emulsion has an average grain size of 0.
．． 9 μm, silver iodide content 2 mol%, aspect ratio 6
．． 0 and a: 0.8.

Using this tabular emulsion, the samples shown in Table 2 were prepared in exactly the same manner as in Example 1.

Table 2 shows the results of sensitometry and sludge generation tests.

From the results of Example 2, even when the emulsion was a tabular silver iodobromide emulsion, the sample according to the present invention showed little deterioration in photographic performance and suppressed the generation of sludge.

Table [Effects of the Invention] According to the present invention, it was possible to obtain an image forming method of a silver halide photographic material that prevents the generation of sludge in a processing solution and has high sensitivity and high density.

[Brief explanation of drawings]

FIG. 1 is a sectional view of a developing device applied to the method of forming an image on a photosensitive material according to the present invention. In the figure, numerals 1 to 3 are conveyance rollers, 4 is a silver halide photographic material, 5 is a conveyance path, and 6 to 8 are supply nostles.

Claims (1)

[Claims] In a method of forming an image by developing a silver halide photographic material containing at least one nucleating agent in the photosensitive layer and/or other hydrophilic colloid layer after imagewise exposure, the processing 1. A method for forming an image on a silver halide photographic material, characterized in that the method comprises supplying a developer containing hydroquinones by coating the exposed surface.