JPS606504B2 - Processing liquid for silver halide photographic materials - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a photographic processing solution for preventing unevenness of water droplets in silver halide photographic materials and a method for preventing unevenness of water droplets. Silver halide photographic materials are generally subjected to various treatments after exposure, such as development and fixing in the case of black and white photographs, and color development, bleaching and fixing in the case of color photographs. However, these processing solutions contain many inorganic and organic processing agents, and if the photographic materials are dried immediately after being processed with these processing solutions, the processing agents may precipitate on the surface of the photographic material or affect the image preservation. Often causes negative effects. Therefore, in most cases, after processing with these processing solutions, the photographic material is washed with water to flush out unnecessary processing agents.
As mentioned above, basically development, fixing, washing with water or color development,
It requires bleaching, fixing, and washing, but if it is dried immediately after washing, the hydrophilicity of the surface of the photographic material is insufficient, so the drying speed differs in some areas, making it impossible to obtain a uniform surface condition. 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, ethylene glycol derivatives, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, carboxylic acid type amphoteric active agents,
There are water droplet prevention liquids containing quaternary ammonium salts, etc., but in either case, a solution has been found by improving the wetting of the surface of the photographic material. However, in recent years, as photographic processing processes have become high-temperature and rapid processes, the drying process is also required to be high-temperature and short-time drying. It has become clear that when drying at high temperatures and for a short period of time, new water droplet unevenness occurs and that the water droplet unevenness prevention liquid used in the past is not practical. In particular, the present inventor has developed a film that has a perforation for film feeding, such as a general-purpose 35-rib film.
When a photographic material is treated with a secondary water droplet prevention liquid, a film of the water droplet prevention liquid is formed on the perforations. We have discovered a phenomenon in which the membrane stretched over the oration ruptures, and at the same time the torn water droplets scatter onto the dry areas of the photographic material, causing uneven water droplets. ) occurs conspicuously.
Therefore, it is an object of the present invention to provide a processing solution for silver halide photographic materials that can prevent unevenness of water droplets even during high-temperature, short-time drying. Yet another object is to provide a method for preventing water droplet unevenness in silver halide photographic materials. As a result of various studies, the present inventors found that by treating with a treatment liquid containing a combination of at least one compound represented by the following general formula [1] and at least one compound represented by the following general formula [D], It was found that the purpose was achieved. General formula [1] General formula [B] (In the formula, R is an alkyl group having 8 or more carbon atoms, preferably an alkyl group having 8 to 20 carbon atoms, R2 is a hydrogen atom or an alkyl group, and a preferable alkyl group is is an alkyl group having up to 20 carbon atoms, R3 is an alkyl group having up to 5 carbon atoms, a phenyl group, or an aralkyl group, R4 is a hydrogen atom or an alkyl group having up to 5 carbon atoms, and A and B are ethylene oxide and propylene, respectively. Represents a divalent group consisting of at least one of oxide t and oxypropylene oxide units, the average degree of polymerization of A is 10 or more, preferably from 10 to 50, and the average degree of polymerization of B is 5 or less.) The above oxypropylene The oxide unit includes oxy-n
-propylene oxide units as well as oxy-lso
-Propylene oxide units are also included. Next, representative examples of compounds represented by the general formula [1] and general formula [b] 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 general formula [1] 1-1 1-2 1-3 1-4 1-5 1-6 ・1-7 1-8 1-9 t・10 Represented by general formula [U) Representative examples of compounds D-I □-2 □-3 □-4 □-5 □-6 〇17 D-8 □-9 □-10 Low 11 ○-12 □-13 U-14 Mouth-1 D- I Next, the above general formula [1] or

An example of the method for synthesizing the compound [0] will be given. General formula [1] and

The compound [0] can be obtained by reacting a phenol compound such as alkylphenol as a raw material with ethylene oxide, propylene oxide, glycidol, etc. in the presence of a catalyst such as sodium hydroxide. When the compounds represented by the general formula [1] and the general formula [D] of the present invention are each used alone, and when the one-day group of the compound represented by the general formula [1] and [D] is changed to -S03Na ,
When at least two types of compounds of general formula [1] are combined,
Or general formula

When at least two kinds of compounds [0] are combined, the time from the formation of a perforation film to the breakage of the film requires 3 minutes or more. In these cases, the drying method can be applied without causing any problems under the conventional low temperature and long drying conditions (4000 or less and around 30 minutes). However, under conditions of high temperature and short drying time (approximately 5,000,015 minutes), the above-mentioned new water droplet unevenness occurs and it cannot be put to practical use. By using the compounds of general formula [1] and general formula [b] in combination, the present invention shortens the time from perforation film formation to film tearing to around 1 minute, making it practical even in high-temperature, short-time drying. The present invention provides a method for preventing uneven water droplets and a treatment solution thereof that causes no problems. Furthermore, the present invention can be similarly applied under low temperature and long drying conditions. The amount of the compounds represented by the general formulas [1] and [n] used in the present invention per treatment solution is:
Type of photographic material to be applied, processing temperature, pH adjuster concentration,
Although it varies depending on the concentration of additives other than the present invention, such as the concentration of the image stabilizer, the concentration of the light brightener, etc., 0.02 to 50 g is generally preferable. Also, general formula [1] and general formula

The mixing ratio of [0] is preferably 10:1 to 1:10. However, it is not limited to this range. The processing temperature, FH, time, etc. of the water droplet unevenness prevention liquid of the present invention vary depending on the type of photographic material to which it is applied, so it can be used under arbitrary conditions depending on the photographic material. Photographic materials applicable to the present invention include black and white negatives, paper,
All kinds of photographic materials can be used, including reversal photographic materials, color negatives, vapors, 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 water droplet unevenness 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 moving 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 shelf acid, citric acid, phosphoric acid, sodium citrate, sodium acetate, acetic acid, sodium hydroxide, etc.; hardeners such as potash alum, chromium alum, etc.;
Image stabilizers such as formalin, various other optical brighteners,
It is optional to add various processing agents such as color brighteners.
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 the photographic material and non-uniformity in the amount of processing solution applied.
In the method of the present invention, the purpose of preventing water droplet unevenness as referred to in the present invention can be achieved by providing a water droplet unevenness preventing liquid preferably in the treatment step immediately before the drying step. Further, the water droplet unevenness 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 D 135/20 (color negative film 35 Yanagi width 2, female photographed, manufactured by Roku Konishi Photo Industry Co., Ltd.) was processed in the following processing steps using a hanger coloring machine TYPEKO-1307 manufactured by Noritsu Koki Co., Ltd. Processing process Color development: 38°C 3 minutes 15 seconds White bath 4 minutes 20 seconds Water wash 3 minutes 15 seconds Fixing solution
Wash with water for 4 minutes and 20 seconds. Apply water droplet prevention liquid for 3 minutes and 15 seconds. Dry for 1 minute and 30 seconds. Dry at 47℃ and 5℃ for 16 minutes and 30 seconds. For each treatment other than the water droplet prevention liquid, use Sakura Coloro treatment agent. Type W (manufactured by Konishiroku Photo Industry Co., Ltd.) was used. The water droplet unevenness preventing liquids A to D shown below are comparative water droplet unevenness preventing liquids not related to the present invention, and E to F are water droplet unevenness preventing liquids according to the present invention. Next, the composition of each of the water droplet unevenness prevention liquids used is shown. Treatment liquid A Exemplary compound 1-2 1 g
Add water 1 and Treatment Solution B Exemplified Compound RO-16 1 g Add water 1 Treatment Solution C 0.5 g Exemplified Compound RO-16 0. Add water syneresis 1. Treatment liquid D Exemplary compound 1-2 0.5g.
Add 5 g of water 1. Treatment liquid E Exemplified compounds 1-2 0.5 g Exemplified compound R 16 Add 0.75 g of water 1. Treatment liquid F Exemplified compounds 1-2 0. Rudder Exemplary Compound Rho 16 0.75g Formalin (37%) Add 8g water
1. The time taken for the film applied to the perforation part of the film treated with each of the water droplet unevenness prevention liquids A to F to break and the number of water droplet unevenness per film were compared. The results are shown in Table 1 below. In addition, water droplet unevenness prevention liquid C,
D includes the general formula [1] of the present invention as a comparative compound,
In place of -A-day and 1B-day of [B], 1A-S03N
A compound substituted with a,-B-S03Na was used. Water drop unevenness prevention liquid F is an example in which formalin is added as an image stabilizer to the combination of general formulas [1] and [b].
- -- - As is clear from Table 1, in the comparison liquids A to D for preventing uneven water droplets, it took more than 3 minutes for the film applied to the perforations to break, and many uneven water droplets were observed. In the liquids E to F for preventing unevenness of water droplets of the present invention, the film applied to the perforation was broken in about 1 minute, and liquids with no surface defects were obtained. It is clear that the effects of the present invention are not lost even in the water droplet unevenness prevention liquid F to which formalin is added as a color image stabilizer. Example 2 Using Konipan SS 135/20 (black and white negative film 35 Yanagi width 2, manufactured by Konishi Roku Photo Industry Co., Ltd.), a spiral developing tank (King Universal roll film developing tank, manufactured by Asanuma Shokai Co., Ltd.) was used. ) was processed in the following two processing steps. Processing steps Development 27°C 7 minutes stop Fixing ``6 minutes Washing'' 6 minutes Water droplet prevention liquid 30 seconds Drying 55°C 15°C 10 seconds The compositions of the developer and stop fixer are as follows. Developer Sodium sulfite (anhydrous) 50g 1-phenyl-3-pyrazolidone 015g Hydroquinone log Soda carbonate (monohydrate) 50g Potassium bromide
Add 0.2g benztriazole 0.01g water
1 Stop fixing solution Ammonium thiosulfate 200g Sodium sulfite (anhydrous) i5g Glacial acetic acid
15.4CC shelf sand
7.5g potash alum
Add 15g water
1. The water droplet unevenness preventing liquids H to J below are comparative water droplet unevenness preventing liquids that are not related to the present invention, and K is a water droplet unevenness preventing liquid according to the present invention. Next, the composition of the water droplet unevenness prevention liquid used is shown. Treatment liquid I Exemplary compound 1-6 1 g Add water 1 Treatment liquid J Exemplary compound R 9 1 g Add water 1 Treatment liquid K Exemplary compound 1-6 0.5 g Exemplary compound D
-9 Add 0.5g water
1. In each treatment, the time taken for the film applied to the perforation of each treated film to break and the number of water droplets on one film were compared for each of the water droplet unevenness prevention solutions H to K. The results are shown in Table 2 below. Table 2 As is clear from Table 2, the comparative water droplet unevenness preventing liquids H to J took more than 3 minutes to break through the perforated film, and many uneven water droplets were observed.

Claims (1)

[Scope of Claims] 1. A silver halide photographic material containing a combination of at least one compound represented by the following general formula [I] and at least one compound represented by the following general formula [II] processing liquid. General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. group, R_3 is an alkyl group having 5 or less carbon atoms, a phenyl group, or an aralkyl group, R_4 is a hydrogen atom or an alkyl group having 5 or less carbon atoms,
A and B each represent a divalent group consisting of at least one of ethylene oxide, propylene oxide, and oxypropylene oxide units, and the average degree of polymerization of A is 10.
As mentioned above, the average degree of polymerization of B is 5 or less. )