JPH0341441A - Silver halide photographic sensitive material improved in spot fault - Google Patents

Abstract

PURPOSE:To prevent the generation of the spots based on heavy metals or the dust form the atm. air without adversely affecting the photographic characteristics of the photosensitive material and to prevent the fading of latent images as well by incorporating a porphyrin compd. into the photosensitive material. CONSTITUTION:The porphyrin compd. (e.g.; the compd. expressed by formula) is incorporated into >=1 layers of the hydrophilic colloidal layers of this photosen sitive material. In the formula, R denotes H or lower alkyl; Y denotes H, aryl, etc.; X denotes H or lower halogen. The compd. with which R and X in the formula are both H and Y is -C6H5, etc., are usable. This compd. may be added to emulsion layers or the layers adjacent to the emulsion layers.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to silver halide photographic materials, and more specifically, metals generated in silver halide photographic materials due to heavy metals, atmospheric dust, and other causes. The present invention relates to a silver halide photographic material that prevents so-called spots (white or black spots that are identified after development) and prevents latent image regression.

[Background of the invention]

It has been known that certain types of atmospheric dust or heavy metal dust can cause scratches on photographic materials. It is believed that spots occur when it is mixed into photographic materials during the process.

The contamination or adhesion of metals and metal oxides into photosensitive materials during the manufacturing process can occur from worn parts of manufacturing equipment made of various metals, or brought in when raw materials are brought in.
This can be caused by various causes, and preventing spots is actually an extremely difficult problem.

These fine particles mainly exist in the form of metals such as iron, copper, zinc, aluminum, chromium, and nickel, as well as their oxides and salts, and these fine particles act as cores to generate circular spots on images after development. let

This is because the adhered fine particles cause the surrounding photosensitive layer to be oxidized or reduced, resulting in partial desensitization or sensitization. The size of the spot is 1
It may range from less than mm to about 10 mm. It is required to prevent the effects of extremely harmful substances on such photographic materials, and many proposals have been made in the past.

For example, Special Publication No. 10243/1973 and British Patent No. 6234.
No. 48, etc., and the latter mentions aldoxime. Other references include acyloin, alkali metal pyrophosphini), metaphos 7A1, tripolyphosphate and hexametaphosphate, alkali metal oxalates, tartrates, silicates, carbonates and bicarbonates, tungstic acid. The use of salts such as molybdates, chromates and derivatives of ethylenediaminetetraacetic acid is recommended.

However, the inventors of the present invention have continued to conduct various studies for many years, including the above-mentioned spot preventive agents. As a result, the effects of conventional spot preventive agents are limited to certain types of photographic emulsions, or their preventive effects are small. In addition, it has various drawbacks such as regression of latent images, fog formation, deterioration of mechanical properties of photographic light-sensitive materials, and undesirable effects of other photographic additives or processing solutions that coexist. It wasn't a kimono.

On the other hand, silver halide photographic materials have a phenomenon in which latent images degrade after photographing.

The generation of a latent image by photographic exposure is chemically an extremely minute change in silver halide crystals, and the latent image itself is inherently unstable. Therefore, the latent image has a tendency to attenuate with the passage of time from photographic exposure to development processing, and this attenuation of the latent image is called latent image regression. The progress of latent image regression generally depends on the storage conditions of the exposed photosensitive material; for example, it is observed that the regression is significant when stored at high temperatures, and less when stored at low temperatures.

Is there any problem with latent image regression as long as it is developed immediately after photographing? Considering the actual usage conditions and usage patterns, in the case of negative material for photographing and reversal material, it is necessary to store it in a greenhouse for several months from exposure to development. There are times when objects are left unattended, and even positive materials for photography may be left unattended for several days.

For the above reasons, it is desirable to take special measures during the production of silver halide photographic photosensitive plates to obtain photosensitive materials in which latent image regression is prevented, and various methods have been tried so far. However, the results of our studies indicate that these known methods, i.e. hydroxy-substituted aromatic compounds as described in German Patent No. 1,107,508, US Pat. No. 3,447,9
1,3-diones described in No. 26, U.S. Pat. No. 3,318
, 702, or the method of U.S. Pat. No. 3,424,583, German Patent No. 1,
All of the methods described in No. 173,339 were unsatisfactory for this purpose.

[Purpose of the invention]

Accordingly, a first object of the present invention is to provide a silver halide photographic material which prevents the occurrence of spots due to heavy metals or atmospheric dust without any adverse effect on photographic properties. .

A second object of the present invention is to provide a silver halogen photographic material in which latent image regression is prevented.

Other objectives will become apparent from the description below.

[Structure of the invention]

As a result of intensive studies on the above-mentioned object, the present inventor has found that the object of the present invention can be easily achieved by the configuration shown below, and has brought the present invention to fruition.

That is, they are closely related to silver halide photographic materials containing at least one type of porphyrin compound in at least one hydrophilic colloid layer on a support.

The present invention will be explained in detail below.

The porphyrin compound used in the hydrophilic colloid layer of the silver halide photographic light-sensitive material according to the present invention is a porphyrin derivative that exists widely in animals and plants, particularly hemoglobin,
Since it constitutes cytochrome or chlorophyll, it has been studied for a long time, and various compounds including isomers are known.

In the present invention, any of these porphyrin compounds can achieve the desired effect of the present invention without being particularly limited, but the following compounds are particularly preferably used:
[■] [However, R in the formula represents a hydrogen atom or a lower alkyl group, and Y may be the same or different, a hydrogen atom, a lower alkyl group, an aryl group, or a hetero represents a ring, and X represents a hydrogen atom or a halogen atom. ] R in the above general formula [■]
and the lower alkyl group represented by Y has a carbon number of 1
Examples of 4 to 4 include a methyl group, an ethyl group, a propyl group, a butyl group, and examples of the aryl group represented by Y include a phenyl group and a naphthyl group, and these aryl groups have a substituent. For example, 4-rupoxyphenyl group, 2.4.6-1-lymethylphenyl group,
Examples include 4-sulfophenyl group, 4-aminophenyl group, 4-dimethylaminophenyl group, 4-trimethylammonium salt 2,6-dichlorophenyl group, and pentafluorophenyl group.

The heterocycle represented by Y is preferably a 5- or 6-membered heterocycle containing at least one heteroatom of N, O, and S.
This heterocyclic group may be a group fused with a benzene ring, and may have an alkyl group having up to 4 carbon atoms, or a hydrophilic substituent such as a carboxyl group or a sulfo group. Good too.

Examples of these heterocycles include 3-pyridine, 4-pyridine, 1-alkyl-4-pyridinium salt, 2-thienyl group, and 5-sulfo-2-thienyl group.

Specific examples of compounds represented by the general formula CI) of the present invention are shown below, but the present invention is limited thereto.
c1. “Porphying and Metallo
porphyins, Elsevier, Sci.
It is described in detail, including the synthesis method, in Pub, Co, Amsterdam (1975), and is also a compound that is easily available as a commercial product.

The above-mentioned porphyrin compound according to the present invention is preferably dissolved in a hydrophilic organic solvent such as methanol or ethanol and added to the constituent layers of the silver halide photographic light-sensitive material.

The layers to be added include a hydrophilic colloid layer, i.e., a silver halide emulsion layer, a protective layer, an undercoat layer, an intermediate layer, a halayone prevention layer,
It may be any constituent layer of the silver halide photographic light-sensitive material, such as a filter layer, dye layer, or backing layer, but preferably an emulsion layer and/or a layer adjacent to the emulsion layer to achieve the effects of the present invention. You can play higher.

The amount added to these colloid layers varies depending on the type of photosensitive material, layer structure, type of compound, etc., but it is 0.01 to 100 mg to the silver halide photographic photosensitive material.
/d m2, more preferably 0.1-
10mg/dm2 may be used.

In the case of a silver halide emulsion layer, more preferably L
X 10-' to 1×1O-2 mol.

It may be added at any time during the photosensitive material manufacturing process, but preferably after the chemical ripening and before the coating process. In the case of a non-emulsion layer, it may be applied at any time before coating.

The above-mentioned compound of general formula CI) according to the present invention has the drawback that the oxidizing agent action due to metal traps found in conventional spot preventive agents, such as metal chelating agents, on the other hand, promotes latent image regression. However, it has an excellent feature that has not been seen before, in that it not only has a spot prevention effect but also prevents latent image regression.

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
It may be entirely isotropically grown like a tetrahedron, a polyhedral crystal like a sphere, a twin crystal with planar defects, or a mixed or composite type thereof. . The grain size of these silver halide grains is 0.1
The particles may be fine particles of .mu.m or less to large particles of 20 .mu.m.

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. 17643 (1978
(December 2013)・Pages 22-23 1・Emulsion manufacturing method (Emul
sionPreparation and type
s) and the same (RD) No. 18716 (1979 no. 1
It can be prepared by the method described in January), 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 thepbotograpbic process
"4th edition, published by Macmillan (1977) 38
- Method described on page 104, G, F, Dauf fin
Author: “Photographic Emulsion Chemistry” “Photographic Emulsion Chemistry”
mulsionChel'1listry, Fo
Cal Press (1966), P. Glaf
“Physics and Chemistry of Photography” by kids, Cbimie et
physique photograhique”P
Published by aul Monte1 (1967 noon), V, L,
“Manufacturing and Coating of Photographic Emulsions” by Zelikman et al.
making and coating photogr
aphicemulsion” Focal pres
It is prepared by the method described in, for example, published by Ssha (1964).

That is, solution conditions such as neutral method, acidic method, ammonia method, etc.
It can be produced using mixing conditions such as forward mixing method, back mixing method, double jet method, Chondral double jet method, etc., particle preparation conditions such as conversion method, core/shell 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.

A monodisperse emulsion as used herein means that when the average particle diameter is measured by a conventional method, at least 95% of the particles in terms of number or weight are within ±40% of the average particle diameter, preferably within ±30%. It is a certain silver halide grain. The grain size distribution of silver halide may be either a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution.

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 two-layer 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. Note that methods for obtaining core/shell emulsions include, for example, British Patent No. 1,027.146 and US Patent No. 3,505,068.
No. 4,444,877, JP-A-60-14331
This is detailed in publications such as No.

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. 2,112,157 and US Pat. No. 4,439, for example.
．． 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 a surface latent image type that forms a latent image on the grain surface, an internal latent image type that forms a latent image inside the grain, or a type that forms a latent image on the surface and inside. good. In these emulsions, 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. may be used in the stage of physical ripening or grain preparation. The emulsion may be subjected to water washing methods such as Tardel water washing method, flocculation sedimentation method, or ultrafiltration method to remove soluble salts. Preferred water washing methods include, for example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group as described in Japanese Patent Publication No. 3516086, or using agglomerating polymer agents such as G 3 and G 8 described in Japanese Patent Publication No. 63-158644. The method used is mentioned as a particularly preferred desalting method.

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 Research Disclosure No. 18716 (November 1979). The following table lists the types of compounds and their descriptions in these two research disclosures.

Additives Chemical sensitizers Sensitizing dye development accelerators Antifoggants Stabilizers Color stain inhibitors Image stabilizers Ultraviolet absorbers Filters Dye brighteners Hardeners Coating aids Surfactants Plasticizers Slip agents Static inhibitors Matting agents Binder RD-17643 page Classification 23 llI 23 IV 29 XX 24 VT 25 ■ 25 ■ 25-26 ■ 24 V 26 X 26-27 XI 26-27 XI 27 X11 27 X1l1 28 48-upper right 648 Right - 649 Left 648 - Upper right 649 - Lower right 650 Left - Right 649 Right - 650 Left 651 Right 650 Right 650 Right l/650 Right 651 Right Supports that can be used in the photosensitive material according to the present invention include, for example, those mentioned above. Page 28 of RD-17643 and RD
-18716, page 647, left column.

Suitable supports include plastic films, and the surfaces of these supports may generally be provided with a subbing layer or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer. The emulsion according to the present invention can then 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 or color 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 preferable 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 referred to here refers to high energy 9 Electromagnetic waves, meaning 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〕

The present invention will be explained in more detail by giving specific examples below.
The present invention is not limited to these.

Example-1 Preparation of emulsion Preparation of seed particles First, the following solutions A to E were prepared.

0 H2SO* (dilute sulfuric acid) 77.0mQ Dr H205-40 L A g N 03
190gE "H206,4+2' A g N O32,82Kg Add solution A to the reaction pot and keep it at 60°C, and keep the other liquids at 59°C.
Added at C. At this time, liquids B and D were added over 30 minutes using the controlled double jet method, and liquids E and E were added over 30 minutes.
The liquid was added using a controlled double jet method over 105 minutes. Stirring was performed at 800 rpm.

The flow rate increases in proportion to the total surface area of the silver halide grains as the grains grow, and when the additive solution flows in, no new growth nuclei are generated, so-called Ostwald ripening does not occur, and the grain size distribution is maintained. Added at a flow rate that did not spread.

When adding silver ion liquid and halide ion liquid,
p/1g was adjusted to 8.3±0.05 using potassium bromide solution, and pH was adjusted to pH=2.0±01 using sulfuric acid.

The resulting emulsion contained 12 mol% Ag and a grain size of 0.3 μm.
/ r = 0. 1L and C111) planes account for 5%, and the rest are (100) planes. It was a monodisperse emulsion of cubic tetradecahedrons with slightly chipped corners.

After growing the seed crystal particles, adjust the pH to 6,000 with sodium carbonate solution.
After adjusting the temperature to ±0.3, the temperature was lowered to 40°C, and desalination was performed by coagulation precipitation using an aqueous naphthalene sulfonic acid formalin resin solution and a magnesium sulfate solution, gelatin and phenol were added, and the pAg was adjusted to 8. 50
．． 16.9 kg of a seed crystal grain emulsion having a pH of 5.85 was obtained.

Preparation of monodispersed particles Using the obtained seed crystal particles of 0.3 μm, the final particle size was 0.3 μm.
An example of a coating layer (layer) with a thickness of 87 μm is shown.

Solution J was added, kept at 45°C, and stirred at 800 rpm with a stirrer. Acetic acid was added to the J solution to adjust the pH to -9.90, and 1.039 kg of seed crystal particles were collected and dispersed and suspended in the J solution. Then, after adding the M solution at a constant speed over 5 minutes, the K solution and the N solution were simultaneously added over 45 minutes.

I)Ag at this time was 8.08.

Then pH was adjusted using KBr solution and acetic acid over 20 min.
After adjusting pAg to 8.83 and pAg to 8.89, 0 liquid and L
The liquids were added simultaneously over 30 minutes. At this time, the inflow velocity ratio at the start of addition and at the end of addition was 1:10, and the flow velocity was increased with time. In addition, the pH is proportional to the inflow amount.
decreased from 8.83 to 8.00. Further, when the O liquid and the L liquid were added in a total amount of 273, the P liquid was added in a rush. At this time, 1) Ag increased from 8.894 to pAgll,l. Furthermore, add acetic acid and
After setting H to 6.0, desalting was performed in the same manner as the seed crystal particles, gelatin was added, pH = 5.90, pAg =
An emulsion of 8.72 was obtained. Particle size dispersion, 6/r
= 0.16, and (111) plane is 20%, (10
0) A monodispersed silver iodobromide emulsion containing 3 mol % of Agl and having 80% facets was obtained.

To the obtained emulsion, sodium thiocyanate, chloroauric acid, and hypo were added, and chemical ripening was performed under conditions that yielded the highest sensitivity, resulting in 4-hydroxy-6-methyl-1,3,3a.
, a gelatin solution of fuchitrazaindene (2×10 −2 mol/silver halide 1 mol) was added, the pH was adjusted to 6,00, and the mixture was cooled, set, and stored.

Preparation of test sample After dissolving the set emulsion, the above-mentioned porphyrin compound according to the present invention was added as shown in Table 1, and as an additive, t-butyl-catechol 4
00+ng, polyhinylpyrrolidone (molecular weight 10,00
0) 1.0g, styrene-maleic anhydride copolymer 2
．． 5gs polyethylene acrylate-1- (molecular weight 250
,000) 2.5 g, l-limethylolpropane 10 g, '; 5 g of ethylene glycol and l-lophenyl]・liphenylphosphonium chloride F 50
mg, 1.3-dihydroxybenzene-4-ammonium sulfonate 4 g12-mercaptobenzimidazole-5-sulfonic acid sorta 1.5 mg, 2-mercaptobenzthiazole 10 mg.

],■-dimethylol Blom ■ nitromethane etc. to make an emulsion, Ma　Iko　, with protective layer additives death The following compounds were added in an amount per 1 g of gelatin.

That is, 27 mg of CIF9SO3 Matting agent consisting of polymethyl methacrylate with an average particle size of 7 μm 7 mg Colloidal silica with an average particle size of 0.013 μm 70 mg Formaldehyde 9 mg Glyoxal 6 mg 2-Hydroxy-4.
A gelatin aqueous solution containing 4 mg of 6-dichlor 1,3,51-riazine sodium salt, etc. was used as a protective layer.
A coating speed of 150 m was applied to both sides of support A prepared according to Example 5436 (1) Support preparation.
/min and dried in 2 minutes and 30 seconds to obtain a sample. The amount of silver coated on both sides was 6.5 g/m2, the amount of gelatin coated in the protective layer was 2.6 g/m2 on both sides, and the amount of gelatin coated in the emulsion layer was 4.8 g/m2 on both sides.

8 Test method These samples were stored for 3 days after coating at a temperature and humidity of 25°C and 550% RH, and then wedge exposed at 3.2 CMS and left again for 12 hours at a temperature and humidity of 25°C and 150% RH. The latent image regression property was examined by developing.

The developing conditions were automatic processor SRX-501 (manufactured by Konica Corp.) and the processing solution was XD-SR and XF-SR (
The treatment was carried out for 45 seconds using both products (manufactured by Konica Co., Ltd.).

The spots in the table are indicated by the number of spots generated per 1 m2 of the sample after development.

Table 1 *: Sample No. 12 has the compound of the present invention added to the protective layer.

Comparison (A), di-1-lium ethylenediaminetetraacetate.

As is clear from Table 1, the samples of the present invention have excellent latent image regression, with extremely few occurrences of spots and only a slight decrease in sensitivity when left for 12 hours after exposure, which is a sign of latent image regression. This indicates that it has preventive properties.

Example-2 Adjustment of tabular grains 30 g gelatin 1 potassium bromide in 112 water], 0.5
g.

Thioether (HO(CI2)2S(CI□)2S(C
H2)2S(C12)20H] 0.5wt% aqueous solution ■O
m0. was added and dissolved in a solution kept at 63°C (pA
g-9.1, pH=6.5) with stirring, add 30 ml of a 0.88 molar silver nitrate solution to and 0.88 mol of a mixed solution of potassium iodide and potassium bromide (molar ratio 97:3) 3
After simultaneously adding 0 ma for 15 seconds, 60 mQ of a 1 molar silver nitrate solution and 60 mQ of a 1 molar mixed solution of potassium bromide and potassium iodide in a molar ratio of 96.5:3.5 were added.
A tabular silver iodobromide emulsion was prepared by simultaneously adding 0 mff and 0 mff over 70 minutes.

The obtained tabular silver halide grains had an average grain size of 115 μm.
m, thickness was 0.10 μm, and silver iodide content was 3.0 mol %. After desalting this emulsion by precipitation method, gold and
After chemical sensitization using sulfur sensitization, a mixture of (A) and (B) shown below at a weight ratio of 200:1 was used as an ortho spectral sensitizing dye.
mg/1 mole of silver halide was added, and a gelatin solution containing 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene was added in the same manner as in Example 1 to adjust the pH to 6.0. It was adjusted and stored in a cooling set.

Preparation of sensitizing dye test sample After dissolving the set emulsion, the above-mentioned porphyrin compound according to the present invention was added as shown in Table 2, and further added as an additive in exactly the same manner as in Example-1 to form a protective layer. Eight types of test samples were prepared.

2 The results obtained by exposure and development treatment in the same manner as in Example 1 are shown in Table 2 below.

As is clear from Table 2, even when tabular silver halide emulsions were used, all of the samples according to the present invention significantly prevented spots and latent image hypersensitivity compared to the comparison.

Example 3 A high-sensitivity silver iodobromide emulsion (containing 7 mol % silver iodide) with an average grain size of 1.2 μm was chemically ripened with gold and sulfur sensitizers to the highest sensitivity.

Next, anhydro-5゜5' was used as a green-sensitive sensitizing dye.
A suitable amount of -diphenyl-9-ethyl-3,3'-di-gamma-sulfofuroviroxacarbocyanine hydroxide sodium salt was added to prepare a green-sensitive silver halide emulsion.

Then, 1-(2,4,6-trichlorophenyl)3- as magenta coupler per mole of silver halide.
80 g of [3-(2,4-di-t-amylphenoxyacetamide)benzamide]-5-pyrazolone as a colored magenta coupler, l-(2,4,6-1
-lichlorophenyl)-4-(1-naphthylazo)-3
Weigh out 2.5 g of -(2-chloro-5-octadecenylsuccinimideanilino)5-pyrazolone, then weigh out 120 g of tricresylbos 7 ale and 2 ethyl acetate.
40g of the coupler solution was mixed and dissolved by heating, and then 400g of the coupler solution was emulsified and dispersed in a solution of 5g of sodium triisopropylnaphthalene sulfonate and 550ml of a 7.5% aqueous gelatin solution, and 34g of the green-sensitive emulsion and gelatin 4.
emulsion containing 0 g], added to 1 kg as a hardening agent.
．． 80 ml of a 2% aqueous solution of 3-dichloro-5-hydroxy-S-triazine sodium salt was added to prepare an emulsion coating solution.

40 g of emulsion on a subbed cellulose triacetate support.
/m2 (moisture content), using a slide hopper with one type of slide hopper at a coating speed of 100 m/min.
30) was created.

The obtained sample was subjected to wedge exposure in the same manner as in Example 1, and then subjected to the following color development treatment, and the occurrence of spots and the stability of the latent image were examined.

The results obtained are shown in Table 3 below.

The development process was as follows.

Treatment process [Processing temperature 38°C] Color development Bleaching Water Washing Fixing Water landing Washing Stabilization Drying Drying processing time 3 minutes 15 seconds 6 minutes 30 seconds 3 minutes 15 seconds 6 minutes 30 seconds 3 minutes 15 seconds 1 minute 30 seconds Each treatment The composition of the treatment liquid used in the process is as follows.

[Color developer]

4-Amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline sulfate 4.75g Anhydrous sodium sulfite 4.25g Hydroxyamine 1/2 sulfate 2.0g Anhydrous potassium carbonate 37.5g Bromide Sodium 1.3g Nitrilotriacetic acid trisodium salt (l hydrate) 2.5g Potassium hydroxide 1.0g Add water to make If, pH 10 using sodium hydroxide,
Adjust to 6.

[Bleach solution]

Ethylenediaminetetraacetic acid iron ammonium salt 100.0g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10.0g Add water to make 112, and adjust to pH 6.0 using aqueous ammonia.

[Fixer]

Ammonium thiosulfate 175.0g Anhydrous sodium sulfite 8.6g Sodium metasulfite 2.3g Add water to IQ
and adjust the pH to 6.0 using acetic acid.

[Stabilizing liquid]

Formalin (37% aqueous solution) 1.5m (
2 Konidax (manufactured by Konica Co., Ltd.) 7.5 mQ Table 3 [Effects of the invention] The present invention provides a silver halide photographic material that is resistant to heavy metals and dust from the atmosphere and has no spot failure. A silver halide photographic material with a stable latent image after photography and no latent image regression even after being left for a long time was obtained.

Claims (1)

[Claims] in at least one hydrophilic colloid layer on the support,
A silver halide photographic material containing at least one kind of porphyrin compound.