JP2859488B2 - Photographic scale inhibitor and method for preventing scale formation using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel anti-scale agent for photographic use and a method for preventing the generation of scale in a photographic light-sensitive material developing process using the same. More specifically,
The present invention provides an agent capable of effectively preventing the generation of scale in a washing tank or the like in a photographic light-sensitive material development step and the agent contained in the washing water used in the development step to effectively prevent the generation of scale. How to do it.

[0002]

2. Description of the Related Art In recent years, in the process of developing photographic light-sensitive materials, from the viewpoint of resource saving and cost reduction, in order to save the amount of water to be washed, various water-saving methods, such as washing water only when the photosensitive material passes, are used. A system for supplying water, a system for circulating water to save water irrespective of the presence or absence of a photosensitive material, a multistage washing system for replenishing a small amount of water, a batch washing system for stored water, and the like have been put to practical use.

[0003] As described above, it is well known that when a small amount of water is replenished in a washing tank or when water is not replenished, the stagnation time of the washing water becomes longer, and scale is easily generated. In particular, under the condition of high temperature and high humidity and a lot of dust, when the automatic developing machine is stopped for a long period of time, scale is remarkably generated.

[0004] Further, in an automatic developing machine part other than the washing tank, a stabilizing tank or a rinsing tank in which water stays for a certain period or more,
Alternatively, scale is generated in a developing tank or a fixing tank into which water is drained while the automatic developing machine is stopped. Further, there is a problem that the scale is similarly fixed to a portion where the scale is brought in from the washing tank by the photosensitive material, for example, a roller portion of the drying tank.

[0005] When the generation of such scales increases, the passage of the photosensitive material deteriorates, and the scales adhere to the photosensitive material and become contaminated, and the gears of the processing machine become extremely contaminated. This causes undesirable situations such as clogging of the filter.

[0006] By the way, as a causative substance of scale, for example, substances derived from photographic materials such as gelatin, gum arabic, fatty acid ester, vinyl acetate, silver chloride, silver bromide, hydroquinone, anhydrous sodium sulfite, alum, sodium thiosulfate, Borax, Boric acid and other substances derived from the developer and fixer, calcium, magnesium, silica,
Substances derived from water, such as iron, chloride, sulfide, and microorganisms, and airborne substances, such as dust and microorganisms, are known.

[0007] These scale-causing substances enter, for example, a washing tank and are combined with adhesive substances such as gelatin, vinyl acetate, polysaccharides such as levan and glucan produced by microorganisms, proteins, fats and muco-complexes. To form Further, once the sticky substance adheres to the inside of the tank or to a roller, a gear, a plate, or the like of a rack provided in the tank, the adhesion of the sticky substance in the tank becomes easy, and the dirt rapidly expands.

Conventional methods for preventing the generation of scale and removing scale are: (1) a method of changing the washing water every day to prevent the formation of scale; and (2) a wall surface such as a washing tank or a rack. A method of physically removing the scales of the gears and rollers by using a sponge, or by applying a detergent or a sodium hypochlorite solution to the sponge, and (3) disinfectant or fungicide in washing water, etc. For example, a method of containing an agent is used.

However, the method (1) is not preferable from the viewpoint of resource saving and cost reduction, and the physical removal method (2) has a problem that it is difficult to completely remove scale. ing. On the other hand, as a method for incorporating the agent (3) into washing water or the like, for example, specific isothiazolones and benzoisothiazolones (Japanese Patent Publication No. 62-39730), alcohols containing bromine and nitro groups in the molecule ( JP-A-60-11947), chlorinated isocyanuric acid or a salt thereof (JP-A-62)
Japanese Patent Application Laid-Open No. 242934/242) and aldehydes and aldehyde adducts (Japanese Patent Application Laid-Open No. 57-157242). However, although the method of incorporating these agents into washing water or the like is effective in some cases, it is not always satisfactory because of the secondary problems caused by the use of harmful substances.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a chemical agent which can effectively prevent the occurrence of scale in a washing tank or the like in an automatic photographic material developing process under such circumstances. It was done as.

[0011]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that a specific isothiazolone compound and 2-bromo-2-nitropropane-
Based on this finding, it has been found that a substance composed of a combination with 1,3-diol can convert a sticky scale substance into a non-sticky one by synergistic action and can extremely effectively prevent scale formation. Thus, the present invention has been completed.

That is, the present invention relates to the following (A):

Embedded image (Wherein R ¹ is a methyl group or an octyl group, R ² and R ³
Is a hydrogen atom or a chlorine atom, and Z is a copper salt or a magnesium salt, respectively; and (B) 2-bromo-2-nitropropane-1,3-diol as a photographic material containing as active ingredients It is an object of the present invention to provide a method for preventing scale generation in a photographic light-sensitive material developing step, which comprises adding a scale inhibitor to the washing water in the step of developing the photographic light-sensitive material.

In the scale inhibitor of the present invention,
As the component (A), an isothiazolone compound represented by the general formula (I) is used. R ¹ in the general formula (I) is a methyl group or an octyl group, and R ² and R ³
Is a hydrogen atom or a chlorine atom, respectively, which may be the same or different. Z is a copper salt or a magnesium salt, and examples of the copper salt include copper chloride, copper nitrate, and copper sulfate.
For example, magnesium chloride, magnesium nitrate, magnesium sulfate and the like can be mentioned.

Specific examples of the isothiazolone compound represented by the general formula (I) include 2-methylisothiazolin-3-one magnesium nitrate, 2-methyl-4-chloroisothiazolin-3-one magnesium nitrate,
-Methyl-5-chloroisothiazolin-3-one magnesium nitrate, 2-methyl-4,5-dichloroisothiazolin-3-one magnesium nitrate, 2-octylisothiazolin-3-one magnesium nitrate, 2-octyl-4 -Chloroisothiazolin-3-one / magnesium nitrate, 2-octyl-5-chloroisothiazoline-
3-one ・ magnesium nitrate, 2-octyl-4,5-
Examples include dichloroisothiazolin-3-one magnesium nitrate and a complex of the corresponding isothiazolone with magnesium chloride, magnesium sulfate, copper nitrate, copper chloride or copper sulfate. These isothiazolone compounds may be used alone or in combination of two or more.

The complex of the isothiazolone represented by the general formula (I) and a metal salt is represented by the general formula:

Embedded image (Wherein R ¹ , R ² and R ³ have the same meaning as described above)
The stability in water is far superior to the isothiazolones represented by Since the isothiazolones represented by the general formula (II) are decomposed with water, water cannot be used as a solvent, and as a solution dissolved in a glycol such as diethylene glycol, for example, caisson-free (Rohm & Haas, trade name), Zonene F (trade name, manufactured by Ichikawa Gosei Co., Ltd.) is commercially available.

On the other hand, the complex of an isothiazolone represented by the above general formula (I) and a metal salt is stable in water and is commercially available in the form of an aqueous solution. For example, as commercial products, there are Caisson WT, Caisson MW, Caisson LX (the above, manufactured by Rohm & Haas Co., Ltd., trade name), Zonene C (manufactured by Ichikawa Gosei Co., Ltd., trade name) and the like.

In the present invention, the compound represented by the general formula (I) used as the component (A) may be a commercially available product, or may be a magnesium salt or a salt of the isothiazolone represented by the general formula (II). Those prepared by reacting a copper salt may be used.

On the other hand, in the antiscaling agent of the present invention, as the component (B), a compound represented by the formula

Embedded image 2-bromo-2-nitropropane-1,3 represented by
-Diols are used.

By using the component (A) in combination with the component (B), the synergistic action changes a sticky scale substance to a non-sticky one, thereby effectively preventing the formation of scale. be able to. The compound represented by the general formula (I) and 2-bromo-2-nitropropane-
1,3-Diol is a drug conventionally known as an industrial bactericide, but its synergistic effect makes non-adhesive substances such as gelatin, vinyl acetate, and polysaccharides produced by microorganisms. Has never been known before.

In the anti-scaling agent of the present invention, the component (A) and the component (B) are in a weight ratio of 1:10 to 1: 1.
It is desirable to mix them in a ratio of 0: 1. If the mixing ratio is out of the above range, the object of the present invention will not be sufficiently achieved.

The anti-scale agent of the present invention may optionally contain other agents conventionally used for photographic anti-scale agents and descaling agents.

By including the thus obtained anti-scaling agent of the present invention in the washing water in the automatic developing step of the photographic light-sensitive material, the occurrence of scales in a washing tank or the like can be effectively prevented. . At this time, since the adhesive substance is always mixed during the work in which the washing water is replenished or the photographic light-sensitive material is processed, it is advantageous to have the anti-scale agent at the end of the work. There is no need to do anything special at the start of the next operation, and water may be replenished as usual. In order to obtain a better effect, it is desirable that the descaling inhibitor always be present on the working day. Also,
The amount of the anti-scale agent used is usually 0.1 to 10 ppm for component (A) and 1 to 50 ppm for component (B) in the wash water.
Is selected so as to be contained at a ratio of

[0023]

The photographic scale inhibitor of the present invention is a combination of a specific isothiazolone compound and 2-bromo-2-nitropropane-1,3-diol. The water-based scale substance can be changed to a non-adhesive substance, and the generation of scale in a washing tank or the like can be effectively prevented. It is particularly effective when applied to a washing tank of an automatic developing machine for photographic light-sensitive materials.

[0024]

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

EXAMPLE A silver halide photographic film was prepared in an average of 100 to 20 for 10 hours a day.
At a site where an automatic development process of 0 m ² was performed, the rack rollers, gears, and plates were significantly stained by water scale, and were washed once every 20 days on average. The cleaning required about 2 hours of work and required a considerable amount of work. In addition, scale was sometimes attached to the film. The amount of water in this washing tank is 30 liters, and the tap water is filtered and replenished during work.

In the washing tank, 2-methylisothiazoline-
9% by weight of 3-one / magnesium nitrate (containing 30% by weight of 2-methyl-4-chloroisothiazolin-3-one / magnesium nitrate) and 6% by weight of 2-bromo-2-nitropropane-1,3-diol As a result of adding 9 ml of the contained aqueous solution every working day after the water stoppage due to the completion of the work, the rollers, gears and plates in the washing tank and the rack were not stained for 120 days, and they could adhere to the photographic film. Not at all.

Further, the drainage system was conventionally blocked with contaminants in about 50 days. However, since the scale was no longer sticky, no contamination of the drainage pipe occurred at all for 120 days. In addition, even when the above-mentioned chemicals were present, no influence such as a change in density on the photographic film and disturbance of the image was observed.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-113539 (JP, A) JP-A-60-239748 (JP, A) JP-A-61-42660 (JP, A) JP-A-60-1985 119547 (JP, A) JP-A-3-130758 (JP, A) JP-B-62-39730 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 11/00

Claims (2)

(57) [Claims] (A) General formula (1) (Wherein R ¹ is a methyl group or an octyl group, R ² and R ³
Is a hydrogen atom or a chlorine atom, and Z is a copper salt or a magnesium salt, respectively; and (B) 2-bromo-2-nitropropane-1,3-diol as a photographic material containing as active ingredients Anti-scale agent. 2. A method for preventing scale formation in a photographic light-sensitive material development step, comprising adding the scale inhibitor according to claim 1 to washing water in the photographic light-sensitive material development step.