JPS6271947A - Production of silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To make handling possible in a light room cut off UV rays by incorporating a silver halide which contains more than a specific mol% a silver chloride and is a cubic crystal and has a monodisperse and is digested with a reducing agent to the silver halide emulsion layer. CONSTITUTION:The silver halide contg. in the silver halide emulsion layer contains preferably >=90mol% the silver halide, and is the cubic crystal and has the monodisperse and is digested with the reducing agent. Thus, the wordings in which the silver halide is the cubic crystal and has the monodisperse, means that the surface of the crystal is preferably >=80% a crystal surface (100) of a complete cubic crystal in which the all crystal surface is the surface (100) and a residual crystal surface is the crystal surface (111) contg. the crystal having 14 surfaces and that as the weight or the number of the silver halide, the prescribed particle of the diameter having <=+ or -4% a mean particle diameter is preferably 90%. The man particle size of the silver halide is preferably <=0.5mu, more preferably <=0.3mu.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for producing a silver halide photographic material,
In particular, it relates to a method for manufacturing silver halide photographic materials that can be handled in a bright room where ultraviolet rays are blocked.

[Prior Art 1 Silver halide photographic materials used in the printing plate-making process require sharp gradation, and usually have a silver chloride content of 70 t% or more. It consists of

In recent years, in this field, silver halide photographic light-sensitive materials (halogenated for bright rooms) that can be used in bright areas 11 silver photographic materials) have been developed.

This silver halide photographic light-sensitive material for bright rooms can be handled in a bright room where ultraviolet rays are blocked, has high sensitivity to the printer light source, and has characteristics such as high contrast and high maximum density. be done.

Many silver halide photographic materials for use in bright rooms are already known.

For example, JP-A-56-125734@ describes an ultra-low sensitivity silver halide emulsion containing 10 to 10-5 mol of rhodium salt per 1 ton of silver halide containing at least 90 mol% silver chloride. has been done. Japanese Patent Publication No. 59-142
No. 540 discloses a silver halide emulsion which is not subjected to chemical ripening and contains at least 80 mol % of silver chloride, and which contains an organic desensitizer in which the sum of the anodic potential and the cathodic potential of a polarogram is positive. Photographic emulsion is described. JP-A-59-193447 discloses that the silver chloride content is 50
A silver halide photographic light-sensitive material for bright room use, in which a rice grain aqueous colloid layer containing a dye that reduces the photosensitivity of the emulsion layer to visible light is provided on a silver halide emulsion layer consisting of silver halide grains of mol% or more. is listed. The above silver halide emulsion is a negative silver halide photographic light-sensitive material.
JP-A-59-142540 and JP-A-59-19
The silver halide photographic material described in Publication No. 34-47 is not chemically sensitized. However, these silver halide photographic materials do not fully satisfy the above characteristics.

Further, JP-A-58-176635 describes a direct positive silver halide photographic light-sensitive material having an ammoniacal silver halide emulsion layer doped with a soluble rhodium salt or a soluble iridium salt and fogged with a reducing agent. has been done. However, this photographic material is for direct positive use,
Not a negative type.

[Problems to be Solved by the Invention] An object of the present invention is to produce a silver halide photocopy of negatives that can be handled in a bright room where ultraviolet rays are blocked. The purpose of the present invention is to provide photosensitive materials.

[Means for Solving the Problems] An object of the present invention is to provide a method for producing a silver halide photographic material containing an organic desensitizer in a silver halide emulsion layer, is 70 mol%
It is made of the above silver chloride, has substantially cubic crystals and is monodisperse, and has been achieved by being ripened with a reducing agent.

The silver halide emulsion used in the present invention includes silver chloride, silver chlorobromide, in which 70 mol% or more of the silver halide is silver chloride,
It is preferably a warm silver iodide, and particularly preferably 90 mol% or more of silver chloride.

The silver halide grains used in the present invention preferably have substantially cubic crystals and are monodisperse. The fact that these silver halide grains are substantially cubic crystals and monodispersed means that from a perfectly cubic crystal in which the crystal surface is all [1001 planes], 70% or more of the crystal surfaces are [100] planes,
Preferably, the silver halide grains contain tetradecahedral crystals that account for 80% or more and the other face is [111], and ff1l of the silver halide grains.
i, or 80%, preferably 90% of the total grains in terms of number, are comprised of silver halide crystals whose diameter is within ±40% of the average grain size.

The average particle diameter of the silver halide grains is preferably 0.5 μm or less, particularly preferably 0.3 μm or less. For details on how to determine average particle size, see Mees, C.E.
and Jimus (T.

THE THEORY OF THE PHOTOGRAPHY PROCESS (H. James)
TIIE PIIOrOGRAPIIICPROCES
S), 3rd edition, pp. 36-43, 1966, Macmillan Co., Ltd. Flj.

The substantially cubic and monodisperse silver halide emulsion used in the present invention is prepared by simultaneously mixing a soluble silver salt and a soluble halide salt, and maintaining a constant pAQ in the liquid layer in which silver halide is formed. A so-called con-rolled double jet can be created by a person.

The silver halide emulsion of the present invention contains a water-soluble rhodium salt, such as rhodium chloride, to reduce the sensitivity in a bright room and increase the sensitivity to ultraviolet light.

It is preferable to use rhodium trichloride, rhodium ammonium chloride, or the like. Furthermore, complex salts of these can also be used. The above-mentioned rhodium salt is preferably added before the first ripening during emulsion production, and is particularly preferably added during grain formation. The amount of addition is preferably from 10 to 10@-8 mol per mol of silver.

The silver halide emulsion of the present invention is ripened with a reducing agent. Reducing agents used include aldehyde compounds (e.g. formalin), hydrazine, organic amine compounds such as thiourea dioxide (nide), terrochemical compounds such as stannous chloride,
Alternatively, amine borane and the like can be mentioned. Specific examples of these are U.S. Pat. Nos. 2,563,785 and 25,889.
8υL No. 2983609, No. 3227552,
No. 4030925, each specification is omitted and JP-A-47-967
No. 7 and No. 53-20318.

Specific examples of preferred reducing agents are shown below.

r-1, hydrazine 5A! i! Salt ■-2, Thiourea dioxide I-3, N-(pt-lyl)-N'-formylhydrazine-4,1-phenyl-3-(4-formylhydrazinophenyl ■-5.1 -(β-Formylethylthyl-benzothiazolium bromide) It is preferable that the amount is within this range.If the amount is more than this, fogging tends to occur, and if it is less than this, the stability in a bright room where ultraviolet rays are cut is decreased.

pl-1 when ripening silver halide with a reducing agent is 8,
0 to 9.5 is preferred, and 8.5 to 9.0 is particularly preferred. Outside this range, the stability in a bright room with a minimum of ultraviolet rays will be low, and the reproducibility will be low.

The silver halide photographic emulsion of the present invention does not undergo the gold 11 sensitization and sulfur sensitization that are carried out in ordinary silver halide photographic emulsions1. This is not preferable because it deteriorates stability and is particularly prone to fogging. Further, sulfur sensitization is not preferred because it increases the sensitivity to visible light.

The silver halide emulsion of the present invention contains an organic desensitizer or a 4'i desensitizing dye. The compounds used are British Patent No. 723019, US Patent No. 2541472'@each specification, JP-A-47-3285, and JP-B-Sho 40-2.
It is described in 6751@ gazette, etc.

Specific examples of preferred desensitizers are shown below.

■-1. Pinacryptol Yellow n-2.4-Methyl-3-(m-nitrophenyl)-thiazolidine-2-thione I [-3.1-p-nitrophenyl-5-mercaptotyrazole I [4.2-mercapto- 6-nito[1benzothiazole II-5.2-mercapto-6-nitrobenzimidazole II-6.5-nitropenzotriazole■-7. The amount of the phenosafranine II-8.5-(m-nitrobenzylidene)-rhodanine 11 desensitizer used is preferably in the range of 10-2 to 10-5 mol per 11 nyl silver halide.

It is added after ripening with a reducing agent.

As the silver halide binder or protective colloid used in the present invention, it is preferable to use gelatin, but other types of pyratine, such as gelatin conductor, can also be used.

As piratine, in addition to lime grains, acid-treated gelatin can be used.
t) Solution 1: Pyrabun enzymatically decomposed products can be used. Examples of zenf-fone derivatives include those described in US Pat. Zeradin, acid anhydride, isocyanate, active ha[]
Can you name a reaction product with a compound that causes cancer? Examples of the filtrate anhydride used in the reaction with gelatin include maleic anhydride, phthalic anhydride, anhydrous TFl11, acetic anhydride, and succinic anhydride.
Examples of the isocyanate compound include phenyl isocyanate, p-[l:I mophenylisocyanate, p-ri[][]nohenyl isocyanate, p-t-
Examples include lylisocyanate, p-nitrophenyl isocyanate, naphthylisocyanate, and the like.

Examples of compounds having active halogens include benzenesulfonyl chloride, p-methoxybenzenesulfonyl chloride, p-bromobenzenesulfonyl chloride, o-toluenesulfonyl chloride, m-nitrobenzenesulfonyl chloride, naphthalene-β-sulfonyl chloride, -Carboxybenzenesulfonyl chloride Zenesulfonyl chloride, ethyl OO carbonate, 2,4-dichloro-6-hydroxys triazine.
Examples include sodium salts.

In the silver halide photographic emulsion of the present invention, soluble salts are usually removed after precipitation or physical ripening.Means for this purpose include the Nodel water washing method, which is performed by gelatin, and inorganic salts consisting of polyvalent anions ( (e.g., sodium sulfate), anionic W surfactants, anionic polymers (e.g., polystyrene sulfonic acid), gelatin derivatives (fat II/ibχ acylated gelatin, aromatic acylated gelatin, aromatic carbamoylated gelatin, etc.) ) may also be used.

The silver halide photographic emulsion of the present invention contains an antifoggant (benzo-1-heriazole, 2-mercabutopenzimigsol, 1-phenyl-5-mercaptotetrazole, etc.), a filter dye, 1-carbon or an inorganic hardener ( It may contain alum alum, formaldehyde, glyogyzal, 2,4-dichloro-6-hydroxy-s-t-riazine sodium salt, etc.), a surfactant, a water-insoluble or sparingly soluble synthetic polymer latex, and the like.

Examples of the support used in the present invention include cellulose acetate film, polyethylene film, polypropylene film, polystyrene film, baryta paper, paper coated with a resin such as polyethylene, and synthetic paper.

For the photographic processing of the silver halide photographic material of the present invention, known methods can be used, and known processing solutions can be used. Processing temperature is usually 18-45℃
is within the range of As the developing agent, dihydroxybenzenes (e.g., hydroquinone), 3-pyrazolidones (e.g., 1-phenyl-3-pyrazolidone), aminophenols (e.g., N-methyl-3-aminephenol), etc. can be used. can.

In addition to the above, the developing solution contains known preservatives, alkaline agents, p
Contains laxatives, anti-foaming agents, etc., as well as solubilizing agents, color toning agents, development accelerators, surfactants, antifoaming agents, water softeners,
It may also contain a hardening agent, a viscous fl'j agent, and the like.

As the fixer, one having a known composition can be used. As the fixing agent, in addition to thiosulfur M salt and thiocyanate, organic sulfur compounds known to be effective as fixing agents can be used. The fixer may contain a water-soluble aluminum compound as a hardening agent.

[Effects of the Invention] The silver halide photographic material produced according to the present invention has the following effects:
Since it has low sensitivity to visible light, it can be handled in a bright room where ultraviolet rays are blocked.

[Example] Hereinafter, the present invention will be explained based on Examples.

Example 1 Silver nitrate aqueous solution (1
7% aqueous solution) and 1-lium chloride aqueous solution (1.2% molar aqueous solution) were added over 20 minutes by simultaneous mixing under stirring, and 2L of medium-dispersed cubic silver chloride with an average particle size of 0.25μ was added.
A drug was prepared.

To this emulsion, phthalic anhydride was added to phthalate the gelatin, and citric acid was added to bring the pt+ to the isoelectric point of the gelatin for coagulation and sedimentation to remove soluble salts. Thereafter, 60 g of inert gelatin per 1'E of silver halide was added, the p day was adjusted to 6.0 with potassium carbonate, and the
Preliminary dispersion was carried out at 0°C for 30 minutes. This was divided into two equal parts, and one part was further aged at 40'C for 40 to 90 minutes. Into this emulsion, pinacrib 1--L-10- was added to halogenated 1n1+
Nils-I L 200■ (5,4X10-4 mol)
In addition, 6-methyl-4-hydroxy-1,3,3a,7 was added as a stabilizer after being adsorbed with 40'Cl2O minutes.
-Tetraon einden, saponin as a surfactant, formalin as a hardening agent, and IH on the film base.
Comparative samples 1 to 6 were prepared by coating and drying so that la was 4.0 g per square meter. On the other hand, instead of aging at 40°C for 40 to 90 minutes as in the comparative sample, 1 ml of silver chloride was added to 25 d of a 10% sodium chloride aqueous solution.
Add 3.4 mL of a 0.2% copper chloride aqueous solution and 17 d of a 5% potassium carbonate aqueous solution, adjust the DH to 8.8, and add hydrazine.
Samples 7 to 12 of the present invention were prepared in the same manner as the comparative sample except that 3.4 m (2.6 x 10 mol) of a 1% sulfate aqueous solution was added and aged at 40°C for 40 to 90 minutes.

This sample was transferred to a wedge with a concentration difference of 0.1 (manufactured by DuPont, A
-64013) and 1 Mingshi printer (Human [Water Screen Manufacturing 1 grade, F3-617-FM-GM)
It was exposed to light, developed for 30 seconds at 38 DEG C. using the following developer, fixed, washed with water, and dried. Furthermore, the comparison sample and the sample of the present invention were tested using a 40W white fluorescent lamp that cut off ultraviolet rays.
The film was exposed to light at 200 lux for 60 minutes at a distance of 1.5 m directly below the film, and was developed in the same manner and the fog density was measured. The above results are shown below.
1 (in Example 2.3, the fog in the i+J visual light was similarly measured).

Developer Potassium bromide 2.03 Potassium hydroxide 20g Potassium carbonate
35gti potassium sulfate
8 (1? Hydroquinone 2
0g triethylene glycol 30g/7s ethylene glycol 2.0U4-nitroingsol 0.1! J Shout 1 water - (Let it be IN (oH=11.7).

The results are shown in Table-1. Note that the sensitivity was expressed as a relative sensitivity, with the sensitivity of the comparative sample at an aging time of 40 minutes being taken as 100 (Example 2.3 was also expressed in the same way).

Also, the contrast is I':lin +Q, 5 and D
The slope of the 1S characteristic curve between two points located at I1 degrees of min+1.5 is shown.

Table 1 From the results in Table 1, the samples of the present invention have a lower
It can be seen that the sensitivity is significantly reduced.

In addition, since the comparative sample is sensitive to visible light, a significant amount of force is generated by fluorescent lamps that cut off ultraviolet rays. on the other hand,
Since the samples of the present invention have low photosensitivity to visible light, they hardly cause fogging caused by fluorescent lamps that block ultraviolet rays, and can be handled in a bright room that blocks ultraviolet rays.

Example 2 Comparative samples 13 to 18 and samples 19 to 19 of the present invention were prepared in the same manner as in Example 1, except that the aging time was 60 minutes and the desensitizer was changed.
No. 24 was prepared, exposed and developed, and the results shown in Table 2 were obtained.

From the results in Table 2, it can be seen that the samples of the present invention were effectively desensitized and almost no capri was produced by the fluorescent lamps that cut off ultraviolet rays.

Example 3 61111! in an aqueous gelatin solution kept at 40°C. A root solution (1 mol% aqueous solution) and an aqueous solution containing Odium chloride = 5 (4 x 10 mol) and sodium chloride (1.15 mol% aqueous solution as an aqueous solution) were added under stirring for 20 minutes.
A monodispersed cubic silver chloride emulsion with an average grain size of 0.25 μm was prepared by simultaneous mixing for 1 minute. Phthalic anhydride was added to this emulsion to convert the gelatin into heptalates, citric acid was added to lower the DH to the isoelectric point of the gelatin, coagulation and precipitation were performed, and soluble salts were removed. Thereafter, 60 SF of inert gelatin per mole of silver halide was added, and the mixture was aged at 40° C. for 30 minutes. Next, 6-methyl-4-hydroxy-1,3,3a as a desensitizer and stabilizer.

7-te] lazaindene, 1-7enyl-5-mercaptotetrazole, saponin as a surfactant, and formalin as a hardening agent, coated on a polyester film base at an lff1 of 4.03 per square meter, and dried. Comparative samples 25 to 30 were prepared.

Instead of aging at 40°C for 30 minutes as in the comparative sample, 3.4 d of a 11% aqueous solution of hydrazine and sulfuric acid, sodium chloride, copper chloride, and potassium carbonate were added to 1 mole of silver chloride, and aged for 30 minutes, in the same manner as in Example 1. Samples 31 to 36 of the present invention were prepared. Exposure and development were carried out in the same manner as in Example 1 (Table 3).
I got the result.

From the results in Table 3, it can be seen that while the comparison sample caused fogging when exposed to a fluorescent lamp that emitted ultraviolet rays, the sample of the present invention hardly caused fogging when exposed to a fluorescent lamp that emitted ultraviolet rays.

Claims (2)

[Claims] (1) In a method for producing a silver halide photographic material containing an organic desensitizer in a silver halide emulsion layer, the silver halide in the silver halide emulsion layer consists of 70 mol% or more of silver chloride, and substantially 1. A method for producing a negative-working silver halide photographic material, which is characterized in that it has cubic crystals, is monodisperse, and is aged with a reducing agent. (2) Silver halide is 10^-^5 to 1 mole of silver
The method for producing a negative-working silver halide photographic material according to claim 1, characterized in that it contains 10^-^8 mol of a water-soluble rhodium salt.