JPS58147739A - Solution for processing silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a soln. for processing a silver halide photographic material prevented unevenness due to water droplets even when the material is dried at high temp. and for a short time, and reduced in stains on the surface of a support, by adding a specified siloxane compd. CONSTITUTION:A final processing soln. used for a silver halide photosensitive material contains a siloxane compd. represented by formulaI(R is lower alkyl, (l) is 2 or 3, (m) is 1, 2 or 3, and (n) is 1-15) and embodies as formulae II, III, IV. It is obtained by additionally reacting a polyoxyalkylene compd. having an unsatd. group at the end of the molecular chain and a hydroxyl group with an organohydrodienesiloxane compd. in the presence of platinum compd. A preferable amt. of it to be added is in general 0.01-30g, especially, 0.05-10g per liter of the processing soln.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a processing solution for silver halide photographic materials that prevents unevenness of water droplets on silver halide photographic materials, and more particularly, a processing solution for silver halide photographic materials that prevents stains on silver halide photographic materials. It relates to processing liquids for materials.

In general, silver halide photographic materials are subjected to various treatments after being exposed to light. In the case of black and white photographs, development and fixing are usually carried out, while in the case of color photographs, color development, bleaching and fixing are carried out. However, these processing solutions contain many inorganic and organic processing agents, and if the material is dried immediately after processing with these processing solutions, the processing agents may precipitate on the surface of the photographic material. This often has a negative effect on image storage stability.Therefore, in most cases, after processing with these processing solutions, the material is washed with water to flush out unnecessary processing agents from the photographic material. be.

As mentioned above, processing steps such as development, fixation, washing with water or color development, bleaching, fixing, and washing with water are basically required. However, if the photographic material is dried immediately after washing with water, the surface of the photographic material will not be sufficiently hydrophilic and will dry partially. The drawback is that the speeds are different and a uniform surface condition cannot be obtained.

This condition is usually called water droplet unevenness, but this defect clearly appears when a photographic material with uneven waterdrops is printed as a negative, and it also appears as a clear 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, quaternary ammonium salts, or British Patent No. 1,281
There is a flukylphenoxyborihyroxyalkylene oxide compound described in No. 619, but in both cases, the problem of ↑ under low temperature and long drying conditions has been found to some extent.

However, in recent years the photo processing process has become a high temperature rapid process.
As a result, the drying process requires high temperature and short time drying.

When dried at high temperatures and for a short period of time, new water droplet unevenness occurs, making it impractical to use conventional water droplet unevenness prevention liquids.

``For example, when a photographic material that has perforations for film feeding, such as general-use 35-day film, is treated with a conventional water droplet prevention liquid, a film of the water droplet prevention liquid is formed on the inside of the perforation. ” When drying under such conditions at high temperatures and for a short period of time, the area around the Par 7 Olasin area dries rapidly, and then the film applied to the Par 7 Olasin area ruptures, and at the same time, the water droplets from the ruptures fall onto the dry areas of the photographic light-sensitive material. A phenomenon that causes water droplets to scatter and cause unevenness appears. This phenomenon is particularly noticeable in automatic processors using a hanging system (
It is generally called a hanger automatic processing machine. 〇 Also, as a technique for preventing water droplet unevenness during such high-temperature, short-time drying, there is a known water droplet unevenness prevention liquid using a siloxane compound published in Japanese Patent Publication No. 49-46262. The processing solution becomes cloudy due to its unique properties, and if this processing solution is used immediately before the drying process, the above-mentioned uneven water droplets will occur after drying, but there will be compounds and effluents from the photosensitive material on the support surface of the photosensitive material. Also, contamination occurs in this processing solution due to the formation of chemicals brought in from before.Therefore, the purpose of the present invention is to prevent uneven water droplets during high-temperature, short-time drying, and at the same time improve /10 silver-genide photography. .

The inventors of the present invention have made various studies, and as a result, a "processing liquid for silver halide photographic light-sensitive materials C" containing at least one compound represented by the following general formula is hereinafter referred to as a water droplet unevenness preventing liquid of the present invention. ) The above objective was achieved by finding the following.゛-Material 4 Rinto general formula (wherein, R represents a lower alkyl group (for example, methyl group, ethyl group, or propyl group); ! represents 2 or 3; s
m represents 1, 2 or &'i3, and n represents an integer of 1 to 15, respectively. ) Representative examples of the compounds represented by the above general formula are listed below, but the compounds according to the present invention are not limited thereto.

Exemplary Compound CI) [1) (m) The siloxane compound can be synthesized by various conventionally known methods. A method of addition-reacting a polyoxyfulkylene compound and an organohydrodiene siloxane compound containing both in the presence of a platinum compound; A method of dehydrohalogenating a polyoxyfulkylene compound with a hydroxyl group at the end of its molecular chain and an organosiloxane compound containing an organic group having a halogen atom at the end of its molecular chain in the presence of an amine compound. Alternatively, a method may be used in which a compound obtained by an addition reaction between a terminal unsaturated group-containing polyoxyfulkylene compound and flukoxysilane is subjected to a dealcoholization reaction with trimethylsilanol in the presence of an organometallic compound such as tin, titanium, or zinc. I can list them.

In addition, when using the siloxane compound, the coexistence of the polyoxyfulkylene compound used in the synthesis is not a problem.

By containing at least one of the compounds represented by the general formula of the present invention, the time from film formation to film tearing of the Bar 7 olefin can be around (4) seconds, and it can also be used at high temperature treatment temperatures. The dissolution state of the processing liquid is very transparent, and there is no unevenness of water droplets, and there is no contamination on the front or back side of the photographic material after drying, which prevents uneven water droplets from causing any practical problems. The method and its treatment solution can be obtained.The present invention can also be applied under low temperature and long drying conditions.

The amount of the compound represented by the general formula according to the present invention is determined by the type of photographic material to which it is applied, the processing temperature, the concentration of the pH adjuster, w
e It varies depending on the concentration of additives not related to the present invention, such as stabilizer concentration, fluorescent whitening side concentration, etc., but in general, it is 0 per 11 processing liquids.
．． 01-30 F is preferable, and 0.05 to 10 g is particularly preferable. The processing temperature, pH, 1 hour, etc. of the water droplet unevenness prevention liquid of the present invention vary depending on the type of photographic light-sensitive material to which it is applied. Can be used.

Photographic materials applicable to the present invention include black and white negatives, paper, reversal photographic materials, and color negatives, paper,
Any photographic material can be used, such as a so-called external color photographic material containing a coloring agent in the reversal and processing solution.

Various developing methods can be applied to the above method for preventing uneven water droplets according to the present invention. For example, a dish developing method, a spiral developing tank method, a roller conveyance 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. As a pH adjuster, for example, boric acid,
Citric acid, phosphoric acid, sodium citrate, sodium acetate, acetic acid, sodium hydroxide, etc., hardeners such as potash bright bread, chromic bread, etc., image stabilizers such as formalin, etc.
It is optional to add various other processing agents such as various fluorescent whitening agents and color toning agents. Furthermore, by adding the compound of the present invention to other processing solutions for photographic light-sensitive materials, it is possible to prevent processing unevenness such as poor wetting of the photographic light-sensitive materials and non-uniformity in the amount of processing solution deposited. In the method according to 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 prevention liquid in the straight treatment step of the drying process, that is, in the final treatment step.

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 Sakura Color N135/20 (color negative film 3511IE11136 manufactured by Konishi Roku Photo Industry Co., Ltd.) was processed using a hanger processor 'rypg K[-1 manufactured by Noritsu Koki Co., Ltd.]
307 and processed in the next processing step.

Processing process Color developing bath 38℃ 3 minutes 15 seconds Bleaching bath
l Wash with water for 4 seconds l Set for 3 minutes and 15 seconds
Wash with water for 3 minutes and 15 seconds. Dry for 1 minute and 1 minute. Dry at 47°C ± 5°C for 16 minutes. Sakura Color is used for all treatments other than the water droplet prevention liquid. ■Processing agent type ■ (manufactured by Konishiroku Photo Industry Co., Ltd.) was used.

Other than the main component of the liquid for preventing uneven water droplets, the base liquid is a treatment liquid to which 0.4N of formalin (37%) is added per 11 parts, and conventionally known compounds and the compound according to the present invention are used. Addition [,ta.

The breakage time of the film applied to the bar 7 olefin part of the film treated with each water droplet unevenness prevention solution, the number of water droplets per film, the transparency of each treatment solution, and the degree of contamination on the back side of the film after drying. The results of the comparison are shown in Table-I below.
Show K.

As is clear from Table 1, water droplet unevenness prevention W11 for comparison
and 2, because it took more than 2.5 minutes for the film applied to Bar 7 Olaysheen to break [many uneven water droplets were observed on the surface of the film]. However, there was no transparency of the L1 treatment solution and no contamination of the film after drying. Comparative prevention liquid 3 had a fast film breakage time of 6 seconds, and there were almost no uneven water droplets, but the transparency of the prevention liquid was poor, and stains were observed on the back of the film after drying. On the other hand, water droplet unevenness prevention liquid A of the present invention.

Although the amounts of B, C, and D added are smaller than those of the comparative prevention liquids, the film breaks quickly and there is no unevenness of water droplets.
In addition, despite the addition of K in a larger amount than in Comparison Prevention Liquid 3, the transparency of the prevention liquid and the contamination of the film after drying were not observed.
It became clear that the effect was large.

Furthermore, when the number of l in the general formula increases to 4 or more, the effect of preventing uneven water droplets decreases rapidly. It can be seen that at 2 or 30, it is the most excellent liquid for preventing uneven water droplets.

Agent Yoshi Kuwahara Beautiful procedural amendment April 13, 1980 Patent + 4 Commissioner Haruki Shimada 2 Name of the invention Processing liquid for silver halide photographic light-sensitive materials: L 1ili, just the right way to live, l111, etc. Patent applicant Address Nishi-Shinjuku, Shinjuku-ku, Tokyo [1126 No. 2 Name r
'+: (127) Roku Konishi Photo Industry Co., Ltd. Agent Inspector ', LI: Location 6, Sakura-cho 1, Kuchino-shi, Tokyo, ``Detailed Description of the Invention'' column 7 of the specification subject to amendment , Contents of the amendment (1) The detailed description of the invention is amended as follows.

Claims (1)

[Scope of Claims] A processing liquid for silver halide photographic materials, characterized by containing at least one siloxane compound represented by the following general formula. In the general formula c, R4: represents a lower alkyl group. No is 2 or 3
, m represents 1, 2 or 3, and n represents an integer of 1 to 15. )