JPS6014336B2 - Shadow image forming method - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for forming a negative image, and more specifically, it utilizes photosensitive silver halide, a metal salt, and a physical development nucleus to obtain a negative image with high sensitivity, high contrast, and maximum density. This invention relates to a novel image forming method. o Silver, which is essential for silver halide photographic materials, is decreasing in supply and increasing in demand, resulting in a significant price increase.As a result, the industry is
Currently, attempts are being made to reduce the amount of silver consumed. For example, one example is a silver salt diffusion transfer method using physical development nuclei. This method has a very high covering power (silver covering power) of the transferred image, so a higher density photographic image can be obtained with a small amount of silver halide, and it also has excellent sensitivity and scalability, making it extremely useful. This is known as an image forming method. However, this method is a negative/positive type diffusion transfer method, and since the final image obtained is a positive image, Z is not suitable for the purpose of the method of the present invention to form a negative image. On the other hand, Japanese Patent Publication No. 45-*O5 proposes a diffusion transfer method using a processing solution containing a development solubilization promoter that can form an insoluble flange compound with silver halide. Since Z is essentially different from the invention, it is far from achieving the purpose of the present inventors, and there is a drawback that it is difficult to obtain a satisfactory negative image. In addition, as a method according to Japanese Patent Publication No. 1982-20, internal latent image type silver halide grains with capri formed and surface two latent image type silver halide grains containing silver iodide and without fogging are used. It is said that it is possible to increase the contrast and maximum density by making the two adjacent to each other. However, with this method, it is not possible to reduce the amount of silver to a large extent, and the Cub 21J property of the internal port image type emulsion causes a loss of sensitivity due to photographic characteristics. hard. Furthermore, Japanese Patent Application Laid-Open No. 54-4 by the applicant to which the present inventors belong
According to Japanese Patent No. 8544, a new method for forming a negative image consists of (i) a photosensitive silver halide layer and (i) a metal salt which is more easily formed and substantially non-photosensitive. A combination structure consisting of a layer in which a solubilizing agent is adsorbed to the grains and physical development nuclei has been proposed, but in this case, the solubility of the metal salt particles (for example, silver halide particles) on which the insoluble agent is adsorbed has been proposed. 3. Naturally, this decreases significantly. In this case, in order to elutriate the easily soluble silver halide grains, it is necessary to add a necessary and sufficient amount of solubilizing agent, so it is necessary to add a necessary and sufficient amount of solubilizer to the photosensitive silver halide grains that coexist or are adjacent to each other. Diffusion migration into the 4-layer or adjacent layers presents a serious drawback causing desensitization. It has become clear that this is particularly remarkable when the photosensitive material is stored. Furthermore, when the light-sensitive material is processed with a processing solution containing at least a reducing agent and a substance that dissolves the solubilized silver halide, in the conventional method, the step of depositing on the physical development nuclei takes an extremely long time. , requiring a long development process. Therefore, the rapid processing that has been desired in recent years cannot be performed. Furthermore, since the efficiency of this process is extremely low, it is not possible to obtain an increase in sensitivity and density, and as a result, there are drawbacks such as the inability to reduce the amount of silver. Furthermore, the present inventors have been searching for a new method that does not have these drawbacks, and as one method, in order to elutriate easily soluble silver halide grains, Tokusekki Akihiro No. 48544 discloses the following method:
While the solubilizing agent is directly added to the photographic emulsion, the present inventors discovered that the object could be achieved by incorporating the solubilizing agent into the processing solution. (Japanese Unexamined Patent Publication No. 55-137528) However, it has been found that the above novel method also has practical drawbacks. That is, since the treatment liquid is alkaline, the scale-solubilizing agent itself partially changes in quality when used at high temperatures. For example, a mercapto compound undergoes oxidation and doubles, reducing its ability to adsorb onto silver halide grains.Also, because a mercapto compound is adsorbed to silver halide during processing, the solubilizing agent in the processing solution is reduced. It was found that adding a refractory agent to the processing solution causes the processing solution to become unstable, as the concentration changes, making it difficult to maintain the desired photographic characteristics of the negative image. did. However, as a result of intensive study of such methods, the present inventors have discovered and developed a novel negative image forming method based on a technical idea that is far superior to each of the conventional methods described above. Therefore, the first object of the present invention is to provide a novel silver halide photographic material capable of producing negative images with high sensitivity, high contrast, and high maximum density in a silver-saving light-sensitive photographic element. It is to provide. A second object of the present invention is to provide the above-mentioned novel halogenated photographic light-sensitive material that maintains excellent properties without any change in photographic properties even when stored at high temperatures for long periods of time. It is. A third object of the present invention is to provide an image forming method with good running characteristics in high-temperature rapid processing of a new silver-saving photographic material. A further fourth object is to provide an imaging method for increasing the contrast of silver halide emulsions having relatively low contrast by a novel silver halide image enhancement method. Other objectives will become apparent from the description below. The inventors have found that the above objects are achieved in the method detailed below. That is, the present invention provides, on a support, (i) a photosensitive silver halide layer and (ii) particles of a metal salt that is more easily soluble than (i) and substantially non-photosensitive. A photosensitive material formed by coating a layer adsorbing a refractory agent and a layer containing Z containing physical development nuclei as a single layer or a composite layer is subjected to a processing solution containing at least a reducing agent and a substance that dissolves the particles of the metal salt. It has been found that the above objective can be achieved by processing the above-mentioned materials.
2. As described above, the present invention comprises (i) a photosensitive silver halide layer and (ii) particles of a metal salt which is more easily soluble than (i) and has substantially no photosensitivity, with a non-diffusible, refractory layer. The photosensitive photographic element 2 according to the present invention, which has a layer on which an agent is adsorbed and a physical development nucleus as its basic constituent elements, can take various forms depending on the purpose or use when concretely implemented. It is. The non-diffusible solubilizing agent used in the present invention is an azole having at least four or more carbon atoms as a ballast group, and these compounds are applied to the particle surface, which is the sliding point of the dissolution reaction of the easily soluble metal trisalt particles. By adsorbing it, it forms a soluble salt or salt salt with the metal ion. Furthermore, this refractory agent is
Since it is imparted with non-diffusibility, it has the characteristic that when it adsorbs to metal salt particles, it does not adsorb and diffuse to other adjacent particles or other layers. The non-diffusive solubilizing agent preferably used in the present invention generally belongs to the class of stabilizers or antifoggants for silver halide emulsions, and specific examples of such compounds include, for example, the following general formula [ 1]. General formula [1] In this), Q is a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing double ring, and the double ring contains an alkyl group having at least 4 carbon atoms, a substituted It represents an alkyl group, a substituted carbamoyl group, an alkylthio group, or a substituted or unsubstituted aryl group. M is a hydrogen atom or an alkali metal. According to a preferred embodiment of the present invention, the compound represented by the general formula [1] is strongly adsorbed by being added to metal salt particles to make the particles solubilized, and at the same time, photosensitive silver halide particles, Alternatively, it imparts non-diffusive properties to adjacent constituent layers. Specifically selected and more preferably used specific compounds from the compounds of the above general formula [1] are the following general formulas:

Represented by [0] or [m]. ．． General formula [□] In this), RI is an alkyl group having 8 to 12 carbon atoms, a substituted alkyl group, or a substituted or unsubstituted aryl group, and M represents a hydrogen atom or an alkali metal. ．． In the general formula [m]), Y is 0. S. Se. N.R3, in which R3 is a hydrogen atom, a lower alkyl group, a substituted alkyl group, or an aryl group. R2 is an alkyl group having 8 to 12 carbon atoms, a substituted alkyl group, a substituted aryl group, an alkylthio group, -NHCOR4 (
R4 is an alkyl group having 8 to 12 carbon atoms), and M represents a hydrogen atom or an alkali metal. Specific examples of compounds that can be used in the present invention are shown below, but the present invention is not limited thereto. general formula

Example of compound [0] Example of compound of general formula [m] The amount of the above compound used in the photosensitive material according to the present invention is preferably in the range of 0.012 to 3 mol per mol of silver halide, more preferably 0. .1 evening to 1 evening. When used, it is customary to add a solution dissolved in water or an organic solvent to a silver halide emulsion before coating. The above compound adsorbs to the metal salt particles and reduces the dissolution of the particles, and at the same time imparts e-diffusive properties to the coexisting or adjacent photosensitive silver halide particles or the adjacent Z layer. It is something. The light-sensitive silver halides of the light-sensitive photographic material used according to the invention include silver chloride, silver bromide, silver iodide, silver chlorobromide.
Silver iodobromide, silver chloroiodobromide, or a mixture thereof is included, but it is preferable to use silver iodobromide with a high degree of Z sensitivity. Silver bromide is preferred in this invention. Although the grain size of these silver halides varies depending on the intended use of the photographic element, it is usually within the range of 0.1 to 3.0 mm. These silver halide emulsions are then chemically sensitized using various chemical sensitizers. Chemical sensitizers include a wide range of well-known sensitizers such as sulfur sensitizers, selenium sensitizers, and yellow metal sensitizers, as well as reduction sensitizers and polyalkylene oxide-based sensitizers. put to use. Furthermore, the above silver halide emulsion can also be spectrally sensitized using various sensitizing dyes. Further, these silver halide emulsions can be prevented from fogging by using known stabilizers such as imidazoles, trisols, and azaindenes. Next, when the surface of the metal salt particles used in the present invention is not coated with a solubilizing agent, the dissolution rate of the photosensitive halogenated metal salt particles is 3 times higher than that of the substance that dissolves the metal salt particles described below. It is a salt of a metal that is larger than silver and has virtually no photosensitivity. More specifically, the conditions regarding the dissolution rate of both of these grains are as follows. The dissolution rate (mass of substance discarded per unit time) (for example, in the processing liquid used in the present invention) is A
, B It is necessary that particle group A be larger than particle group B under the condition that the total mass of particles included in both particle groups is equal. Measurement methods when such conditions are actually applied include the following methods. First, two types of emulsions each containing photosensitive silver halide particles and metal salt particles in a hydrophilic colloid are prepared, and each emulsion is coated onto a support and dried to prepare two types of samples. 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. The obtained sample is soaked without soaking in a 5% aqueous sodium thiosulfate solution (temperature 20°C). The immersion time is set to several levels, such as 2 seconds, 5 seconds, and 8 seconds.
Next, the sample is immediately transferred to a water tank, washed with water, and then dried. The amount of residual photosensitive silver halide and residual metal salt of the sample treated in this manner is analyzed and measured by a known method, and the residual percentage (%) is determined for each. Draw a graph of residual distillation rate and immersion time, find the immersion time t of the photosensitive silver halide sample corresponding to a residual distillation rate of 50%, the immersion time of the metal salt particle sample, etc., and find the value of t2/t. seek. The t2/t. calculated in this way. The value of is required to be smaller than 1, and preferably smaller than 0.7. The substance that dissolves the metal salt particles used in the present invention (hereinafter referred to as metal salt dissolving agent) is a substance that acts on the metal salt particles used in the present invention to generate metal ions or soluble metal tin ions. may be the solvent of the treatment liquid used in the present invention, such as water. According to a preferred embodiment of the present invention, the dissolving agent is a substance that does not substantially dissolve the photosensitive silver halide used in the present invention, or is a metal in an amount that does not substantially dissolve the photosensitive silver halide. The photosensitive silver halide, which is a salt particle, is a substance that dissolves fine particles of silver halide that have different solubility. Typical specific examples include sulfites such as sodium sulfite, sodium thiosulfate, and potassium thiosulfate. , thiosulfates such as ammonium thiosulfate, cyanates such as potassium cyanide and sodium cyanide, thiocyanates such as sodium thiocyanide and potassium rhodan, amino acid compounds such as cystine and cysteine, thiourea "phenylthiourea, 3,6-dithia" Examples include thiourea compounds such as -1,8-octadiol, and thioether compounds. Among these solubilizing agents, sodium sulfite is a preferred example;
Rhodan potassium or a thioether compound may be used in combination with this. Furthermore, in the method of the present invention, the term "substantially not having photosensitivity" means "non-photosensitive" in relation to the photosensitive halogenated synthetic fiber, Specifically, it should be understood that when the light energy necessary to sensitize the light-sensitive silver halide is applied to the light-sensitive photographic element according to the present invention, the light-sensitive silver halide is not substantially sensitized by the light energy. be. More specifically, the particles of the metal salt of the present invention are generally fine particles of the metal salt that do not have a photosensitivity of at most 1'I0 relative to the photosensitive silver halide. The metal ions or metal rust ions produced as a result of the dissolution of the metal salt particles are reduced to metal on the physical development nucleus in the presence of a reducing agent. The metal salt particles used in the present invention may be appropriately selected from those having the above-mentioned properties, but in a preferred embodiment of the present invention, the metal salt particles are substantially photosensitive. Silver halide grains that do not have a silver halide grain and have a higher dissolution rate for a substance that dissolves silver halide grains than the photosensitive silver halide grains are selected. More specifically, the metal salt particles preferably applied to the present invention are pure silver bromide, pure silver chloride, or a mixture thereof that has not been subjected to chemical sensitization treatment. It is preferable that the silver halide has finer crystals than the photosensitive silver halide. The metal salt particles used in the present invention are used in an amount ranging from 0.1 mol to 100 mol per mol of the photosensitive halide beam. Furthermore, as the physical development nuclei used in the present invention, for example, noble metal colloids such as gold, silver, and platinum, metal sulfides such as silver, palladium, and box salts, and metal selenides can be used. Among these, metal silver particles obtained by reducing silver compounds (for example, silver nitrate, silver halide, etc.) and palladium sulfide are particularly preferred. These physical development nuclei are substances that have the function of catalytically promoting the process in which the metal ions or metal ions produced by dissolving the metal salt are reduced to metal by a reducing agent, or have such a function. It contains G-active sites,
It does not necessarily have to be a physical particle. The content of the above-mentioned physical development nuclei in a photographic element varies depending on the type thereof, but for example, in the case of silver sulfide, the content of the physical development nuclei is 0.001 μm to 1 μm as metallic silver.
．． In the case of metallic silver (produced by reducing fine particles of silver chloride), a range of 0.01 to 3.0 is suitable. Furthermore, the physical development nucleus used according to the present invention is a substance having the function of catalytically promoting the process in which metal ions or metal rust ions generated by dissolving the metal salt particles are reduced to metal by a reducing agent. It includes any chemically active point that has this function. Specific examples thereof include metal colloids dispersed in a binder, metal sulfide colloids, and other metal salt colloids. In this case, binders include gelatin, siligasol, polyvinyl alcohol, gum arabic, agar, cellulose derivatives, etc. Regarding the method of preparing physical development nuclei, for example, Photograph Sil/Ino Ride Difusing Process (The Focal Press 1972 main edition London New York). Furthermore, any developer can be used as the developing agent of the developer used in the method of the present invention. Examples include hydroquinone, 4-N methylaminophenol (metol), ascorpic acid, isoascorpic acid, 2,6-dimethyl-4-aminophenol, toluhydroquinone, 2,6-dimethylhydroquinone, 2-
Methyl-4-amino-6-methoxyphenol, 2,6
-dimethoxy-4-aminophenol, 2,5-dimethylhydroquinone, 2,4,6-monotriaminophenol, 2,4-diaminophenol (amidol), N,
Examples include N-diethylhydroxylamine and 4,6-diamino-ortho-cresol. Further, as alkaline agents, for example, inorganic alkaline agents such as caustic soda and soda carbonate, as well as diethylamine and the like are added to the developing solution. In addition, commonly used additives such as a development inhibitor, a color toning agent, a curing agent, and a development accelerator can be added to the developer as required. In particular, as development inhibitors, derivatives of imitazole, indazole, and triazole described in Japanese Patent Application No. 54-11193 are preferred. As described in detail above, the present invention utilizes the principle of the silver disc diffusion transfer method to quickly produce high-sensitivity negative images with less desensitization through the use of a silver-saving silver halide composition and the use of a physical developer. It is characterized by the fact that it is formed. We have also found that the above effects can only be achieved by the presence of a non-diffusible azole compound having a structure as shown in the above general formula as a solubilizing agent for the above-mentioned easily soluble metal salts, I put it out. Z Also, in the present invention, regarding the structure of the photosensitive layer, ``Several embodiments are possible, but a highly sensitive halogenated line, a metal salt having substantially no photosensitivity,
For example, a Z configuration in which silver chloride and physical development nuclei are contained in the same emulsion layer and coated on a support, or a metal salt having substantially no photosensitivity on the support;
For example, it is most preferable to apply an emulsion layer containing silver chloride and physical development nuclei in the same layer, and further apply an emulsion layer containing high-sensitivity silver halide thereon.
2 Below, the present invention will be explained in more detail with reference to typical examples, but the technical scope of the present invention is not limited in any way by the following examples, and various embodiments are possible. be. Example 1 [Preparation of easily soluble metal salt grains (substantially non-photosensitive silver halide) emulsion] After preparing a pure silver chloride emulsion consisting of silver nitrate and sodium chloride by an ordinary neutral method, precipitation was carried out. An emulsion was obtained by washing according to the method. The average particle size of the silver chloride particles was about 0.1 micron. [Preparation of physical development nuclei] Physical development nuclei consisting of silver sulfide are prepared with sodium sulfide and silver nitrate in an aqueous gelatin solution. Next, the above-mentioned easily soluble pure silver chloride emulsion was divided into equal parts, and each portion was divided into equal parts, each having the general formula (m) according to the present invention, as shown in Table 1 below.
and the compound [m] and the comparative compound 1-phenyl-
After adding 5-mercaptotriazole (comparison A), after adsorbing it sufficiently, add an appropriate amount of the above-mentioned physical development nuclei, and then add saponin as a coating aid, and then spread it evenly on the undercoated polyester base. Coated. At this time, the amount of coated silver in the silver chloride emulsion was 2.1 days/end, the amount of silver in the physical development nuclei was 0.1 days/end, and the amount of gelatin was 3 days/end. Next, on this layer, an appropriate amount of sodium succinate-2-ethylhexyl ester monosulfonate was added to the photosensitive silver iodobromide emulsion as a coating aid, and the amount of silver was reduced to 2.
．． It was applied uniformly so that the amount of gelatin was 3:0 and the amount of gelatin was 3:0. Furthermore, on top of that layer, an appropriate amount of hardening agent (formalin) and coating aid (same as above) was added as a protective layer, 2.5%.
A photosensitive material according to the present invention was prepared by applying a gelatin aqueous solution in multiple layers. 3. The obtained film piece. After wedge-lighting with the light of this MS, it was developed with a 35 qo 3-machi sand spacing using a developer with the following formulation, then fixed, washed with water and dried, and then subjected to sensitometry. [Developer formulation] Hydroquinone 12.0 anhydrous sodium sulfite 65.0 taufenidone 1.0 sodium hydroxide 15.0 sodium thiosulfate (pentahydrate) 2.0 potassium bromide
Add 0.2 tsp of Yusui
Make it 1k. The results obtained are shown in Table 1 below. As is clear from Table 1, when the compound according to the present invention is contained, a negative-tone photosensitive material with high gamma and high sensitivity with lower fog (minimum density) than the comparative sample can be obtained. . Example 2 The above-mentioned easily soluble silver chloride emulsion was mixed with the compound according to the present invention and Comparative A and 3-merkabuto-*1 as comparative samples.
, 2,4-triazole (comparison B) respectively as shown below.
A sample was prepared in the same manner as in Example-1 except that the ingredients were added as shown in the table. The obtained samples were subjected to a film preservation test, followed by exposure and development in the same manner as in Example 1, and the results are shown in Table 2 below. Table 2 As is clear from Table 2 above, according to the method of the present invention, desensitization during film storage is extremely small, and stable photographic properties can be maintained. In particular, it is unique in that the sensitivity at high temperatures is significantly improved compared to the comparative sample. Example 3 Comparative A and the compounds according to the present invention were added to the same easily soluble silver chloride emulsion as used in Example 1 as shown in Table 3 below, and then Example 1 was added to the silver chloride emulsion. A photosensitive silver iodobromide emulsion similar to that used in the above and physical development nuclei were added and mixed. The mixing ratio was determined by adding and mixing silver chloride emulsion and silver iodobromide emulsion so that the silver ratio was 3:1 by mole to prepare a coating solution. The amount of silver coated at this time was 2.0 evenings/day. A protective layer of the same type as in Example 1 was coated on this film to obtain a photosensitive material of the present invention. The development results for the obtained samples are shown in Table 3 below.
The exposure conditions were the same as those in Example 11, and the developing solution was 30OO with the following formulation, and 4 Asa was developed. [Developer prescription] Hydroquinone 12.0 ta Anhydrous sodium sulfite 65.02 Phenidone 1. 0 Potassium hydroxide 15.0 Sodium tathiosulfate (pentahydrate) 0. 5 evening* 61 Nitroindazole 0
．． 2 ethanolamine 10
Z Potassium Bromide Add 0.5 of Yusui and make 1. As is clear from Table 3 below, even in the case where the three types of readily soluble silver chloride emulsion, photosensitive silver iodobromide emulsion, and physical development nuclei are mixed, the compound according to the present invention can be used as a silver chloride emulsion. It can be seen that by adsorbing the compound to an emulsion and solubilizing it, a light-sensitive material with less desensitization than the comparative compound can be obtained. That is, it is presumed that this is the result of no diffusion and transfer to other particles or other adjacent layers. Table 3 Example-4 This example shows good results regarding the running characteristics of the photosensitive material according to the present invention. 3 In exactly the same manner as shown in Example 1, a readily soluble pure silver chloride emulsion containing an elutriator (see Table 4 below) and physical development nuclei was coated, and then a photosensitive silver iodobromide emulsion was applied as an upper layer. A coated photosensitive material according to the present invention was prepared.
3.The obtained film piece is 3. After exposure with the light of this MS, Example 11
Development was carried out at 35oo for 30 seconds using a developer solution. Using the developer repeatedly in this way, about 50 samples were
The changes in the characteristics of the photosensitive material due to the running of the developer were tested by comparing the first process with 0 cc of developer and the 3q-th process. The results obtained are shown in Table 4 below. Table 4 Table 4 above shows that the method of the present invention results in small fluctuations in photographic properties during the running process of development. The above examples show that the method of the present invention can provide high gamma, high sensitivity negative images with low silver content through rapid processing.

Claims (1)

[Claims] 1. On a support, (i) photosensitive silver halide, (ii) formula [
particles of a metal salt whose surface has been rendered insoluble by a compound represented by [II] or [III], which itself is more easily soluble than the photosensitive silver halide and has substantially no photosensitivity, and (iii) ) A light-sensitive silver halide photographic material having a layer containing physical development nuclei coated as a single layer or a composite layer is treated with a processing liquid containing at least a reducing agent and a substance that dissolves the particles of the metal salt. A negative image forming method characterized by processing. [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ Here, R' is an alkyl group having 7 to 12 carbon atoms, a substituted alkyl group, a substituted or unsubstituted aryl group, and M represents a hydrogen atom or an alkali metal. . ▲There are mathematical formulas, chemical formulas, tables, etc.▼Here, Y is O, S
, Se, N, R^3, and R^3 in this case is a hydrogen atom, a lower alkyl group, a substituted alkyl group, or an aryl group. R^2 is an alkyl group having 7 to 12 carbon atoms, substituted alkyl group, substituted alkyl group, substituted aryl group, alkylthio group, -NHCOR^4 (R^4 is an alkyl group having 8 to 12 carbon atoms), M is hydrogen Represents an atom or an alkali metal.