JPH053576B2 - - Google Patents

Description

[Detailed description of the invention]

(A) Industrial Application Field The present invention relates to a material for diffusion transfer. In particular, it relates to a photosensitive material for silver complex diffusion transfer. (B) Prior art and its problems The principle of silver complex diffusion transfer method (hereinafter referred to as DTR method) is described in US Pat. No. 2,352,014 and is well known. In the DTR method, an imagewise exposed silver halide emulsion layer is superimposed in contact with an image-receiving layer in the presence of a developing agent and a silver halide complexing agent. In the exposed parts of the silver halide emulsion layer, the silver halide is developed to silver (chemical development) and therefore it cannot be dissolved any further;
Can't spread. In the unexposed areas, the silver halides are converted to soluble silver complexes, which are transferred to the image-receiving layer, where they form a silver image, usually in the presence of physical development nuclei. The advantage of the DTR method is that it uses a simple processor.
By superimposing the light-sensitive material for diffusion transfer and the image receiving material in the processing solution for DTR, it is possible to obtain ultra-high contrast and halftone developability comparable to commercially available Lith film, while controlling the processing solution better than the Lith system. This is an easy point. Although the DTR method is superior in terms of simple processing, as the processing liquid is used more and more, it becomes more fatigued, halftone dot reproducibility decreases, and halftone dot unevenness becomes more likely to occur. Usually, the processing liquid for DTR is
Many of the new solutions have a pH > 11.0, but with such processing solutions, as the number of processing increases and the length of time they are left standing increases, the PH decreases, and if it is below 10.5, halftone dot unevenness is likely to occur. . In recent years, for processing using such DTR method,
There is an increasing demand for durability of processing solutions. As the processing liquid is used, the pH decreases and fatigue occurs, but this effect is generally more visible in halftone images than in line images, and the DTR currently on the market
Even in photosensitive materials for use in photosensitive materials, the occurrence of halftone dot unevenness with fatigued solutions has been a major problem, regardless of new solutions. In order to reduce such halftone unevenness caused by fatigue liquid, the present inventors have worked on improving light-sensitive materials for diffusion transfer and have conducted various studies. the result,
All layers on the silver halide emulsion-coated side of the light-sensitive material for diffusion transfer contain substantially no aldehyde hardener, and 2,4-dichloro-6-hydroxy is contained in the silver halide emulsion. It has been discovered that by including -S-triazine salt, it is possible to reduce halftone dot unevenness in fatigue liquid. Aldehyde hardener and 2,4-dichloro-6
-Hydroxy-S-triazine salt is a well-known hardening agent, but its effects during film formation have not been clarified, and there are still some unknown points, especially regarding the swelling effect of DTR processing liquids. There were many. As shown in the embodiments of the invention, DTR
It should be noted that the effectiveness of the invention appears only with the method, and the effect with fatigue fluids is not seen with normal chemical phenomena. (C) Object of the Invention One object of the present invention is to provide a light-sensitive material for diffusion transfer in which the fatigue solution of the DTR processing solution has less deterioration in halftone dot reproducibility and less halftone unevenness. . Other objects of the invention will become apparent from the description below. (D) Structure of the invention The 2,4-dichloro-6-hydroxy-S-triazine salt used in the present invention is 2,4-dichloro-6-hydroxy-S-triazine salt.
It is composed of a -hydroxy-S-triazine anion and a counter cation, and the counter cations include, but are not limited to, L ⁺ ₄ ', K ⁺ , N ⁺ _a , NH ⁺ ₄ ', etc. isn't it. The 2,4-dichloro-6-hydroxy-S-triazine salt can be synthesized, for example, by the method described in Japanese Patent Publication No. 47-6151, but the synthesis method is not particularly limited. 2,4-dichloro-6 used in the present invention
The amount of -hydroxy-S-triazine salt used varies depending on various conditions, but is in the range of 5 to 200 mg, preferably 10 to 200 mg, per 1 g of gelatin in the emulsion layer.
It is 100mg. In the present invention, aldehydes such as formalin, glyoxal, malealdehyde, and glutaraldehyde, N-methylol compounds such as urea and ethylene urea, and aldehyde analogues such as mucochloric acid and 2.3-dihydroxy-1.4-dioxane are substantially shall not be included in These hardeners have a tendency to increase dot unevenness, especially in fatigue solutions. In the present invention, the pH of the silver halide emulsion is
It is preferably 4.5 or less, thereby making it possible to obtain a light-sensitive material for diffusion transfer that has excellent stability over time (storability) and less uneven halftone dots. In the present invention, it is preferred that 2,4-dichloro-6-hydroxy-S-triazine salt be added immediately before coating. It was found that this stabilized the dura mater level and made it less susceptible to the effects of time elapsed before application. Hydrophilic binders that are advantageously used for preparing light-sensitive emulsions include lime-treated gelatin, acid-treated gelatin, gelatin derivatives (e.g. Japanese Patent Publication No. 38-4854)
No., No. 39-5514, No. 12237-12237, No. 42
−26345, U.S. Patent No. 2525753, U.S. Patent No. 2594293
No. 2614928, No. 27639, No. 3118766
No. 3132945, No. 3186846, No. 3186846, No. 3132945, No. 3186846, No.
3312553, British Patent Nos. 861414, 1033189, etc.), proteins such as albumin and casein, cellulose compounds such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, natural polymers such as sodium alginate, polyvinyl alcohol, Synthetic hydrophilic binders such as poly-N-vinylpyrrolidone, polyacrylic acid copolymer, polyacrylamide or derivatives thereof, and partial hydrolysates are available, and these hydrophilic binders may be used alone or in combination. Can be used. These hydrophilic binders are also advantageously used to form non-photosensitive layers such as antihalation layers, interlayers, protective layers (or release layers), back layers or image-receiving layers. The binder in the silver halide emulsion layer has a weight ratio of 0.3 to silver halide converted to silver nitrate.
5, preferably in the range of 0.5 to 3. The silver halide may be any one of silver chloride, silver bromide, silver chlorobromide, or a combination thereof with silver iodide. Emulsions containing silver chloride as a main component are considered preferable for image reproduction in terms of both chemical development speed and dissolution speed. It is preferable to use a silver chloride, silver chlorobromide, silver chloroiodide, or silver chloroiodobromide emulsion containing 90 mol % or more of chloride. Silver halide emulsions can also be spectrally sensitized in blue, green, and red. It can be a merocyanine, cyanine dye or other image-sensitive dye. Furthermore, the silver halide emulsion can be chemically sensitized with various image sensitizers. For example, sulfur sensitizers (e.g. hypo, thiourea, gelatin containing labile sulfur, etc.), noble metal sensitizers (e.g. gold chloride, gold rhodan, ammonium chloroplatinate, silver nitrate, silver chloride, palladium salts, rhodium salts, iridium salt,
rutinium salts, etc.), polyalkylene polyamine compounds described in U.S. Pat. No. 2,518,698, imino-amino-methanesulfinic acid described in German Patent No. 1,020,864, reduction sensitizers (e.g., stannous chloride, etc.) are advantageous. used for. The back layer desirably provided on the back side of the support contains a hydrophilic colloid in an amount necessary to maintain curl balance with the photosensitive layer side. The amount depends on the total amount of hydrophilic colloid on the photosensitive layer side, the amount of white inorganic pigment, etc. The silver halide emulsion layer of the present invention can improve image reproducibility when combined with an antihalation layer containing a black pigment. Furthermore, when the silver halide emulsion layer of the present invention is combined with an antihalation layer containing a white pigment, image reproducibility can be improved. Furthermore, image reproducibility can also be improved when combined with an antihalation layer containing a combination of the above-mentioned black pigment and white pigment. The constituent elements of the diffusion transfer material according to the present invention may further contain various additives. For example, mercapto compounds, antifoggants or stabilizers such as tetraazaindene, saponins as surfactants, sodium alkylbenzene sulfonates, sulfosuccinic acid ester salts, anionic compounds such as alkylaryl sulfonates described in U.S. Pat. No. 2,600,831. Compounds and U.S. Patents
In addition to amphoteric compounds such as those described in No. 3133816, waxes, polyol compounds, wetting agents such as higher fatty acid glycerides or higher alcohol esters, N-guanyl hydrazone compounds,
Mordants such as quaternary onium compounds and tertiary amine compounds, diacetylcellulose, styrene-perfluoroalkylene sodium maleate copolymers, alkalis of reaction products of styrene-maleic anhydride copolymers and P-aminobenzenesulfonic acid Antistatic agents such as salts, polymethacrylic acid esters,
Matting agents such as polystyrene and colloidal silicon oxide, acrylic acid esters, film property improvers such as various latexes, styrene-maleic acid copolymers, thickeners such as those disclosed in Japanese Patent Publication No. 36-21574, antioxidants, and developers. Main drugs, PH regulators, etc. can be used. A plurality of hydrophilic colloid layers can be applied in several parts or can be applied simultaneously. Any known coating method may be used.
Not restricted. The processing liquid used in the diffusion transfer method includes an alkaline substance such as sodium hydroxide, potassium hydroxide, lithium hydroxide, trisodium phosphate, etc., a silver halide solvent such as sodium thiosulfate, ammonium thiothianate, a cyclic imide compound, Preservatives such as thiosalicylic acid, such as sodium sulfite, thickening agents such as hydroxyethylcellulose, carboxymethylcellulose, antifoggants such as potassium bromide, 1-fer-5-mercaptotetrazole, etc., developer modifiers such as polyester, etc. Oxyalkylene compounds, oniyu compounds, developing agents such as hydroquinone, 1-phenyl-3
- pyrazolidones, etc., alkanolamines, etc. can be included. However, in a highly alkaline processing solution containing this developing agent, the developing agent suffers from air oxidation and loses its effectiveness.
That is, this drawback can be largely avoided by incorporating it into the halogen silver emulsion layer and/or the hydrophilic colloid layer which has a water-permeable relationship therewith. In diffusion transfer materials containing such a developing agent, an alkaline active liquid containing no or substantially no developing agent is usually used. The DTR method using an alkaline activated liquid was developed in 1977.
-27568, Sho 47-30856, Sho 51-43778, etc. can be referred to. The present invention will be explained below using examples. (E) Examples Example 1 While maintaining an aqueous solution of inert gelatin at 60°C and stirring vigorously, an aqueous solution of sodium chloride and potassium bromide and an aqueous silver nitrate solution were simultaneously added at an addition rate of 4 ml/min. Contains % bromide,
A silver chlorobromide emulsion was prepared. These emulsion grains had an average size of 0.3μ, cubic crystal habit, and more than 90% by weight of all grains were within ±30% of the average grain size. After these emulsions were precipitated, washed with water and redissolved,
Sulfur sensitization and gold sensitization were performed using sodium thiosulfate and potassium chloroaurate. A sensitizing dye was added to the emulsion thus prepared to ortho-sensitize it, and a surfactant was added to make it up. A 110 g/ ^m3 paper support coated on both sides with polyethylene was coated with 0.3 g/m3 on one side to prevent halation.
g/m ³ carbon black, 1.0 g/m ³ hydroquinone and 0.2 g/m ³ 1-phenyl-4.4
- Gelatin 4 containing dimethyl-3-pyrazolidone
g/m ³ of the undercoat layer, and on top of that, a hardener was added to the make-up emulsion according to Table 1 to give a coated silver amount of 1.3 g/m ³ and a coated gelatin amount of 2.0 g/m ³ . An emulsion layer is provided so that the Regardless of the undercoat layer and emulsion layer, the pH is adjusted to 4.0. A gelatin layer necessary for curl control is provided on the back side of the support, and the pH of that layer is
Set it to 4.5. Uniform 50% halftone dot exposure was performed by closely photographing these samples using Dainippon Screen's plate-making camera ARTGRAPHICA 601 on Dainippon Screen's screen GN2, 150L/inch. These samples were brought into close contact with an image-receiving material and passed through a conventional processor containing the following diffusion transfer processing solution for 60 minutes.
It peeled off after seconds. The treatment temperature was 25°C. Diffusion transfer processing solution water 800ml Sodium phosphate (12H ₂ O) 75g Anhydrous sodium sulfite 40g Sodium hydroxide 5g Sodium thiosulfate (5H ₂ O) 20g Potassium bromide 1g 1-phenyl-5-mercapto-tetrazole
0.1g Make the total amount 1 with water. The treatment solutions used were a new solution and a model fatigue solution whose pH had been lowered to 10.5 with sulfuric acid.

[Table] Here, comparative compounds (1) and (2) are the following compounds, and compounds (A) and (B) are the following compounds. Comparative compound (1) Comparative compound (2) Compound (A) 2,4-dichloro-6-hydroxy-S-triazine sodium salt Compound (B) 2,4-dichloro-6-hydroxy-S-triazine potassium salt As is clear from Table 1, the new solution Both samples have the same halftone uniformity, but sample 1.2 using comparative compounds (1) and (2), which are aldehyde-based hardeners, has a lot of halftone unevenness in the model fatigue solution, whereas the present sample has a lot of halftone unevenness. Samples 3 and 4, which contain the compounds (A) and (B) of the invention and do not contain aldehyde hardeners, showed good dot uniformity even with the model fatigue solution, although it was inferior to the new solution. Ta. However, Feed 5 containing Compound (A) and Comparative Compound (2) in combination had a lot of uneven halftone dots and was added. This example demonstrates the superiority of embodiments of the present invention. Example 2 A sample was prepared in accordance with Table 2 in the same manner as in Example 1 except that carbon black was removed from the undercoat layer.

[Table] The sample was exposed to light in the same manner as in Example 1, brought into close contact with an image receiving material, and treated with a model fatigue solution in the same manner as in Example 1. (DTR development) This model fatigue solution was used in Example 1.
Mitsubishi One Step NE-
I used the same IP that had been processed and left alone, and the pH had dropped to 10.5. On the other hand, after being exposed in the same manner, it was passed through the model fatigue solution described above without being combined with the image-receiving material, and fixed with a fixing solution after 60 seconds. (chemical development). Table 2 shows the uniformity of these halftone dots. As is clear from Table 2, even in the fatigued state of the diffusion transfer developer, halftone dot unevenness does not occur in chemical development, but is a development characteristic of DTR development. This is where the effectiveness of the embodiment of the present invention lies; in other words, while sample 7 had good halftone dot uniformity, both samples 6 and 8 had a lot of halftone dot unevenness. . From this example, 2,4-dichloro-6-hydroxy-
It has become clear that embodiments containing S-triazine salts are effective in diffusion transfer methods. Example 3 In this example, the halftone dot uniformity of fatigue liquid was evaluated after a period of one month at 35° C. using a material in which the pH of the silver halide emulsion was changed. A sample was prepared in the same manner as in Example 1 except for making adjustments according to Table 3. Compound (B) 20 mg/m ³ was used as a hardening agent. 35 of these samples
After aging for one month at ℃80%RH, the halftone uniformity of the model fatigue liquid was examined in the same manner as in Example 1, and the results are shown in Table 3.
The results were obtained. As is clear from Table 3, the silver halide emulsion
If the pH is below 4.5, even after one month at 35℃,
Good

[Table] Shows good halftone uniformity, but when the pH is 5.0 or higher,
After one month at 35℃, the uneven halftone dots became more noticeable.
Therefore, it has been found that in the present invention, it is preferable that the silver halide emulsion has a pH of 4.5 or less. Example 4 This example is an example in which a hardening agent is included in the undercoat layer. except adding hardener according to Table 4.
An undercoat layer was provided in the same manner as in Example 1. Example 1 was then added, except that the hardener was added according to Table 4.
An emulsion layer was provided in the same manner as in Example 1, and further, in the same manner as in Example 1,
Provide a backing layer. The halftone uniformity of the model fatigue liquid was examined using these samples in the same manner as in Example 1, and the results shown in Table 4 were obtained. As is clear from the table, if the comparative compound (2) of the aldehyde hardener is included in the undercoat layer, the milk

[Table] Even if compound (A) was present in the agent layer, the halftone dot uniformity in the model fatigue solution was poor and there were many irregularities. (Sample 14). On the other hand, Sample 16, which is an embodiment of the present invention, showed good dot uniformity. Therefore, in this example as well, all the layers on the side coated with the silver halide emulsion contained substantially no aldehyde hardener, and 2,4-dichloro-6
It has been found that embodiments having silver halide emulsion layers containing -hydroxy-S-triazine salts give good dot uniformity even in fatigue fluids.

Claims (1)

[Scope of Claims] 1. In a light-sensitive material for diffusion transfer that is subjected to processing in a processing solution for silver salt diffusion transfer, overlapping with an image-receiving material, the light-sensitive material for diffusion transfer is placed on the surface coated with a silver halide emulsion. It is characterized by having a silver halide emulsion layer containing a 2,4-dichloro-6-hydroxy-S-triazine salt in all the layers without substantially containing an aldehyde hardener. Photosensitive material for diffusion transfer. 2. The light-sensitive material for diffusion transfer according to claim 1, wherein the silver halide emulsion has a pH of 4.5 or less. 3. The light-sensitive material for diffusion transfer according to claims 1 and 2, which is coated by adding a 2,4-dichloro-6-hydroxy-S-triazine salt immediately before coating.