JPS593431A - Composition containing photographic processing agent for silver halide - Google Patents

Abstract

PURPOSE:To obtain a concd. soln. in which pyrazolidone and an org. antifoggant are stable over a long term by using specified amounts of glycol, dimethylsulfoxide or N-methyl-2-pyrrolidone, and water as solvents. CONSTITUTION:A solvent used in a composition contg. 1-phenyl-3-pyrazolidone and an org. antifoggant is composed of dimethylsulfoxide and/or N-methyl-2- pyrrolidone, glycol, and water. The amount of glycol is 2-25pts.wt. of the amount of dimethylsulfoxide and/or N-methyl-2-pyrrolidone, and the amount of water is 0.05-0.25pts.wt. of the total amount of glycol and dimethylsulfoxide and/or N-methyl-2-pyrrolidone.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a developer composition for silver halide photographic materials. In particular, it relates to a developer composition for rapid processing of X-ray sensitive materials.

The X-ray sensitive materials commonly used in recent years are developed in a short time of 70 seconds to IIO seconds.
The electrolyte solution contains organic antifoggants such as hydroquinone, /-phenyl-3-pyrazolidones, dialdehyde hardeners, penztriazoles, indazoles, or benzimidazoles as essential ingredients, and this also includes preservatives. As agents, sulfites, alkaline agents, small amounts of calcium chelating agents, etc. may be included.

These developing solutions are usually commercially available as concentrated solutions consisting of one to three parts, and are mixed and diluted with water before use. These concentrates may be stored for two to three years before being used, sometimes exposed to high temperatures of 0 to 0C to 0C, so they are sufficiently stable and do not suffer from loss of sensitivity, contrast, or throughput. Therefore, the composition of the processing agent in each part must be carefully considered. Regarding this, for example, G, C, Al
etag“photographic 5cienc
e andEngineer tng ″volu
It is described in me+2,2/J~coit page (/911).

If the above concentrate is composed of three parts, taking into account long-term storage stability and solubility, the first part contains hydroquinones, alkaline agents, and sulfites. sodium, potassium sulfite, potassium metabisulfite, sodium metabisulfite), the second part is phenyl-3-pyrazolidones, and the organic antifoggant is indazoles, imidazoles, etc., and the third part is dialdehyde type. Usually consists of a hardening agent.

Special care is required when handling cocote/-phenyl-3-pyrazolidones. In other words, nophenyl-3-pyrazolidones are hydrolyzed during storage in alkaline aqueous solutions, resulting in a decline in photographic performance, so dissolution in the first alkaline concentrate in which hydroquinones are dissolved must be avoided. .

However, it is known that hydrolysis occurs even in the presence of water, and that acid hydrolysis occurs particularly under strong acidity.

Further, in a developing solution system using the dialdehyde compound as a hardening agent, fogging caused by the above-mentioned dialdehyde compound is significant, so indazoles, benzimidazoles, etc. are required as an organic antifoggant. However, these organic antifoggants are difficult to dissolve in water and require an organic solvent that is miscible with water to supply them as a concentrated solution. Therefore,! It has been desired to create a structure in which the phenyl-3-pyrazolidones and the above-mentioned organic antifoggants do not change even if they are stored as a concentrated solution for a long period of time.

In addition, the specification of U.S. Patent No. 3,349,12 describes a mixed solvent system of acetic acid and water, but there are problems in that it is difficult to dissolve organic antifoggants and l-phenyl-3-pyrazolidones. It is not practical due to the problem of poor stability over time. Although a three-component mixed solvent of glycols and acetic acid and water has been used to improve solubility and manufacturing suitability, it is still insufficient in terms of stability of phenyl-3-pyrazolidones.

Therefore, an object of the present invention is to provide a concentrated solution containing /-phenyl-3-pyrazolidones and an organic antifoggant such as indazoles or benzimidazoles that is stable for a long period of time. A second object is to provide the above-mentioned concentrate which is economically efficient and has excellent manufacturing suitability.

The above objects of the present invention can be effectively achieved by the following. That is, in a photographic processing agent composition prepared by mixing a plurality of parts and containing hydroquinones, /-phenyl-3-pyrazolidone, an organic antifoggant, and a dialdehyde compound, l-phenyl-3-pyrazolidones and an organic The solvent used in the hair solution containing an antifoggant is composed of dimethyl sulfoxide and/or N-methyl-λ-pyrrolidone, glycols, and water, and the glycol is dimethyl sulfoxide and/or N-methyl-λ-pyrrolidone.
The composition is 2 to 25 parts by weight based on methyl-cobyrrolidone, and the water is 01OS to 0.25 parts by weight based on the sum of the glycols and dimethyl sulfoxide and/or N-methyl-λ-pyrrolidone. This was achieved using a photographic processing agent composition.

A wide range of studies were conducted on organic solvents capable of dissolving l-phenyl-3-pyrazolidones and the above-mentioned organic antifoggants in a highly concentrated manner, including the organic solvents described in U.S. Patent No. 3,031,10/C. However, the stability of the concentrated solution during long-term storage, especially the stability of /-phenyl-3-pyrazolidones, the stability of the solvent itself, the influence on photographic properties, solubility, cost, handleability such as odor, etc. It has now been found that a mixed solvent consisting of a glycol-dimethyl sulfoxide and/or N-methyl-cobyrolidone-aqueous system is the most superior in terms of toxicity. In this system, the glycols mentioned above-
/-phenyl-3 compared to acetic acid-water 3-component mixed solvent
- Not only is pyrazolidone excellent in stability, but also its solubility is greatly increased, so that it is possible to dissolve a part of hydroquinone in other substances, which is advantageous because it can be further concentrated. In addition, there is no problem in terms of manufacturing suitability and liquid preparation suitability in practical terms.

Examples of l-phenyl-3-pyrazolidones used in the present invention include /-phenyl-3-pyrazolidone, goomethyl-/-phenyl-3-virasoliton, ≠, ≠-dimethyl-1-7enyl-3-pyrazolidone, Hiroshi -Methyl-μmhydroxymethyl-7-phenyl-3-birasoliton, g,4A-dihydroxymethyl-7-phenyl-
3-Pyrazolidone,! -Methyl-7-7enyl-3-pyrazolidone,! , 5-dimethyl-7-phenyl-3-virazolidone, /-(41'-methyl)-7enyl-3-
One example is zolidone.

As the hydroquinones used in the present invention, other known hydroquinones may be used.

Glycols used in the present invention include ethylene glycol, diethylene glycol, triethylene glycol,
Examples include tetraethylene glycol, fluoropylene glycol, and hexylene glycol.

If the above-mentioned solvent is composed of glycols alone, the viscosity of the solvent itself is high, so there are many inconveniences in terms of manufacturing efficiency and accuracy when filling the concentrated liquid into containers in unit packaging quantities, and it is also difficult for the customers who use it. There are also many inconveniences when preparing liquids by transferring them.

Therefore, it is preferable that the viscosity of the concentrate is at most uj-centipoise or less. Furthermore, using glycols alone is disadvantageous because the amount used is large and the cost of raw materials is high.

A mixed solvent of glycols and water has a lower viscosity and improves suitability for production and liquid preparation, but it has low solubility for l-phenyl-3-pyrazolidones, so it cannot be used to create a concentrated solution suitable for the present invention. Can not.

Dimethyl sulfoxide alone has a relatively high freezing point, which causes many inconveniences in production and makes it difficult to put it into practical use. A mixed solvent of dimethyl sulfoxide and water is also excellent in dissolving each component at room temperature, but there is a problem of precipitation of each component at low temperatures (such as in cold regions). It cannot be created.

On the other hand, although the solubility of each component in N-methyl-pyrrolidone is very good, the cost of raw materials is high and it is not practical. Although a mixed solvent of N-methyl-λ-pyrrolidone-water is excellent in dissolving each component at room temperature, there is a problem with precipitation of each component at low temperatures, so it is difficult to create a concentrated solution that meets the purpose of the present invention. I can't.

A mixed solvent system of glycols-dimethylsulfoxide or glycols-N-methyl-2-pyrrolidone provides good solubility, but is not suitable for production in terms of viscosity, ease of handling (because dimethylsulfoxide has a high freezing point), etc. On the other hand, there are problems in terms of suitability for liquid preparation, making it impractical.

In the present invention, the concentrated solution heart containing /-phenyl-3-pyrazolidones and an organic antifoggant (in some cases also containing hydroquinones) is concentrated and dissolved to a higher concentration, in terms of manufacturing cost. Although preferable in terms of transportation cost, packaging container cost, and stock space, glycols and dimethyl sulfoxide and/or N-methyl-
The amount of the solvent consisting of λ-pyrrolidone is preferably from 10 to 50 parts by weight, and more preferably from /j to 30 parts by weight. The concentration of glycols added is developer solution/l after preparation.
2 to toy is preferable, and j to 30f is more preferable. In addition, the solvent composition of the part containing /-phenyl-3-pyrazolidone and the organic antifoggant is such that water is 0.10% of the sum of glycols, dimethyl sulfoxide and/or N-methyl-corbyrolidone. -0.20 part by weight is more preferable.

The concentrated liquid of the present invention mainly contains l-phenyl-3-pyrazolidones, indazoles, benzimidazoles,
This part concerns the part for dissolving organic antifoggants such as penztriazoles, but in addition to this, hydroquinone can also be dissolved in this concentrate part, and other organic agents and antifoggants can also be dissolved. You can also do that.

The organic antifoggants that are dissolved together with l-phenyl-3-pyrazolidones to form a concentrated solution include indazoles,
Henzimitasol L-<y refers to a compound that effectively prevents fogging that occurs when a dialdehyde compound is used in a developer, such as citriazole, but specific examples include: ,! - Nitroindazole! - Nitropenzimidazole (nitrate or hydrochloride), j-methylbenztriazole,! - Nitrobenttriazole, penttriazole, etc. These organic antifoggants can be dissolved in the concentrate either singly or in combination, and can also be added to other concentrate parts (for example, parts in which hydroquinone, sulfites, alkaline agents, etc. are dissolved). An inhibitor can also be dissolved and used in combination.

As a dialdehyde compound, Re5earchDi
sclosure /7za1 year v issue/4rijM, 2
Glutaraldehyde and the like described in 0≠03 are used, and these dialdehyde compounds are also used in the form of bisulfite adducts of alkali metals or alkaline earth metals.

The chelating agent (generally included in the concentrated liquid part in which hydroquinone, sulfite, and alkaline agents are dissolved) used in the developer is the above-mentioned Re5earch.
1) Nitrilotriacetic acid, ethylenediaminetetraacetic acid, and (N-hydroxymethyl)ethylenediaminetriacetic acid as described in isclosure are used.

As described above, the concentrate of the present invention is mixed with a concentrate in which other processing agent components are dissolved and mixed with water.

Dilute from j to Hiro times, pH 7.j to 10. J de one 2
It is developed from j 0C to jOoC. This development is followed by treatment with a fixer solution of pi(4) containing trivalent aluminum ions at λs 0C to ao 0C, preferably with a fixer solution of pH g to r3, and then washed with water so that ≠θ 0C Dry with hot air at 1000C.

These developing treatments are carried out in an automatic developing machine using opposed roller conveyance or staggered roller conveyance, but may also be carried out manually in a tank or vat.

The developer concentrate of the present invention is filled into containers such as polyethylene bottles or bags (part name: Cubitenar), bottles or bags made of polyethylene laminated with nylon, etc., polyester bottles or bags, vinyl chloride bottles, glass bottles, etc. After being held, it is mixed and diluted with water as described above to form a developer, and then developed.

The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto.

Example/-phenyl-3-pyrazolidone/,! f and! -Nitroindazole 0.2! A concentrated solution (partco) is made up of solvents with the composition shown in Table 1, and the solubility of each
The stability, manufacturing suitability, and solution suitability of the concentrate were evaluated.

(Note) - Solubility: Each concentrate was allowed to stand at θ0C for one week, and those in which precipitation was observed were marked with an X.

- Stability over time: Each concentrate! The sample was placed in a polyethylene container ioomt with a stopper for 00Cl and left for a month, and the change in absorbance at 350 nm was expressed as an increase rate relative to the absorbance of the concentrated solution over time. This can be evaluated as a measure of the hydrolytic stability of l-phenyl-3-pyrazolidone.

The decrease in sensitivity is expressed as logE, which is the change in the density of Capri 10 and S when the development process shown in the example was carried out using Fuji Photo Filmo's X-ray sensitive material X.

Manufacturing suitability and liquid preparation suitability: Items with a viscosity of 10 centipoise or higher, items with poor handling (due to high freezing point), or items with high raw material costs are marked with an X.

The other parts of the developer are as follows. Part 1 Ethylenediaminetetrastyl acid disodium 3rf Potassium hydroxide Potassium thiosulfite
l≠oo (1 sodium bicarbonate
l hirolamb, sg boric acid
'rifj-methylbenztriazole 1. l≠
gHydroquinone jllOf diethylene glycol, 221f/water
1. /(J) resistance 3 Glutaraldehyde 239 Sodium bisulfite 76g with water
j, 00 ml of the above part/1.
/l, Partco was dissolved in the above prescription nt, v/l, and hair-to 3 was dissolved in the order of zoo shoulder l, potassium bromide was diluted to 191 with water, potassium bromide was dissolved in the solution, and the pH was adjusted to 10 with acetic acid. ．．
The solution adjusted to /j was used as a developer for development processing.

The fixer used had the following composition.

waterjooIIIt ammonium thiosulfate coOOf sodium sulfite (anhydrous 1 20f boric acid
ry Disodium ethylenediaminetetraacetate 0.'f Potassium sodium tartrate jf Sodium hydroxide 06 Coj II Aluminum sulfate
/If sulfuric acid
,zg glacial acetic acid
λ, add 2f water /lp
H4A, t.

In addition, the processing steps are development 3z'C, 25 seconds, fixing 3j 0
It was washed for Cλj seconds, washed with water at 200C for 2θ seconds, and dried at 00C.

The following is clear from the results in Table/.

Since triethylene glycol alone has a high viscosity, it is not suitable for production and is not practical. Mixing water with triethylene glycol tends to improve manufacturing suitability, but the solubility of l-phenyl-3-pyrazones becomes poor9, which is not practical.

It is known that acetic acid ha/-phenyl-3-pyrazolidones have excellent solubility, and triethylene glycol-acetic acid systems have good solubility, but are not suitable for production because the freezing point of the solvent increases. The triethylene glycol-acetic acid-water system, which is a mixture of triethylene glycol-acetic acid and water, has excellent solubility and manufacturing suitability, but the liquid tends to be colored due to the poor stability of l-phenyl-3-pyrazolidone ( There is a problem of an increase in the rate of increase in absorbance), making it impractical.

In addition, acetic acid alone or an acetic acid-water system is poor in both production suitability and stability of l-phenyl-3-pyrazolidone, and cannot be used practically.

l-phenyl-
It can be seen that the increase in coloring due to deterioration of 3-pyrazolidones is significantly reduced. At this time, there is a preferable range for each solvent composition ratio, and if the ratio of triethylene glycol/dimethyl sulfoxide and/or N-methyl-λ-pyrrolidone is 12j or more, the viscosity is high and the suitability for production becomes poor. If you increase the water ratio to improve l-
It can be seen that the solubility of phenyl-3-pyrazolidone deteriorates and is not practical. Furthermore, if the proportion of triethylene glycol is reduced to make the solvent ratio less than λ, there will be problems with handling of dimethyl sulfoxide (high freezing point) and increased raw material costs due to N-methyl λ pyrrolidone. It can be seen that increasing the water ratio in order to eliminate this problem deteriorates the solubility of /-phenyl-3-pyrazolidone, making it impractical.

When the ratio of triethylene glycol/dimethyl sulfoxide and/or N-methyl λ pyrrolidone is 0~21 and the ratio of water to the above solvent amount is 0~0j~0.2, the solubility, stability, manufacturing suitability and It was found that all of the suitability for liquid preparation were satisfied.

Of course, in this range, the cost of the solvent is more preferable and the solubility is high, so the concentration is also lower than V-
) can be filled in a small container, which has the advantage of requiring less packaging materials, transportation costs, and storage space.

Example 2 1-phenyl-3-birasoliton1. ! Table 3 shows f and 3-nitroindazole θ, 2jf and no-hydroquinone 3f.
Concentrates (referred to as Nosate/) were prepared with the following solvent composition, and the dissolution ability, stability of the concentrate, suitability for production, and suitability for preparation were evaluated in the same manner as in Example 1.

As the photosensitive material, X-ray photosensitive material Ratio X (manufactured by Fuji Photo Film Co., Ltd.) was used.

Further, the other parts of the developer are as follows.

Noku-to 1 Ethylenediaminetetraacetic acid/Ninato 1 No. 7,
3-1 ≦l Potassium hydroxide
Potassium sulfate
/ 4'001 Sodium bicarbonate
l≠J,,! f boric acid
fj-methylbenztriazole /, /4
11 Hydroquinone V♂ty diethylene glycol -2,2Iry Add water to make s,/l. 3 Same as Part 3 of Example 1.

Further, the method of preparing a developing solution from each notebook, the composition of the fixing solution, and the processing steps were carried out in the same manner as in Example 1.

The following is clear from the results in Table 3.

As is clear from Example 1, in order to improve solubility and manufacturing suitability, triethylene glycol-acetic acid-hydrogen and triethylene glycol-dimethyl sulfoxide or N-
Methylcopyrrolidone-aqueous systems are excellent, but Samples A/ and #, in which 3 y of hydroquinone was added to these systems, could not be used due to poor solubility of hydroquinone due to acidic conditions, but Sample 16 of the present invention. A, 7.10 and l/ is the moisture ratio o, or ~ 0,2. It can be seen that it can be satisfactorily tolerated as a concentrated liquid within the range of t.

Furthermore, although hydroquinone is dissolved in Part 1 of Example 1, its solubility has almost reached the saturated range, and part of it (approximately 10 tlA) can be dissolved in the above-mentioned mixed solvent system. It is very advantageous in terms of manufacturing suitability and solution suitability.

Patent Applicant: Fuji Photo Film Co., Ltd. (Monday, 1982) - 9th Director of the Japan Patent Office, Mr. l← 1. Indication of the case: 1982 Patent Application No. 1/2371
No. 2, Title of the invention Silver halide photographic processing agent composition 3
, Relationship with the case of the person making the amendment Patent applicant Address 210-4 Nakanuma, Minamiashigara City, Kanagawa Prefecture Subject of amendment The description in the "Explanation" section is summarized below.

(1) Change the 1st bencitrian on the 82nd negative line to ``
Penztriazole” is corrected.

(2) Correct "wo" in line 17 of page 2 to "ga".

(3) Correct "3 digits" on the 3rd page/3rd line to 13.

(4) Correct “hydrogen” in the horizontal line of page 33 to “water”.

Claims (1)

[Claims] Prepared by mixing multiple parts, hydroquinones,
In the photographic processing agent composition containing /-phenyl-3-pyrazolidone, an organic antifoggant, and a dialdehyde compound, the solvent used in the part containing l-phenyl-3-pyrazolidones and the organic antifoggant is dimethyl sulfoxide and or N-methyl-copyrrolidone, a glycol, and water, the glycol is in a composition of 2 to 25 parts by weight based on dimethyl sulfoxide and/or N-methyl-λ-pyrrolidone, and the water is o, or to O, 25 for the sum of glycols and dimethyl sulfoxide and/or N-methyl-virolidone
A photographic processing agent composition characterized in that it has a composition of parts by weight. 2. A photographic processing agent composition according to claim 1, characterized in that the other parts are a part containing a hydroquinone and a part containing a dialdehyde compound. 3. In claim 1, an organic antifoggant 75
1. A photographic processing agent composition characterized by being an indazole, a benzimidazole, or a benzotriazole.