JPS6256498B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photographic processing solution that prevents uneven water droplet sagging in silver halide photographic light-sensitive materials. Silver halide photographic materials are generally subjected to various treatments after exposure. In the case of ordinary black and white photographs, development and fixing processes are performed, and in the case of color photographs, color development, bleaching, and fixing processes are performed.
In either case, many of the processing agents contained in the processing solution will precipitate on the surface of the image or have an unfavorable effect on the storage stability, so it must be removed from the surface of the photographic material. Therefore, a water washing step is provided as the final step of treatment. As mentioned above, the processing steps of developing, fixing, washing with water or color development, bleaching, fixing, and washing with water are basically required, but if the photographic material is dried immediately after washing, the surface of the photographic material will not have sufficient hydrophilicity, so it will partially dry out. The drawback is that the speeds are different and a uniform surface condition cannot be obtained.
This condition is usually called water droplet unevenness, and this defect clearly appears when a photographic material with waterdrop unevenness is printed as a negative, and also appears as an obvious defect when screen projection is performed on a reversal photographic material. In order to solve these drawbacks, many liquids for preventing unevenness of water droplets have been proposed. For example, there are water droplet prevention liquids containing ethylene glycol derivatives, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, carboxylic acid type amphoteric surfactants, quaternary ammonium salts, etc., but in any case, it is difficult to wet the surface of the photographic material. In a good way, we are looking at a solution. However, in recent years, as the photo processing process has become a high-temperature, rapid process, the drying process has also become a high-temperature, short-time drying process, which has caused a new phenomenon called uneven water droplets that cannot be prevented by using conventional water droplet unevenness prevention liquids. are doing. In particular, when a photographic material that has a perforation for film feeding, such as general-use 35 mm film, is treated with a conventional water droplet prevention liquid, a film of the water droplet prevention liquid is formed on the perforation, and the film remains exposed to high temperatures. If the photographic material is dried for a short period of time, the area around the perforation area dries rapidly, causing the film on the perforation to break and at the same time the broken water droplets scatter onto the dry areas of the photographic material, causing a phenomenon called uneven water droplet sagging. This phenomenon is particularly noticeable in a hanging type automatic developing machine (generally called a hanger automatic developing machine). Accordingly, an object of the present invention is to provide a photographic processing solution for silver halide photographic materials that can prevent uneven water droplet sagging even when drying at high temperatures and short times. According to the present invention, the above object is achieved by using a photographic processing solution containing a combination of at least one compound represented by the following general formula [] and at least one compound represented by the following general formula []. I discovered that. general formula In the formula, R ₁ is an alkyl group having 6 or more carbon atoms, R ₂ is a hydrogen atom or an alkyl group, and A is a divalent group consisting of at least one of ethylene oxide, propylene oxide, and oxypropylene oxide units, which are average polymerized. Groups with a degree of 10 or more,
Rf represents a perfluoroalkyl group having 1 to 14 carbon atoms, R represents a divalent alkylene group having 1 to 12 carbon atoms, M represents a hydrogen atom, an alkali metal, ammonium or substituted ammonium, and m
represents a number from 1 to 2.5. The oxypropylene oxide units include not only oxy-n-propylene oxide units but also oxy-iso-propylene oxide units. Next, representative examples of compounds represented by the general formula [] and general formula [] of the present invention will be listed, but the compounds of the present invention are not limited to these. Representative examples of compounds represented by the general formula [] Representative example of compound represented by general formula []-1 (C ₃ F ₁₇ CH ₂ CH ₂ O _{) 1.5} P(O)(OH-NH ₂ CH ₂ CH ₂ OH) _{1.5 -2} (C ₃ H ₁₇ CH ₂ O) _1.5 P(O) [OHNH(C ₂ H ₄ OH _{) 2} ] _{1.5 −3} (C ₃ F ₁₇ CH ₂ CH ₂ O) _{1.5 P} (O) [OHN( CH ₂ CH ₂ OH) ₃ ] ₁ . ₅ −4 (C ₆ F ₁₃ CH ₂ CH ₂ O) ₂ PO (ONH ₄ ) −5 [C ₄ F ₉ (CH ₂ ) ₄ O] ₂ PO (ONH ₄ ) −6 [C ₃ F ₇ (CH ₂ ) ₁₁ O] ₂ PO (ONH ₄ ) −7 [C ₇ F ₁₅ (CH ₂ ) ₂ O] ₂ PO (ONH ₄ ) −8 [C ₈ F ₁₇ CH ₂ CH ₂ O] ₂ PO−OH −9 [C ₁₀ F ₂₁ CH ₂ CH ₂ O] ₂ PO OH −10 [C _{6 F 13} CH ₂ CH ₂ O] _1.5 PO(ONH ₄ ) _{1.5 −11} [ C ₇ F ₁₅ CH ₂ O] ₂ PO(ONH ₄ ) Next, a general method for synthesizing the compounds represented by the general formulas [] and [] will be described. The compound of the general formula [] is produced by using a phenol compound such as alkylphenol as a raw material and converting it into ethylene oxide in the presence of a catalyst such as sodium hydroxide.
It can be synthesized by reacting propylene oxide or glycidol. In addition, the compound of the general formula [] is produced by reacting polyfluoroalcohol and phosphorus oxyhalide with the addition of water to produce a polyfluoroalkylphosphohalide as a partially hydrolyzed compound, and then It can be obtained by decomposition and reaction with alkali metal ammonium or substituted ammonium salts. Water-soluble primary, secondary or tertiary amines such as methylamine, diethylamine, monoethanolamine, diethanolamine, morpholine, triethanolamine and bisamine can also be used as bases for obtaining substituted ammonium salts. Can be done. The compound represented by the general formula [], that is, a polyalkylene oxide derivative, is known as a compound that improves wetting, and the perfluoroalkyl phosphate derivative represented by the general formula [] is known as a surfactant. It is a type of compound that The effects described above in the present invention cannot be obtained by using each of these compounds alone, but by using both compounds together. That is, even if a combination of two or more compounds of the general formula [] is used as a treatment solution, it takes 3 minutes or more from the formation of a perforation film to the breakage of the film. In this case, conventional relatively low temperature and long drying conditions (38
However, under high temperature and short drying conditions (15 min at 50°C), this is not a problem.
(around 10 minutes), uneven dripping of water droplets occurs, which poses a practical problem. And this fact can be said to be exactly the same when using only the compound of the general formula []. On the other hand, when using a photographic processing solution using a combination of compounds of general formula [] and general formula [] in the present invention, the time from the formation of a perforation film to the breakage of the film is 1 to 2 minutes. It is shortened back and forth, and even when drying at high temperature for a short time, uneven water droplets do not sag and do not cause any practical problems. The amount of the polyalkylene oxide derivative of the general formula [] and the perfluoroalkyl phosphate derivative of the general formula [] used in the present invention per processing solution depends on the type of photographic material to which it is applied,
Although it varies depending on the processing temperature, PH adjustment concentration, image stabilizer concentration, fluorescent whitening agent concentration, etc., and the concentration of additives other than the present invention, generally, 0.02 to 50 g is preferable. Further, the mixing ratio of both of the above derivatives is preferably 10:1 to 1:10. If a large amount is used in excess of the above-mentioned amount, there is a risk that the processing liquid will become cloudy or the back side of the film will be stained white, causing problems. Treatment temperature, PH, of the water droplet unevenness prevention liquid of the present invention,
Since the time etc. differ depending on the type of photographic material to be applied, it can be used under arbitrary conditions depending on the photographic material. The photographic materials applicable to the present invention include black and white negatives, paper, reversal photographic materials, color negatives, papers, reversals, and so-called external color photographic materials containing a coloring agent in the processing solution. Various developing methods can be applied to the method of preventing uneven water droplet sagging of the present invention. For example, a dish developing type, a spiral type developing tank type, a roller conveying type automatic developing machine, a hanger type automatic developing machine, a continuous type automatic developing machine, etc. can be used. Various additives can be added to the water droplet unevenness prevention liquid of the present invention as required. Examples of PH adjusting agents include boric acid, citric acid, phosphoric acid, sodium citrate, sodium acetate, acetic acid, sodium hydroxide, etc., hardening agents such as potash alum, chromium alum, etc., image stabilizers such as formalin, and various others. It is optional to add various processing agents such as fluorescent whitening agents, color toning agents, and the like. Furthermore, by adding the compound of the present invention to other processing solutions for photographic materials, it is possible to prevent processing unevenness such as poor wetting of photographic materials and non-uniformity in the amount of processing solution applied. In the method using the treatment liquid of the present invention, the purpose of preventing uneven water droplet sagging as defined in the present invention can be achieved by providing the liquid for preventing uneven water droplet sag in the treatment step, preferably immediately before the drying step. Furthermore, the water droplet sag prevention liquid of the present invention can be applied not only to photographic materials but also to various other materials to achieve the same purpose. The present invention will be specifically explained below with reference to Examples, but the embodiments of the present invention are not limited by these. Example 1 Sakura Color 135/20 (20 sheets of color negative film 35 mm width manufactured by Konishi Roku Photo Industry Co., Ltd.) was taken using a hanger processor TYPE K-1307 manufactured by Noritsu Koki Co., Ltd.
and processed in the following processing steps. Processing process Color development bath 38℃ 3 minutes 15 seconds Whitening bath 〃 4 minutes 20 seconds water washing 〃 3 minutes 15 seconds fixer 〃 4 minutes 20 seconds water washing 〃 3 minutes 15 seconds water droplet prevention solution 〃 1 minute 30 seconds drying 47℃ ±5°C 16 minutes 30 seconds Among the treatments, Sakura Color processing agent type (manufactured by Konishiroku Photo Industry Co., Ltd.) was used for the treatments other than the water droplet unevenness prevention liquid. Water droplet unevenness preventing liquids A to D below are comparative water droplet unevenness preventing liquids not related to the present invention, and E to K are water droplet unevenness preventing liquids according to the present invention. Next, Table 1 shows the composition and results of each of the water droplet unevenness prevention liquids used.

【table】

[Table] In addition to the combination of general formulas [] and [], water droplet unevenness prevention liquid G has formalin added thereto as an image stabilizer. Table 1 compares the time it takes for the film applied to the perforation portion of the films treated with each of the water droplet unevenness prevention liquids A to K to break and the number of waterdrop unevenness per film. As is clear from Table 1, it took more than 3 minutes for the film applied to the perforation to break in the comparative liquids A to D for preventing uneven water droplets, and many uneven water droplets were observed. Water droplet unevenness prevention liquid E to K of the present invention
The time required for the film applied to the perforation to break was approximately 1 to 2 minutes, and a product with no surface defects was obtained. It is clear that the effects of the present invention are not lost even when water droplet unevenness prevention liquid K is prepared by adding formalin as a color image stabilizer. Example 2 Using Konipan SS135/20 (20 pieces of black and white negative film 35 mm width manufactured by Konishi Roku Photo Industry Co., Ltd.), the following was carried out using a spiral type developing tank (King Universal roll film developing tank, manufactured by Asanuma Shokai Co., Ltd.) It was processed using the following processing steps. Processing process Development 27°C 7 minutes stop fixing 6 minutes water washing 6 minutes water droplet prevention solution 30 seconds drying 55°C ± 5°C 10 seconds The compositions of the developer and stop fixing solution are as follows. Developer solution Sodium sulfite (anhydrous) 50g 1-phenyl-3-pyrazolidone 0.5g Hydroquinone 10g Sodium carbonate (monohydrate) 50g Potassium bromide 0.2g Benztriazole 0.01g Add water 1 Stopping agent Ammonium thiosulfate 200g Sodium sulfite ( (Anhydrous) 15g Glacial acetic acid 15.4cc Borax sand 7.5g Potassium alum 15g Add water 1 The water droplet unevenness prevention liquids L to N listed in Table 2 below are comparative water droplet unevenness prevention liquids, and O is the water droplet unevenness prevention liquid according to the present invention. It is a prevention liquid. Next, Table 2 shows the composition and results of the water droplet unevenness prevention liquid.

[Table] In each treatment, the tearing time of the film applied to the perforation of each treated film and the number of water droplet irregularities on one film were compared for each of the water droplet irregularity prevention solutions L to O. As is clear from Table 2, in the comparison liquids L to N for preventing unevenness of water droplets, it took more than 3 minutes for the film applied to the perforation to break, and many unevenness of water droplets were observed. With the water droplet unevenness prevention liquid O of the present invention, the film applied to the perforation was broken in about 1 minute, and a liquid with no unevenness of water droplets and no surface defects was obtained.

Claims (1)

[Scope of Claims] 1. A photographic processing solution containing a combination of at least one compound represented by the following general formula [] and at least one compound represented by the following general formula []. general formula In the formula, R ₁ is an alkyl group having 6 or more carbon atoms, R ₂ is a hydrogen atom or an alkyl group, and A is a divalent group consisting of at least one of ethylene oxide, propylene oxide, and oxypropylene oxide units, and has an average degree of polymerization. 10 or more groups, Rf
is a perfluoroalkyl group having 1 to 14 carbon atoms, R is a divalent alkylene group having 1 to 12 carbon atoms, M is a hydrogen atom or an alkali metal, ammonium or substituted ammonium, and m is 1 to
Shows the number 2.5.