JPH03211546A - Method of developing silver halide recording material - Google Patents

Abstract

PURPOSE: To improve a method for developing a photographic silver halide recording element, especially elements used for an X-ray diagnosis and reprography by carrying out processing at <11.5pH with a specified developing soln. CONSTITUTION: A photographic silver halide recording element contg. a nonionic fluorinated surfactant is developed at <11.5pH with a developing soln. contg. at least 15g/l dihydroxybenzene compd., 0.15mol/l alkali metallic sulfite and 0.1g/l wetting agent. When the element is developed with a roll developing device, a recorded image is not deteriorated by the presence of light spots.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application Photographic silver halide recording elements of the present invention, especially X-
This invention relates to a method for developing materials used in radiographic diagnosis and reprography.

BACKGROUND OF THE INVENTION DeGeest, U.S. Pat. No. 3,754,924, discloses a photosensitive silver halide emulsion layer and a nonionic
The preparation of photographic silver halide recording elements by coating a flexible support with an outer coating containing a bare surfactant is described. The resulting element has many advantages, including the property that it has a low tendency to build up static electricity.

However, when such elements are developed on a roll developing device, the recorded image is a bright spot (
) is impaired by the presence of These bogs come in a variety of shapes and sizes and irregular distribution. These are extremely troublesome, as they can lead to errors in, for example, X-ray diagnosis. These occurrences are due to c′ of 15 g/L or more.
This is especially true when concentrated developers containing citroquine benzene developers, such as hydrokyl, and an alkali metal sulfite of 0.15 mol/L or more are used with pi values not greater than 11.5.

Such developers are preferred for use in roll development equipment because of their stability, activity, and efficiency (see, eg, F., A., Mason).

“Processing Chemistry, 7
(See table on p. 151, published by Karpres, 1966).

The above problem has been solved by using at least one photographic silver halide recording element containing a nonionic fluorinated surfactant.
It has been found that this can be overcome by development using a developer containing 5 g/L of a dihydroxy/benzene compound, at least 0.15 mol/L of an alkali metal MWt salt, and a wetting agent as described below.

According to the invention, the development of a photographic silver halide recording element consisting of a support carrying at least one silver halide emulsion layer and containing a nonionic fluorinated surfactant is carried out at least 15 g/L of dihydroxy Said silver halide record by treatment at a pH not greater than 11.5 with a developer comprising a benzene compound, at least 0.15 mol/L alkali metal sulfite, and a wetting agent at a concentration of at least 19/L. A method of developing an element is provided. The preferred pH range is 9
~11.5.

The wetting agent in the developer should be chosen so that it can be transparently dissolved in the developer at a concentration of at least O,ly/L. Wetting agents that simply disperse are unsuitable because they promote sludge formation and contaminate the developed element. There is basically no upper limit to the concentration, but for practical reasons (foam generation, cost, etc.) it should not exceed 10 g/L. The preferred concentration range of wetting agent is 0.5 g/L or more.

Anionic wetting agents are preferred for carrying out the method of the invention. These generally dissolve more easily in weakly alkaline developers than cationic or nonionic wetting agents. Moreover, they generally have less effect on photographic results than cationic wetting agents.

The following wetting agents were found to be particularly good for carrying out this method: (0011 C11, -CI+ COO+1 N-CO-CH, -CI+ (1,1) HCo+c; 11 CIllCIl, C00- c, I+,,-)1 2Na" (I, 2) CH, CH, COO- The following mixture (1,3) where R is alpha C3° alkenyl (trade name Dow7 3B2, manufactured by Dow Chemical Netherlands).

CH.

C,,H,,-Co-N-CH,-COONa (
1,4) The wetting agent concentration in the developer solution generally decreases somewhat during use as it is removed for developer replenishment and by absorption of the silver halide element being processed. This is especially true when starting concentrations are low. Therefore, in order to maintain a constant low concentration, it is effective to inject an aqueous solution of a wetting agent into the developer replenisher line or developer tank depending on the throughput of the material.

The silver halide recording element can contain any silver halide emulsion layer known to those skilled in the art, but
Particularly useful are those for X-rays. A protective layer of a hydrophilic colloid, such as gelatin, is preferably present as an outer layer of this element. Although gelatin is the preferred hydrophilic colloid material, other hydrophilic colloidal materials or mixtures thereof may also be used, such as hydrophilic natural colloids, modified hydrophilic natural colloids, or synthetic hydrophilic polymers. More particularly, these colloids include film-forming natural or modified natural hydrophilic colloids such as glue casein, zein, hydroxymethylcellulose, carboxymethylcellulose, methylcellulose, carboxymethylhydroxymethylcellulose, gum arabic, sodium alginate and the like. and hydrophilic derivatives of colloids. These also include synthetic hydrophilic polymers such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyvinylamine, polyethylene oxide,
One may also choose from such materials as polystyrene sulfonic acid, polyacrylic acid, hydrophilic copolymers and derivatives of these polymers, and the like.

Fluorinated nonionic surfactants within the scope of this invention useful in photographic silver halide recording elements include polyalkylene oxide moieties and partially or fully fluorinated alkyl or aryl moieties, such as ether Or, it has a molecule preferably composed of those linked by a crosslinking group such as sulfonecarbamide. Examples of such surfactants include, for example, F(CF, CF2)Ill-CH2CH2-0-(CH
, CH2-0-)I□Hm-2-8 (trade name “
Zonir”FSN.

Manufactured by E.I. DuPont) (11
,1)F(CF2)n (CHzCHx-0-)mHn
= 6.8 or 10 and m-6 to 12 (trade name "Rodyne 5107", manufactured by Civer Geigi) (II, 2) CJ
ll-502-N(CH3)-Co-0-(CJCH2
-0-)+5-C4Hs (trade name FT2+9. Bayer AG) (II, 3) Other fluorinated nonionic surfactants are also useful, and these can be used in a hydrophilic colloid protective layer such as gelatin with about 1- It is present in an amount of 125 mg/m'.

The method of the present invention allows the advantageous effects of fluorinated nonionic surfactants on the properties of silver halide materials to be exploited without limitation.

The method of the invention is suitable for photographic silver halide recording materials, especially for X-
It can be used in the field of medical diagnostics using lines and repgraphs.

Examples will be shown below, but the invention is not limited thereto.

EXAMPLE A silver iodobromide emulsion having crystal grains with an average grain volume of 0.4 μm and an iodide content of 2 mol % was coated on both sides of a polyethylene terephthalate support.

The emulsion contains 100 g of gelatin per mole of silver and contains the usual additives for chemical sensitization and stabilization and the usual coating aids. The silver coating amount on each side is 2.6 g/m'. A protective gelatin layer was coated over the emulsion layer on both sides at a coating weight of 1.3 g/II+2.

In addition, the protective layer includes various types of 7 types as shown in the table below.
Add a nonionic surfactant.

A 35X43cII+ sheet of each test film,
Exposure was performed so that the optical density after treatment was between 1 and 2.

Exposure: Each sheet was processed in a roll developer with one of the following developer formulations and a commercially available fixing bath at 34°C for a total processing time of 90 seconds. Hydroquinone (g/L) Alkali metabisulfite (mol/L Benzotriazole Cmg/L) Phenylpyrazolidone (g/L) Potassium bromide (g/L) Potassium hydroxide (g/L) Boric acid (g/L) 'L) SOl ) 25.0 0.22 5 1.7 6.0 50.0 10.5 0 0, 10 5 1.7 6.0 50.0 10.5 Wetting agents shown in the table below The developed film sheet was inspected for the presence of white spots using a light box for observation. The results are shown in the table below.

The solubility of comparative wetting agents A, B and C is less than 1 g/L in the developer of formulation A. The structural formulas of these compounds are as follows.

Claims (1)

[Scope of Claims] 1) A photographic silver halide recording element comprising a support carrying at least one silver halide emulsion layer and containing a nonionic fluorinated surfactant, containing at least 15 g/L of of a dihydroxybenzene compound, an alkali metal sulfite of at least 0.15 mol/L and a wetting agent at a concentration of at least 0.1 g/L.
A method of developing said silver halide recording element by processing at a pH not greater than 1.5. 2) The method of claim 1, wherein the wetting agent is an anionic wetting agent. 3) The concentration of wetting agent dissolved in the developer is at least 0.
．． The method according to claim 1, wherein the amount is 5 g/L. 4) The concentration of wetting agent dissolved in the developer is at least 0.
．． 3. The method according to claim 2, wherein the amount is 5 g/L. 5) The method of claim 1, wherein the wetting agent is represented by one of the following formulas: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ( I , 1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( I , 2) The following mixture ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ( I , 3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ R is alpha C_1_0 alkenyl. ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I, 4) 6) The method according to claim 3, wherein the wetting agent is represented by one of the following formulas. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ( I , 1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ ( I , 2) The following mixture ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ and ( I , 3) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ R is alpha C_1_0 alkenyl. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I, 4)