JPS6052416B2 - Negative silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a negative silver halide photographic material,
More specifically, the present invention relates to a negative-working silver oxide photographic material with improved storage stability and excellent photographic properties.

Metallic silver, which is an important raw material for silver halide photographic materials, is a natural product and its supply is decreasing year by year, but demand in industry is on the contrary increasing. A trend in manufacturing technology for silver halide photographic materials is the so-called ``silver saving'', which reduces the amount of silver used.
At present, attempts to '' are becoming a very important research topic. From this point of view, the present inventors previously disclosed in JP-A-54-48544 a light-sensitive material with a low silver content, high frequency range, high contrast, and high maximum density, and a processing method thereof. did. The above method is
A photosensitive material containing photosensitive silver halide grains, substantially non-photosensitive metal salt particles made difficult to solubilize with an insoluble agent, and physical development nuclei is prepared using a developer containing a substance that dissolves the metal salt particles. It is something to be processed. However, the photographic properties of the above-mentioned photosensitive materials deteriorate during raw storage, and
Sensitivity, gamma, etc. decrease, and fog increases. In particular, fog increases significantly under high temperature and low humidity conditions, and when photosensitive materials are stored under high temperature and high humidity conditions, so-called safelight fog is likely to occur even when exposed to safe light. The inventors further:
In the above processing method, a material in which a poorly soluble agent is added to a photosensitive material as a precursor, or a material in which a poorly soluble agent is added as a non-diffusive compound, etc. is disclosed in JP-A-55-1.
No. 8564 and No. 56-66846.

By improving these refractory agents, the decrease in sensitivity has been particularly improved. However, it was found that the increase in fog could not be improved with respect to raw storage under the above-mentioned high temperature and low humidity conditions. Following the above, the present inventors applied for a patent application filed in 1983.
-15078 (Refer to Japanese Patent Application Laid-open No. 13274/1983)
In , as the refractory agent, 1-phenyl-5-mercabutotetrazole derivatives are used, or in Japanese Patent Application No. 57-167654 and JP-A-134628, 1,3-dihydroxybenzene or We proposed the combined use of a 1,3-dihydroxynaphthalene derivative and a heterocyclic mercapto compound.

However, although the improved method described above improves raw storage under high temperature and low humidity conditions and can suppress the increase in fog, it is not effective against fogging caused by safe light when raw storage is performed under high temperature and high humidity conditions. It also became clear. Therefore, the first object of the present invention is to provide a negative type film containing photosensitive silver halide grains, substantially non-photosensitive metal salt particles made difficult to solubilize using an insoluble agent, and physical development nuclei as described above. The purpose is to prevent deterioration of photographic properties, especially fog, when photosensitive materials are stored raw under high temperature and low humidity conditions, and the second purpose is to improve safety when stored raw under high temperature and high humidity conditions. The objective is to improve fogging properties against light.

The present inventors conducted various studies to solve the above problems, and found that photosensitive silver halide grains on a support, the surfaces of which were made difficult to solubilize using a refractory agent, were themselves better than the above-mentioned photosensitive silver halide grains. A compound represented by the following general formula in any one of the constituent layers having a layer containing at least one of metal salt particles and physical development nuclei that are easily soluble and have no photosensitivity in practice. It has been found that the above object can be achieved by a negative-working silver halide photographic material containing.

In the formula, M represents an alkali metal, an alkaline earth metal, or an ammonium group, X represents a chlorine atom or bromine, and n is an integer of 1 to 2.

That is, according to the present invention, when a compound represented by the above general formula is contained in a negative photosensitive material having the composition as described above, the shelf life of the photosensitive material under high temperature, low humidity and high temperature and high humidity conditions is improved. was found to be significantly improved. It is already known among those skilled in the art that the compound represented by the above general formula according to the present invention reduces fog when a photosensitive material is stored under high temperature and low humidity; It is also well known that significant fogging occurs.

However, as the present invention has revealed. When the compound represented by the above general formula is applied to a negative photosensitive material having the above composition, it not only suppresses the occurrence of fogging during storage under high temperature and low humidity conditions, but also improves safety during storage under high temperature and high humidity conditions. It was discovered for the first time by the present invention that it has the effect of suppressing the occurrence of fogging due to light. Hereinafter, the present invention will be explained more specifically and in detail.

In the present invention, the compound represented by the general formula that is effectively used in the negative-working silver halide photographic light-sensitive material having the above composition (hereinafter abbreviated as the negative-working material of the present invention) can contain chloride ions or It is an inorganic compound that dissociates bromine ions. Therefore, typical specific examples of the compound represented by the above general formula will be listed below, but the present invention is not limited to these. (Compound example) (1) LiCe (2) Nace (3} Kce (4) NH
4c' (5) MgC'2 (6) CaCe2 (7) Z
nCf2 (8) BaC'2 (9) LiBr [phase] N
dBr(11)KBr(12)NH4Br(13)M,
Br2・6H20 (14) CaBr2・2H20 (15
)ZnBr2(16)BaBr2.2H20 The above-mentioned compounds according to the present invention are usually used in the constituent layers of the negative-tone photosensitive material according to the present invention, such as photosensitive silver halide grains,
Although it may be added to and contained in a constituent layer containing a mixture of metal salt particles and physical image nuclei, it is preferably added to and contained in a layer containing photosensitive silver oxide particles.

Water or a hydrophilic organic solvent is generally used as a solvent when adding the compound according to the present invention to the constituent layers of the above-mentioned photosensitive material. When the compound related to the present invention is a chloride, the amount added is 1×1 per mole of silver halide.
The preferred range is 0-3 mol to 5 x 10-1 mol, and when it is a bromide, the range is 1 x 10-5 mol to 1 x 10-2 mol. Further, the above compound may be added at any time during the process of producing a photosensitive silver halide emulsion, but it is preferable to add it after chemical ripening and before coating the emulsion in order to achieve the object of the present invention. On this premise, the photosensitive silver halide grains contained as essential components in the negative-tone sensitive material of the present invention include silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, It includes silver chloroiodobromide or a mixture thereof, but it is preferable to use silver iodobromide, which has high sensitivity.
In particular, silver iodobromide containing 50 mol% or less of silver iodide is suitable in the present invention.

Such photosensitive silver halide grains are applied to the present invention in the form of a silver halide emulsion, but the emulsion to be used may be manufactured by various manufacturing methods including the usual manufacturing method, such as Japanese Patent Publication No. 46-J. They can be prepared by methods such as those described in US Pat. can. Further, the photosensitive silver halide grains used in the present invention include those having various crystal habits.

Although the particle size varies depending on the purpose of use of the photographic element, it is usually within the range of 0.1 to 3.0 .mu.m. This photosensitive silver halide emulsion is then chemically sensitized using various sensitizers.

Chemical sensitizers include known sensitizers such as sulfur sensitizers, selenium sensitizers, and noble metal sensitizers, as well as reduction sensitizers,
Polyalkylene oxide-based sensitizers can also be widely used. Furthermore, the light-sensitive silver halide emulsion can be spectrally sensitized using various sensitizing dyes, and the emulsion can be stabilized using known photographic additives such as tetrazaintenes and tetrazoles. You can also do that.

Next, when the surface of the metal salt particles used in the present invention is not coated with the refractory agent,
The metal salt has a higher dissolution rate than the above-mentioned photosensitive silver halide with respect to a substance (described later) that dissolves metal salt particles, and is made of a metal salt having substantially no photosensitivity.

That is, to explain in more detail, the dissolution rate (or dissolution rate per unit time) of metal salt particle group A and photosensitive silver halide particle group B in the presence of at least one of the metal salt dissolving agents described below When the mass of the substance is measured under the condition that the total mass of the particles contained in both particle groups A and B is equal to each other, it is necessary that the mass of particle group A is larger than that of particle group B. be. As a measurement method for actually verifying whether or not such conditions are met, the following method is suitable.

First, two types of emulsions containing photosensitive silver halide grains and metal salt grains in hydrophilic colloids were prepared,
Two types of samples are prepared by applying each onto a support and drying.

The amount of coating at this time is such that the amounts of photosensitive silver halide, metal salt, and hydrophilic colloid per unit area are equal between the two types of samples. In the measurement, sodium thiosulfate is used as a standard metal salt dissolving agent, and the obtained sample is immersed in a 5% sodium thiosulfate solution (temperature 2(s)) without stirring.

The immersion time is set at several levels, for example 2 seconds, 5 seconds and 8 seconds. Next, the sample is immediately transferred to a water tank, washed with water, and then dried. The residual photosensitive silver halide and residual metal salt amounts of the sample treated in this manner are analyzed and measured by a known method, and the residual rate (%) is determined for each. A graph of residual ratio versus immersion time is drawn, and the immersion time t1 of the photosensitive silver halide sample and the immersion time T2 of the metal salt particle sample corresponding to a residual ratio of 50% are determined to determine the value of T2/t1. The value of T2/t1 determined in this way needs to be smaller than 1, and preferably smaller than 0.7. The metal salt particles are easily soluble in the above sense, but at the same time they are substantially free of photosensitivity.

In this case, 1.Substantially not having photosensitivity, in the present invention, means 1.Non-photosensitivity in a relative relationship with the photosensitive silver halide. It should be understood that when the photosensitive material of the present invention is given the light energy necessary to sensitize the photosensitive silver halide, it will not be substantially sensitized depending on the light energy.

More specifically, the metal salt particles of the present invention are fine particles of metal salts that generally have a photosensitivity of at most 1110 with respect to the photosensitive silver halide. The metal salt particles used in the present invention may be appropriately selected from those having the above properties.

However, in a preferred embodiment of the present invention, the metal salt particles are silver halide particles that have substantially no photosensitivity, and are more capable of dissolving silver octaride particles than the photosensitive silver halide particles. Particles are selected that have a high rate of dissolution into the substance.

More specifically, the metal salt particles preferably applied to the present invention are pure silver bromide, pure silver chloride, or a mixed silver halide thereof that has not been subjected to chemical sensitization treatment, and is It is preferable that the crystals be finer than the above.
The metal salt particles used in the present invention are used in an amount of 0.1 mol to 100 mol per 1 mol of photosensitive silver halide.

Note that the metal ions or metal complex ions generated as a result of dissolving such metal salt particles in the presence of the metal salt dissolving agent described below are those that are reduced to metals on the physical development nuclei in the presence of a reducing agent. be.

The surface of the metal salt particles used in the present invention is coated with a refractory agent, which is adsorbed onto the surface of the metal salt particle or forms a part of the particle surface that becomes an active site for the dissolution reaction. This is a compound that slows down the dissolution rate of particles in the presence of the metal salt dissolving agent by adsorbing to the metal salt dissolving agent.This poorly soluble agent also adsorbs to the surface of the easily soluble metal salt particles and dissolves the metal ions of the metal salt. It also includes compounds that form poorly soluble salts or complex salts.

According to one preferred embodiment of the invention.

The refractory agent is selected from compounds that adsorb to non-photosensitive silver halide grains, which are easily soluble metal salt grains, and reduce the solubility thereof. These compounds are preferably, for example, mercapto compounds, more specifically cysteine, 1-phenyl-5-mercaptotetrazole, mercaptobenzthiazole, mercaptobenzselenazole, mercaptobenzoxazole, mercaptobenzimidazole, benzylmercaptan, 4- Ethyl-2-thio-oxazoline, 2-mercapto-6-azauracil, 4-
Hydroxy-2-mercapto-6-methyl-pyrimidine, 3-mercapto-4-phenyl-5-methyl-1,2
, 4-triazole, etc. are included as typical examples.

Further, thiourea, intazoles, triazoles, imidazoles and the like are also preferred compounds that can be used in the present invention. Among these, mercaptotetrazole compounds are particularly preferred.

On the other hand, physical development nuclei used in the present invention include, for example, noble metals such as gold, silver, and platinum, preferably colloids thereof, metal sulfides such as silver, palladium, and zinc,
Alternatively, metal selenide or the like can be used.

Among these, metal silver particles obtained by reducing silver compounds (for example, silver nitrate, silver halide, etc.), noble metal colloids,
Alternatively, palladium sulfide and silver sulfide are particularly preferred.

Note that this physical development nucleus is a substance that has the function of catalytically promoting the process in which metal ions or metal complex ions produced by dissolving the metal salt described above are reduced to metal by a reducing agent, or such a substance. It does not necessarily have to be a physical particle.

The content of such physical development nuclei in a photosensitive material varies depending on the type thereof, but for example, in the case of silver sulfide, it is 0.001 to 1.0 g/i as metallic silver; (manufactured by reducing fine particles of silver chloride),
A range of 0.01 g to 3.0 g/i is appropriate. The structure of the photosensitive material of the present invention can take various forms depending on its purpose or use.

That is, in the light-sensitive material of the present invention, 1. photosensitive silver halide grains and 2. metal salt particles which are more easily soluble than silver halide and have substantially no photosensitivity are coated with a retarding agent on a support. Although it contains the above-mentioned particles 1 to 3 in separate layers, or any two or more of the above-mentioned 1 to 3 in the same layer. Good too. For example, on the support, from the support side, a constituent layer containing physical development/nuclei, a constituent layer containing metal salt particles,
Starting with a layer structure in which the constituent layers containing photosensitive silver halide grains are laminated in the order of the constituent layers containing the silver halide developer described below, if necessary, the order of the stacking may be reversed. It's okay, it's okay. Further, for example, from the support side, a constituent layer containing physical development nuclei and, if necessary, a silver halide developer described below is coated, and on this, photosensitive silver halide grains and metal salt grains are coated in the same layer. It is possible to have a two-layer structure by laminating constituent layers in which photosensitive silver halide grains, metal salt particles and physical development nuclei are mixed in the same layer. It can also be coated on a support to form a single layer structure.

Furthermore, as another method, it is possible to coat the constituent layers on both sides of the support, prepare two supports, and form the constituent layers separately for each support, or even coat the constituent layers on both sides of the support. A body may be prepared and the constituent layers may be coated one by one on each support.

The preferable layer structure of the sensitive material of the present invention is as follows:
A layer structure in which photosensitive silver halide grains, metal salt particles, and physical development nuclei are mixed in the same constituent layer and coated on the same support as a single layer, or metal salt particles and physical development from the support side. It is preferable to form a two-layer structure by coating a constituent layer containing a mixture of nuclei and a constituent layer containing only photosensitive silver halide grains thereon.

The layer structure of the photosensitive material of the present invention is as described above, but the photosensitive material of the present invention may include, if necessary,
For example, auxiliary layers such as a protective layer and an antihalation layer can be provided, and photographic additives other than those mentioned above can also be added to these layers.

In the present invention, the photosensitive silver halide, metal salt particles, and physical development nuclei are each used alone or in a mixture of two or more, dispersed in a suitable binder, and present in a predetermined constituent layer.

Various hydrophilic colloid layers can be used as the binder, and gelatin is typically preferably used.

Furthermore, in order to improve the physical properties of a coating film using the hydrophilic colloid layer as a binder, it is preferable to use various film properties improving agents, such as a hardening agent, if necessary. Coating film compositions containing a hydrophilic colloid layer as a binder include:
If necessary, photographic additives other than the hardening agent may be used, such as gelatin plasticizers, surfactants, ultraviolet absorbers, anti-stain agents, PH regulators, antioxidants, anti-Teiden agents,
Thickeners, graininess improvers, dyes, mordants, brighteners, development speed regulators, matting agents, silver halide developers described below, etc. can be used within the range without impairing the effects of the present invention. .

Supports used in the photosensitive material of the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, glass plates, cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyamide films, polypropylene films, and polycarbonates. Typical examples include film, polystyrene film, etc., and each of these supports is appropriately selected depending on the intended use of the photographic element.

After exposure, the photosensitive material of the present invention is processed with a developer containing a reducing agent and a substance that dissolves metal salt particles.

As the reducing agent used in the developer, a developing agent is advantageously used. Examples of developing agents include those well known in the art, such as hydroquinone, toluhydroquinone, and
, 5-dimethylhydroquinone, etc., for example, 3-pyrazolidones such as 1-phenyl-3-hyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, etc., e.g.
-Aminophenols represented by aminophenol, p-aminophenol, etc., such as 1-(p-hydroxyphenyl)-3-aminopyrazoline, 1-(p-
1-aryl-3-aminopyrazolines typified by (methylaminophenyl)-3-pyrazoline, ascorbic acid, others, C.I. B. K. Mees and T. H. Ja
co-authored by mesRTheOryOfthePhOtO
graphlcPrOcessJ 3rd edition (1966,
MacmillanCO. ,N. Y), Chapter 13 and L.
P. A. Written by MasOn RPhOtOgraphicPr
Occessing Chemistry J (1966,
TheFOcalPress. IJ)NdOn)16~
The compounds listed as developing agents on page 30 can be used alone or in combination. Substances that dissolve metal salt particles (metal salt dissolving agents) used in developer solutions are:
A substance that acts on metal salt particles to generate metal ions or soluble metal complex ions, and this may be the solvent of the developer itself, such as water.

In this case, the metal salt dissolving agent is a substance that does not substantially dissolve the photosensitive silver halide, or it is a substance that does not dissolve the photosensitive silver halide in an amount added that does not substantially dissolve the photosensitive silver halide. The material is preferably a substance that dissolves metal salt particles such as fine particles of silver halide having different ions.

Typical specific examples of such metal salt dissolving agents include sulfites such as sodium sulfite, thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate, cyanates such as potassium cyanide and sodium cyanide, and thiocyanates. thiocyanates such as sodium chloride and potassium chloride, amino acid compounds such as cystine and cysteine, thiourea, phenylthiourea, 3,6-dithia-1
, thiourea compounds such as 8-octadiol, thioether compounds, and the like.

The metal salt dissolving agent is normally contained in the developer, but in some cases it may be contained in the sensitive material as described above.

Among the above metal salt dissolving agents, sodium sulfite in particular is generally used as a preservative for developing solutions, so the amount used per 1e is preferably 1g to 70g, more preferably 1g to 100g. It is preferable that there be.

The pH of such a developer is 5 or more, preferably PH5.
．． Approximately 5 to 131 is optimal. Further, the developer may contain various additives such as an alkaline agent, a PH buffer, a development accelerator, and an antifoggant, if necessary.

The above treatment temperature is suitably in the range of 20°C to 50'C. Hereinafter, the present invention will be explained in more detail with reference to specific examples. Example 1 [Preparation of photosensitive silver halide emulsion] A high-sensitivity iodide emulsion containing 4.0 mol % of silver iodide that was gold-enriched, sulfur-enriched and ripened to the highest degree by a conventional method. A photosensitive silver halide grain emulsion was prepared by adding 4-hydroxy-6-methyl-1,3,3a7-tetrazaindene as a stabilizer to the silver halide emulsion per mole of silver halide. .

The average grain size of this emulsion was about 1.3 microns. [Preparation of metal salt grains (substantially non-photosensitive silver halide grains)] A pure silver chloride emulsion consisting of silver nitrate and sodium chloride was prepared by a neutral method.

The average grain size of this emulsion was easily soluble silver chloride grains of about 0.1 μm. [Preparation of physical development nuclei] Add 50 m of 0.2% chloroauric acid to 10 nt of an aqueous solution of 1% polyvinyl alcohol (a polymer with a degree of saponification of 99% and a degree of polymerization of 1000).
1 and stirred at room temperature, 10 ml of 1% sodium borohydride was added to form physical development nuclei for gold colloid.

First, a silver chloride emulsion with virtually no photosensitivity was taken from among the three types prepared as described above, and 1.2 g of 1-phenyl-5-mercaptotetrazole was added per mole of silver halide as a refractory agent. Then, the above-mentioned physical development nucleus is
120 m9 of chloroauric acid was added per mole of silver chloride emulsion, and then an appropriate amount of saponin was added as a coating aid to prepare a coating solution.

At the time of application, it was applied uniformly to both sides of a polyethylene terephthalate base that had been subjected to undercoat processing. Subsequently, the photosensitive emulsion prepared as described above was collected, divided into equal parts, and the compound according to the present invention was added as shown in Table 1 below, and at the same time, a comparative sample without the addition was also prepared. .

Next, an appropriate amount of saponin was added as a coating aid, and the mixture was uniformly coated on both sides of the silver chloride emulsion layer. Furthermore, on top of this layer, a 2.5% gelatin aqueous solution containing an appropriate amount of a hardening agent (formalin) and a coating aid (sodium succinic acid-2-ethylhexyl ester monosulfonate) is coated as a protective layer. Then, various negative-working silver halide photographic materials were prepared.

The amount of coating on both sides of the obtained sample was as follows: the amount of silver in the silver chloride layer as a non-photosensitive silver halide emulsion layer was 1.0 g/d, the amount of gold as physical development nuclei was 1.0 Tn9/d, and the photosensitive layer was 1.0 Tn9/d. The amount of silver in the silver iodobromide layer as a silver halide emulsion is 3.0 g.
It was /wl.

After conducting a raw storage test on each sample obtained above under the conditions listed in Table 1 below, the film pieces of each sample were wedge exposed to 3.2 CMS light, and the following formulation was applied. Developing was carried out for 9 seconds at 35° C. using L in a developer solution, followed by fixation, washing with water and drying, followed by sensitometry.

[Developer prescription]

Hydroquinone 12.0g Anhydrous sodium sulfite 65.0g Phenidone 1.0g Sodium hydroxide 15.0g 5-Methylbenzotriazole 0.5g Potassium bromide
Add 2.0g water and 1'
) The results obtained are shown in Table 1 below.

Note that the sensitivity values in the table are expressed as a 10 powder ratio with respect to sample NOl. As is clear from the above table, all of the samples containing the compound according to the present invention are more effective in reducing fog that occurs during storage under high temperature, low humidity and high temperature and high humidity conditions, compared to comparative samples that do not contain any additives. It turns out that there is.

Example 2 A part of the sample prepared in Example 1 was prepared, and at the same time, as a comparative sample for this example, only the photosensitive emulsion prepared in Example 1 was uniformly coated on both sides of a polyethylene terephthalate base. One was prepared by coating the photosensitive emulsion on both sides of a polyethylene terephthalate base, and the other was prepared by uniformly coating both sides of a polyethylene terephthalate base with the photosensitive emulsion prepared by adding the compounds shown in Table 2 below.

Then, a protective layer was applied on each of the photosensitive emulsion layers of this comparative coating to prepare a comparative sample.

The amount of silver coated on both sides was 3.0 g/d. The film of each sample obtained was subjected to a raw storage stability test treatment under the conditions shown in Table 2, and then exposed and developed in the same manner as in Experimental Example 1. The results are shown in Table 2 below. In addition,
The sensitivity values in the table are for sample No. It is shown as a powder ratio of 10 to 15. As can be understood from the results in the above table, the sample of the present invention to which the compound according to the present invention J was added (NQ.
It is clear that methods 6 to 19) are effective in suppressing the increase in fog without reducing sensitivity, especially when storing photosensitive materials under high temperature and high humidity conditions.

It has also been proven that adding the compound of the present invention to a silver halide photosensitive emulsion only increases fog when the photosensitive material is stored under high temperature and high humidity conditions, as seen in conventionally known techniques. . Example 3 A sample prepared in the same manner as Example 1 was heated at 50°C and 80% R.
After storing for 3 days under high temperature and high humidity of H, under safelight (Sakura Highlight, 20 Watt tungsten lamp), 1.
Two questions were left at a distance of 0rr1.

After this sample was developed in the same manner as in Example 1, the fog density was measured. The results obtained are shown in Table 3 below. The fog values in the table are expressed as the difference between the fog values that occur when two exposures are made to safelight and when exposed to Song exposure.

As is clear from the above table, all the samples (No. 2l to 24) to which the compound according to the present invention was added were particularly effective in reducing fogging that tends to occur when exposed to safelight while being stored under high temperature and high humidity. It has been shown that it is possible to reduce the

Claims (1)

[Scope of Claims] 1. Photosensitive silver halide grains on a support, the surface of which has been made difficult to solubilize with an insoluble agent, are themselves more easily soluble than the above-mentioned photosensitive silver halide grains, and substantially A negative characterized in that a compound represented by the following general formula is contained in any one of the constituent layers having a layer containing at least one of non-photosensitive metal salt particles and physical development nuclei. type silver halide photographic material. General formula M(X)n (wherein M represents an alkali metal, alkaline earth metal, or ammonium group, X represents a chlorine atom or a bromine atom, and n is an integer of 1 to 2.)