JPH06332125A - Processing method of industrial x-ray film of prehardened silver halide photography - Google Patents

Abstract

PURPOSE: To produce a film hardly causing a damage on a film surface due to adherence during treatment, consequently, the film giving an image increased in diagnostic value. CONSTITUTION: In an image forming method in which an industrial silver halide photographic X-ray material is exposed, and the material is treated with an automatic treating machine in a developer which does not contain a curing agent and a fixing liq. which does not contain the curing agent, and the material is washed and dried by infrared ray drying means in a film drying station, a supporting body, at least one gelatine silver halide emulsion layer at its at least one side and at least one non-photosensitive protective stress preventive layer are incorporated in the material, and at least one kind polyoxyalkylene compd. is incorporated in these layers, and an amount of the silver halide per 1m<2> at one side is equivalent to 2-20g silver nitrate, and the material is cured with at least one kind vinylsulfon compd.

Description

Detailed Description of the Invention

FIELD OF THE INVENTION The present invention relates to halogenation by imagewise exposure followed by processing in an automatic processor filled with hardener free chemicals and processing in a drying station with a processor having infrared drying means. It relates to a method of making images on silver photographic industrial X-ray film.

BACKGROUND OF THE INVENTION For industrial radiography, the normal processing cycle is characterized by the following steps: development at 28 ° C. and fixing at 26 ° C., washing and drying. Developers usually consist of three concentrates to be diluted to the correct concentration: alkaline solution A contains hydroquinone, acidic solution B is 1-phenyl-.
The acidic solution C contains 3-pyrazolidinone and contains glutardialdehyde as a curing agent. The need for a complex three-part packaged developer concentrate is that glutaraldehyde tends to react with 1-phenyl-3-pyrazolidinone, that this pyrazolidinone is unstable in alkaline media, And glutaraldehyde by virtue of their tendency to polymerize in alkaline media. The fixer consists of two concentrated solutions,
Thus, solution A contains the commonly used highly active ammonium thiosulfate as fixing agent and solution B contains aluminum sulphate as hardening agent. Hardeners are necessary to guide the film through the processor without damaging it, thus reducing water uptake and, consequently, drying time and increasing drying capacity.
This is especially important for industrial X-ray films, because these films contain large amounts of eg about 30 g.
This is because it is coated with gelatin / m ² . The large amount of gelatin is a result of the need to have a large coverage of silver halide crystals capable of absorbing linear X-rays in industrial X-ray applications.

Film damage in the processor is due to the phenomenon of sticking, which can occur, for example, by improper drying methods.
The drying process can be improved, for example, by using an infrared dryer.

From an environmental and economic point of view, it has become important to move away from the idea of hardener-containing treatment solutions and to act in a user-friendly manner.

The removal of the toxicologically questionable glutaric dialdehyde from the developer and the removal of aluminum sulphate from the fixer can provide the user with a packaged drug. From an environmental point of view, the particular advantages resulting therefrom are the reduction of packaging waste and the convenient processing for users who do not require the production of a mixture of two or three separate parts before the start of the processing cycle. .

Besides the small number of packages to be processed and the small number of products, there is also a reduction in the total cost to the user, which is considered a great economic advantage. Finally, and not a little, the practical advantages arise in automated processors such as less crystal formation on the rollers and less sludge in the processing solution resulting in less dust on the film surface.

However, the introduction of hardener-free treatment chemicals is not limited to the use of infrared dryers, even when the film should be cured with formaldehyde as a well-known and often used hardener. Reduces drying capacity in the processor. The phenomenon of sticking of the film on the transport rollers causes distortion of the image and must be outstanding in giving the image quality, especially details, for diagnostic purposes such as inspection of weld seams for applications such as pipelines. In order to make them unusable.

OBJECT OF THE INVENTION It is an object of the present invention to image by treating industrial X-ray film with a curing agent-free treatment chemical in an automatic processor with infrared drying means in a drying station to improve drying. To provide the law.

In connection therewith, another object of the present invention is to provide a film which exhibits improved physical surface properties, which causes damage to the surface of the film due to sticking during the processing. Without having to have an increased diagnostic value in the resulting image.

Further objects of the present invention will be apparent from the following description.

SUMMARY OF THE INVENTION In accordance with the present invention, a silver halide industrial X-ray photographic material is exposed and the material is processed in a hardener-free developing solution and a hardening-free fixing solution in an automatic processor, followed by Providing an imaging method by washing and drying in an infrared drying means in a film drying station, said material comprising a support, and on at least one side thereof at least one gelatin silver halide emulsion layer and at least one. Including one non-photosensitive protective antistress layer, on one side, the total amount of silver halide per 1 m ² corresponds to 6 to 20 g of silver nitrate, said material being hardened with at least one vinyl sulfone compound ,
This is characterized by reducing the water uptake of the treated film just before drying to less than 2.5 g water per gram coated gelatin. Furthermore, by adding a polyoxyalkylene compound to at least one of the hydrophilic layers of the photographic material and / or during processing of said material in an automatic processor, a hardener-free developer serves as a surfactant and at least one anion. Further improved physical surface properties can be obtained if they contain a soluble alkylphenoxy and / or alkoxypolyalkyleneoxyphosphate ester, sulphate ester, alkylcarboxylic acid, sulphonic acid or phosphonic acid and / or salts thereof.

DETAILED DESCRIPTION OF THE INVENTION According to the present invention, the gelatin binder of the X-ray material for silver halide photographic industry is hardened with a vinyl sulfone type hardener.
Particularly preferred are di- (vinyl-sulfonyl) -methane and ethylene-di-vinyl sulfone. Contrary to aldehyde-based curing agents such as formaldehyde, vinyl sulfone-based curing agents used to cure industrial X-ray materials are automated using infrared dryers as drying means in the drying area of automatic processing equipment. It does not show the disadvantageous sticking phenomenon between the film and the roller in the dry area of the processor.

The hardener may be added to the coating composition of the emulsion layer and / or the protective composition of the protective antistress layer before or during the coating treatment. If a curing agent is added during the coating process, it is further possible to make a correction to the water uptake of the material that has to be coated by controlling the water uptake on the already coated material immediately after coating.

Hardening is preferably such that when the photographic material is washed at the end of the processing cycle immediately before drying, less than 2.5 g of water is absorbed per gram of coated gelatin.

According to the present invention, the silver halide emulsion coated in the silver halide emulsion layer contains silver chloride, silver chlorobromide, silver chlorobromoiodide, silver bromide or silver bromoiodide. . Suitable silver chloride and silver chlorobromide emulsions are described, for example, in EP application no. 91202761.2.

Silver bromoiodide emulsions containing at most 10 mol% silver iodide, preferably at most 3 mol% silver iodide, more preferably 1 mol% silver iodide are preferred. Equiaxed silver halide crystals commonly used for industrial radiographic materials and known to have good development characteristics in relation to high sensitivity, especially silver bromoiodide emulsions with cubic habit are used. Preferably. The parameter that determines whether cubic to octahedral crystals are formed during the precipitation process of the emulsions produced is the pAg of the solution.

The pAg of the solution can be adjusted by any means known in the art of emulsion manufacture, such as the electronic controller and method described in US Pat.

Bunsengesellschaft fuer physikalisch
e Chemie Brechte Vol. 67, 947-957 (1963)
No.) 9, 10 E. Moisar and K. Klein, Der Einfluss der Wachstumsbedingungen auf
From die Kristalltracht der Silberhalogenide (effect of growth conditions on crystal behavior of silver halide),
When tetradecahedral crystals of a homodisperse silver bromide emulsion were grown by the controlled addition of a solution of silver nitrate and potassium bromide, cubic crystals were obtained under the condition of a slight excess of bromide concentration in the solution phase. It is known to be obtained. A preferred embodiment of making the emulsions used in accordance with the present invention involves the preparation of high sensitivity silver bromoiodide emulsions as these X-ray emulsions by precipitation under double jet conditions. At present, the method for producing a homogeneous silver halide emulsion has a special control device for adjusting the shape of the silver halide crystal to be formed, but the shape is mainly determined by the pAg value and the temperature of the reaction vessel, and the silver ion concentration is Research Disclosure 10308
It can be kept constant during precipitation by using a special inflow method as described in.

The average grain size of the silver halide emulsions made according to the invention is preferably between 0.1 and 1.0 μm. The grain size of silver halide is, for example, The Photographic
Journal, 69 (1939), pages 330-338.
As published by Trivelli and S. Smith, and ASTM symposium on light microscopy 195
3rd year, as published by Loveland on pages 94-122, and by Mees and James, The Thesry of
It can be measured using conventional methods as described in the photographic process (1977), Section II.

In order to obtain a reproducible grain size, especially the flow rate and concentration of the solution, the temperature and the pAg must be adjusted very carefully. Grain growth inhibitors or accelerators can be added from the beginning or during the production of the emulsion crystals.
The initial conditions during precipitation allow one to make monodisperse emulsions as desired for the present invention. Monodisperse emulsions, as opposed to heterogeneous dispersions, are at least 95% by weight or number of grains.
Within about 40% of the average particle diameter, preferably about 30%
Characterized in the art as an emulsion having a diameter of within, more preferably within about 10-20%.

Silver halide grains having a very narrow grain size distribution can therefore be obtained by strictly controlling the conditions for producing silver halide grains using the double jet method. In such a method, a water-soluble silver salt such as silver nitrate and a water-soluble halide such as a mixture of potassium bromide and potassium iodide are added to a rapidly stirred aqueous solution of a silver halide peptizer, preferably gelatin, a gelatin derivative or other protein peptizer. Silver halide grains are made by the simultaneous inflow of an aqueous solution. Colloidal silica may be used as protective colloid as described in EP application 320992.

In a preferred embodiment, the addition rates of silver nitrate solution and halide salt solution are steadily increased so that re-nucleation does not appear in the reaction vessel. This method
It is especially recommended not only for avoiding physical ripening of the silver halide crystals during precipitation, the so-called Ostwald ripening phenomenon, which also leads to an expansion of the silver halide crystal distribution, but also for saving time.

Once the grains have reached their ultimate size and formation, the emulsion is generally washed after aggregation to remove grain formation and grain growth by-products. It can be varied during washing to remove excess water soluble salts, but with the use of flocculants such as polystyrene sulphonic acid 3.7-
A wash is applied with a pH value lying between 3.0. Emulsions are diafiltered through a semipermeable membrane, also called ultrafiltration.
Ion) cleaning, thus eliminating the need for the use of polymeric flocculants which can disturb the stability of the coating composition before, during and after coating. This method is described, for example, in Research Disclosure Vol. 102 (197).
October 2), Item 10208, and Research Dis
Closure 131, Item 13122, and Mignot, US-P 4334012. Preferably, at the start of ultrafiltration, without any adjustment step,
No pH and pAg adjustments are made to keep the pH and pAg to the same extent as at the end of the previous precipitation.

According to the present invention, the emulsions are prepared by the acid coagulation method using an acid coagulable gelatin derivative or an anionic polymer compound, or when precipitation occurs in a silica medium,
It is preferred to wash with a polymer capable of forming hydrogen bridges with silica in an amount sufficient to form aggregates which can coagulate with silica particles as described in EP application 517961.

The coagulation method using an acid coagulable gelatin derivative is described in, for example, US-P 2614928, US-P 261492.
9 and US-P2728662. The acid-coagulable gelatin derivative is a reaction product of gelatin with an organic carboxylic acid or sulfonic acid chloride, a carboxylic acid anhydride, an aromatic isocyanate, or a 1,4-diketone. The use of these acid-coagulable gelatin derivatives is generally carried out in an aqueous solution of the acid-coagulable gelatin derivative, or in an aqueous solution of gelatin to which acid-coagulable gelatin is added at a ratio sufficient to impart acid coagulability to the whole, Precipitating the silver halide grains. Alternatively, the gelatin derivative can be added after the emulsification step in normal gelatin, and even after the physical ripening step, provided that it is added in an amount sufficient to allow it to aggregate under acidic conditions. Examples of acid-coagulable gelatin derivatives suitable for use in accordance with the present invention can be found in, for example, the aforementioned US patent specifications. Particularly suitable are phthaloyl gelatin and N-phenylcarbamoyl gelatin.

The agglomerates formed can be removed from the liquid by any suitable means, for example by decanting or siphoning the supernatant and washing the agglomerates once or several times.

Washing the agglomerates can be effected by simply washing with cold water. However, the first wash water is preferably acidified to lower the pH of the water to the pH of the freezing point. Published German patent specification (DOS) mentioned above
As described in 2337172, it is possible to add anionic polymers such as polystyrene sulphonic acid in the wash water, even when using acid coagulating gelatin derivatives. Alternatively, washing may be done by redispersing the aggregates in water at elevated temperature with a small amount of alkali such as sodium or ammonium hydroxide, adding acid to lower the pH to the freezing point and re-solidifying, followed by removal of the supernatant. You may go by This redispersion and recoagulation operation may be repeated as many times as necessary.

After the washing operation, the agglomerates are redispersed for a sufficient time, preferably 35 to 7 to completely redisperse the agglomerates.
Treatment with the required amount of water, gelatin and, if desired, alkali at a temperature in the range of 0 ° C. forms a photographic emulsion suitable for subsequent finishing and coating operations.

Instead of or in addition to the usual gelatins which are preferably used, other known photographic hydrophilic colloids for redispersion, such as gelatin derivatives as described above, albumin, agar, sodium alginate, hydrolyzed cellulose esters. , Polyvinyl alcohol, hydrophilic polyvinyl copolymers, colloidal silica and the like can also be used.

The photosensitive silver halide emulsion is chemically sensitized with sulfur and gold sensitizers. This is for example P. Glafkides
By Chimie et Physique Photographique; GF
Duffin, Photographic Emulsion Chemistry;
VL Zelikman et al., Making and Coating Photograp
hic Emulsion ； and Akademische Verlagsgesellscha
ft 1968, edited by H. Frieser, Die Grundlagen
der PhotographischenProzesse mit Silberhalogeni
This can be done as described in den. Sulfur sensitization, as described in the above-referenced document, refers to compounds containing small amounts of sulfur such as thiosulfates, thiocyanates,
It can be carried out by aging in the presence of thiourea, a sulfite, a mercapto compound, and rhodamine. Gold sensitization is caused by gold compounds. A smaller amount of Ir,
Rh, Ru, Pb, Cd, Hg, Tl, Pd, or Pt compounds can be used. The emulsion can be further sensitized with reducing agents such as tin compounds, amines, hydrazine derivatives, formamidinesulfinic acid and silane compounds as described in GB-A789823.

When using one or more silver halide emulsions in one or more emulsion layers, the silver halide emulsions are separately chemically sensitized.

EP application N filed on February 14, 1992
o. No. 92200420.5, the image tone is as follows: chemically aged cubic monodisperse silver bromoiodide crystals and chemically aged cubic monodisperse silver chloride and / or silver chlorobromide and / or chloroodor. The non-silver iodobromide crystals added, which can be improved by making a mixture of silver iodide emulsions, are also separately ripened.

According to the invention, it is possible to supplementarily add compounds for stabilizing the photographic properties or preventing the formation of fog during the manufacture or storage of the photographic material or during its photographic processing. Examples of such stabilizers are heterocyclic nitrogen-containing stabilizing compounds such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles. , Mercaptothiadiazole, aminotriazole, benzotriazole (preferably 5-methyl-benzotriazole), nitrobenzotriazole, mercaptotetrazole, especially 1-phenyl-5-
Mercapto-tetrazole, mercaptopyrimidine, mercaptotriazine, benzothiazoline-2-thione,
Oxazoline-thione, triazaindene, tetrazaindene and pentazaindene, especially Z. Wiss. Phot. 4
7 (1952), pp. 2-58, triazolopyrimidines such as GB-A1203757, G.
B-A1209146, those described in JP-A-50-39537 and GB-A1500278, and US
-7-hydroxy-as described in P4727017
There are s-triazolo- [1,5-a] -pyrimidines, and other compounds such as benzenethiosulfonic acid, benzenethiosulfinic acid, benzenethiosulfonic acid amides and other disulfide derivatives, which, if used as the sole stabilizer Addition gives unsatisfactory results and is therefore combined with stabilizers belonging to the group of stabilizers as described above. On the other hand, mercury salts and
Research Disclosure No. 17643 (1978
), Other metal salts that can be used as antifoggants, such as the cadmium salts and related compounds listed in Section VI, should be avoided for environmental pollution reasons.

The weight ratio of gelatin to silver halide (designated as silver nitrate) in the silver halide emulsion layer of the photographic material according to the present invention is between 0.3 and 1.2, preferably between 0.6 and 1. Included between 1.

For industrial radiography, the silver halide emulsion layer is from 6 to 6, expressed as the equivalent amount of silver nitrate, per side of the total amount of silver halide coated per m ² .
Contains 20 g.

The photographic material under consideration may further contain various surfactants in the photographic emulsion layer and / or in at least one other hydrophilic colloid layer. When one or more polyoxyalkylene compounds are present as surfactants,
It has been stated in a preferred embodiment that the dust disappears on the film side after processing to an acceptable level for materials having a high silver content such as silver halide industrial X-ray photographic films as described above. The total amount obviously promotes the appearance of dust.

The preferred polyoxyalkylene compounds which reduce dust to acceptable levels are castor oil and about 40 parts.
Is a condensation product of polyethylene oxide having a repeating unit of formula (I), which is shown below. Said at least one polyoxyalkylene compound is preferably present on one side of the film support in an amount of from 10 to 200 mg / m ^{2 and} preferably on one side of the film support.
More preferably it is present in an amount of ²⁰ to 100 mg per m ² . Preferred compounds of this type include:

[0038] _{R-COO- (CH 2 -CH 2} -O) 40 -H (I.1) ( the R is a castor oil radical) C ₉ H ₁₉ - phenyl -O- (CH ₂ -CH ₂ - O) _n -H (I.2) H- (O-CH ₂ -CH ₂ ) _n -O- (CH ₂ ) ₈ -CH = CH-C ₈ H ₁₇ (I.3) C (CH ₃ ) _{3 -CH 2 -C (CH 3) 2} - phenyl _{-O- (CH 2 -CH 2 -O)} n -H (I.4)

Compounds (I.1) to (I.4) are 300 to
It preferably has a molecular weight of about 400.

Both the polyoxyalkylene compound and the hardener mentioned above are preferably present in at least one non-photosensitive layer, both compounds preferably being present as outermost layers on both sides of the support. More preferably, it is added to

Other preferred surface-active coating agents are compounds containing perfluorinated alkyl groups. Other suitable surfactants include saponins, alkylene oxides such as polyethylene glycol, polyethylene glycol / polypropylene glycol condensation products, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan. ester,
Nonionic surfactants such as polyalkylene glycol alkyl amines or alkyl amides, silicone polyethylene oxide adducts, glycidol derivatives, fatty acid esters of polyhydric alcohols and alkyl esters of saccharides; such as carboxy, sulfo, phospho, sulfuric acid or phosphate ester groups. Anionic surfactants containing acid groups; amphoteric surfactants such as amino acids, aminoalkyl sulphonic acids, aminoalkyl sulphates or phosphates, alkylbetaines, and amine-N-oxides; and alkylamine salts, aliphatics, aromatics, Alternatively, it includes a cationic surfactant such as a heterocyclic quaternary ammonium salt, an aliphatic or heterocyclic ring-containing phosphonium or sulfonium salt. Such surfactants are used for various purposes, such as coating aids, antistatic compounds, compounds that improve lubricity, compounds that facilitate dispersion emulsification, compounds that prevent or reduce adhesion, and photographic properties. For example, it can be used as a compound which improves high contrast, sensitization and development acceleration.

Development acceleration is effected by various compounds, preferably for example US-P 3038805, US-P 403807.
5, can be achieved with the aid of polyalkylene derivatives having a molecular weight of at least 400, such as those described in US Pat.

The photographic material may further comprise various other additives such as compounds which improve the dimensional stability of the photographic material, UV absorbers,
Spacing agents and plasticizers can be included.

Suitable additives for improving the dimensional stability of photographic materials include, for example, dispersions of water-soluble or almost insoluble synthetic polymers, such as alkyl (meth) acrylates.
Alkoxy (meth) acrylate, glycidyl (meth)
Acrylate, (meth) acrylamide, vinyl ester, acrylonitrile, polymers of olefins and styrene, or those mentioned above with acrylic acid, methacrylic acid,
There is a dispersion of a copolymer of α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate and styrene sulfonic acid.

Suitable UV absorbers include, for example, US-P3
Aryl-substituted benzotriazoles as described in 533794, US-P3314794 and US-P335.
4-thiazolidone compounds as described in 2681, J
Benzophenone compounds as described in P-A2784 / 71, US-P3705805 and US-P3707.
There are cinnamic acid ester compounds as described in 375 and benzoxazole compounds as described in US-P 3,700,545.

Generally, the spacing agent has an average particle size of 0.2.
10 to 10 μm. Spacing agents can be soluble or insoluble in alkali. The alkali-insoluble spacing agent usually remains permanently in the photographic material, while the alkali-soluble spacing agent is usually removed therefrom in the alkaline processing bath. Suitable spacing agents can be made, for example, from polymethylmethacrylate, copolymers of acrylic acid and methylmethacrylate, hydroxypropylmethylcellulose hexahydrophthalate. Other suitable spacing agents are described in US-P 4,614,708.

The photographic material may contain an antistatic layer during coating, processing and other handling of the material, for example to avoid electrostatic charging. Such an antistatic layer can be the outermost layer of one or more antistatic agents or a coating applied directly to the film support. The antistatic layer may be overcoated with a barrier layer of, for example, gelatin. Suitable antistatic compounds for use in such layers include, for example, vanadium pentoxide sols, tin oxide sols, or conductive polymers such as polyethylene oxide, polymer latices and the like.

The photographic material according to the present invention is a double-sided coating material having at least one emulsion layer and at least one protective antistress layer on both sides of the film support.
d material).

The support of the photographic material according to the present invention may be a transparent resin, preferably a blue colored polyester support such as a polyethylene terephthalate support. The thickness of such organic resin film is preferably about 175 μm. The support is provided with subbing layers on both sides to provide good adhesion between the emulsion layer and the support.

Finer tuning of the appearance of the film may be required. The absorption spectrum of the material as obtained after the processing cycle described below is thus obtained by adding a suitable non-migratory dye to the subbing layer, the emulsion layer or the protective antistress layer or the top layer on both sides of the support. . Therefore blue colored dyes are especially recommended.

Photographic X-ray materials are image-wise exposed by an X-ray radiation source, the energy expressed in kV of which is determined by the particular application. Another representative source of radiation is the radioactive Co ⁶⁰ source. Metal screens, usually lead screens, are used in combination with photographic film to reduce the effect of scattering radiation. Besides that, the generation of secondary electrons enhances the sensitivity.

For processing, an automatic operating device provided with a device for automatic replenishment of the processing solution is used as specified in the examples. According to the invention, the treatment of the exposed material as described above comprises the steps of hardener-free development and hardener-free fixing,
And subsequent washing and drying steps in an automatic processor with infrared drying means at the film drying station. The infrared drying means corresponds to an infrared lamp.

The developer solution according to the invention is not only due to the reduction of the liquid volume due to the crossing into the next processing solution,
It must also be replenished due to pH changes due to the oxidation of developer molecules. This can be done on a regular time interval basis or on a quantity of processed film basis or a combination of both. The developing step can be followed by a washing step, a fixing solution step and another washing or stabilizing step. Finally, after the final washing step, the photographic material is dried by infrared drying means as described above.

According to the invention, a completely unexpected improvement in the physical properties of the film surface is seen. After the film has passed through the drying station of a processor equipped with infrared drying means, no sticking and / or damage of the film surface appears.

Yet another improvement is that the developer solution comprises, as a surfactant, at least one anionic alkyl-phenoxy and / or alkoxypolyalkyleneoxyphosphate ester (compounds II.1 and II.2), a sulfate ester. (Compound II.3), an alkylcarboxylic acid, a sulfonic acid or a phosphonic acid (compound II.
4, II. 5 and II. 6) and / or a measure for treating the materials described above in an automatic processor containing salts thereof.

Preferably, said at least one anionic alkylphenoxypolyalkyleneoxyphosphate ester surfactant present in the developer solution is:
Alkyl-phenoxy- (ethyleneoxy) in salt form
_n phosphoric acid mono- or diester compounds and mixtures thereof [see compounds (II.1) and (II.2)],
n is a positive integer of at least 4 and the alkyl group is C ₈
Is a C ₂₀ alkyl group.

[0057]

In the formula, R, R ₁ and R ₂ each independently represent a substituted or unsubstituted alkyl group or R ₃ -phenyl group or R ₄ -phenyl group, and R ₃ and R ₄ are each independently an alkyl group, preferably represents a C ₈ -C ₂₀ alkyl group, m and n are integers from each 3,4 to about 30.

The preferred amount of said at least one ionic surfactant present in the developer is about 25 to 200 m.
g / l.

The treatment of the exposed material represented by the steps of development and fixing, the developer preferably containing at least one of the compounds (II.1) or (II.2) as described above is carried out by the curing agent according to the invention. It can be carried out in a free solution.

The developer solution according to the invention must additionally be replenished not only for the reduction of the liquid volume due to the intersection with the next processing solution, but also for the pH change due to the oxidation of the developer molecules. This can be done on a regular time interval basis, or on a quantity of processed film basis, or a combination of both. The developing step can be followed by a washing step, followed by a fixing solution step, another washing step or a stabilizing step. Since aluminum sulphate is excluded in the hardener-free fixing solution, the elimination of aluminum salt deposits on the rollers in the fixing zone of the automatic processor further leads to an improvement in the surface properties of the treated film material. The transfer of said deposits from the roller to the film is no longer seen, and vice versa, so that no dust deposits occur on the film surface.

Post-cleaning processor following fixing (Agfa-Geva
Product name STRUCTURIX marketed by ert
NDT-3 and the conventional machines marketed by Eastman Kodak under the trade name EK-Mod.B) resulting in the elimination of extra physical means for removing dust from the film surface, eg brush rollers. it can. For the user, this results in lower costs.

Of course, processing conditions and processing solutions will depend on the particular type of photographic material. For example, for materials for industrial X-ray diagnostic purposes, according to the invention, an automatically operated processing device provided with a device for automatic regeneration of the processing solution is used. It is clear that the pre-cured material can be treated with one or three packaging chemicals, but if one packaging chemical can be applied, the solution mixing can be eliminated, which is preferred because it is convenient for the user. . A total processing time of 90 seconds is applicable. From an environmental point of view, it is even possible to use sodium thiosulfate instead of ammonium thiosulfate in the fixer.

The improvements mentioned for industrial X-ray films also apply to X-ray medical films with high silver halide content.

The following examples illustrate the invention but do not limit it.

Examples Example 1 A gelatin silver iodobromide X-ray emulsion containing 99 mol% silver bromide and 1 mol% silver iodide was prepared by the following method. An aqueous solution containing 3 g of ammonia was added at 45 ° C. to a reaction vessel containing 1550 ml of a 3% by weight aqueous solution of gelatin. In the reaction vessel, 2000 ml of an aqueous 1.5 molar solution of potassium bromide and an aqueous 1.5 molar solution of silver nitrate 20
00 ml was introduced at a constant rate of 86 ml / min under vigorous stirring conditions. During the precipitation, the pAg value was determined with reference to a silver / saturated calomel electrode with an E. M. F. Adjusted to a value equivalent to and kept it. 0.54 μm with this method
Homogeneous and cubic silver halide grains having a crystal diameter of

At the end of the precipitation step, the pH value of the emulsion in the reaction vessel was adjusted to 3.5 with sulfuric acid and polystyrene sulfonic acid acting as a flocculant was added to flocculate the emulsion.
After rapid precipitation of the silver halide emulsion, the supernatant was decanted. To remove water-soluble salts from the agglomerates, deionized water at 11 ° C was added under controlled stirring conditions, followed by further sedimentation and decanting. This washing process was repeated until the emulsion was fully desalted. The agglomerates were redispersed in water at 45 ° C after addition of sufficient gelatin to obtain a gelatin to silver halide ratio of 0.4, expressed as silver nitrate. PH with reference to silver / saturated calomel electrode
The value was adjusted to 6.5 and the pAg value was adjusted to a value of +70 mV.

Chemical sensitization of the emulsions was carried out by adding sulfur and gold sensitizers and ripening at 50 ° C. to the point where maximum sensitivity was reached for still acceptable fog levels.

The emulsion was coated on both sides with a blue polyethylene terephthalate support having a thickness of 175 μm, so that for 1 m ² there was a corresponding amount of silver halide of 14.5 g of silver nitrate and 12.3 g of gelatin.
5-Methyl-7-hydroxy-5-triazolo- [1,5-a] -pyrimidine and 1-phenyl-5-mercaptotetrazole were added to the emulsion before coating.

From a sample of the material thus formed, the emulsion layer was covered on both sides with a protective layer of gelatin 1.5 g / m ² . Comparative material No. Cured with 0.066 g of formaldehyde (FMD) per 1 m 2 to ² ,
Material No. as shown in Table 1 0.0 of di- (vinyl-sulfonyl) -methane (DVS) for 1 m ² per 1
Cured at 93 g.

The coated and dried film was used with a 235 kV radiation source with a copper filter 8 mm thick I
Exposed according to SO 7004.

The exposed radiographic film was developed, fixed, washed and dried in an automatic mechanical processing cycle of 8 minutes. The film is commercially available from Agfa-Gevaert S
The paper was fed through a tructurix NDT-1 machine, developed in a one-pack developer described later at 28 ° C., and then fixed in one-pack fixer.

An infrared drying device was present in the drying area. It was possible to evaluate the surface condition of the treated film at 8 drying levels.

The composition of the concentrated one package developer is as follows:

Water 200 ml Potassium bromide 6 g Potassium sulfite (65% solution) 247 g Ethylenediaminetetraacetic acid tetrasodium salt trihydrate 9.6 g Hydroquinone 112.0 g 5-Methylbenzotriazole 0.076 g 1-Phenyl-5-mercaptotetrazole 0.040 g Sodium tetraborate (decahydrate) 18.0 g Potassium carbonate 38.0 g Potassium hydroxide 42.0 g Diethylene glycol 100.0 g Potassium iodide 0.088 g 4-Hydroxymethyl-4-methyl-1-phenyl-3 -Pyrazolidinone 12.0 g made up to 1 l with water.

The pH is 11.1 at 25 ° C. with potassium hydroxide.
Adjusted to 5.

To start the process, 1 part of concentrated developer was mixed with 3 parts of water. No initiator was added. PH of mixture is 2
It was 10.40 at 5 ° C.

The composition of the concentrated one-pack fixer is as follows:

Ammonium thiosulfate (59% solution) 552 g Boric acid 20.8 g Sodium sulfite 45 g Sodium acetate (trihydrate) 58 g Sulfuric acid (99% solution) 48.5 ml Water was made up to 1 liter.

The pH was adjusted to 4.80 at 25 ° C. with sulfuric acid.

To start the process, 1 part concentrated fixer was mixed with 4 parts water. The pH of this mixture was 4.73 at 25 ° C.

Table 1 shows the evaluation of the drying rate and the sticking phenomenon observed on the film surface in the automatic processor filled with the one-pack curing agent-free chemical having the composition as described above.

[0083]

For both the material (1) according to the invention and the comparative example material (2), the water uptake per 1 m ² is 59 g.

As can be seen from Table 1,
The (vinyl-sulfonyl) -methane cured material (Emulsion No. 1 as an example of the invention) dries faster:
Already at the dryer level 2, the drying characteristics were satisfactory as shown by the evaluation mark 0 without causing tackiness.
For the formaldehyde-cured comparative examples, problems were encountered, resulting in the phenomenon of sticking with the first pair of rollers at different dryer levels, causing clogging and wrapping around them. Occurrence of such an unfavorable effect is indicated by (*) mark.

Example 2 A gelatin silver iodobromide emulsion having an average crystal diameter of 0.2 μm and a cubic crystal habit and containing 99 mol% silver bromide and 1 mol% silver iodide was prepared.

Sensitization of the emulsion was carried out by addition of sulfur and gold sensitizers and ripening at 50 ° C., to the point where maximum sensitivity was still reached at acceptable fog levels.

The emulsion was coated on both sides with a blue polyethylene terephthalate support having a thickness of 175 μm, thus for every 1 m ² 8.5 g gelatin and 1 silver nitrate.
An amount of silver halide corresponding to 0.0 g was present. Prior to coating, stabilizers of 5-methyl-7-hydroxy-5-triazolo- [1,5-a] -pyrimidine and 1-phenyl-5-mercaptotetrazole were added to the emulsion. From the sample of material thus formed, the emulsion layer on both sides of it,
Covered with a protective layer of 1.5 g of gelatin per 1 m ² , which was prepared according to Material No. 2 as shown in Table 2 below. For 1 and 2, it was cured with 0.195 g di- (vinyl-sulfonyl) -methane (DVS) per m ² .

Material No. The protective layers on both sides of the film support of No. 2 additionally contain a polyoxyalkylene compound corresponding to formula (I.1) (designated as POAC in Table 2) in an amount of 0.042 g / m ² of film. It was
The coated and dried film was exposed according to ISO 7004 with a 235 kV radiation source with a 8 mm thick copper filter.

The exposed radiographic film was developed, fixed, washed and dried in an automatic mechanical processing cycle of 8 minutes. Experiment No. In No. 1, development was conducted at 28 ° C. with Agfa −
Hardener-containing developer G1 marketed by Gevaert
35 (trade name) (hereinafter referred to as DEV), which was hydroquinone, phenidone, potassium sulfite, 1-
It contained phenyl-5-mercaptotetrazole, 5-nitroindazole and glutardialdehyde.
Same experiment No. In No. 1, the fixing temperature is 28 ° C, and Agfa-
Hardener-containing fixer G335 marketed by Gevaert
(Trade name) (hereinafter referred to as FIX), which contained aluminum sulfate, sodium sulfite, boric acid and sodium acetate.

Experiment No. In No. 2, the same material No.
Example 1 was performed with a curing agent-free processing solution made from the same one package concentrated developer and one package concentrated fixer as in Example 1 above.

The hardener-free solutions of the developer and fixer are hereinafter referred to as HFDEV and HFFIX, respectively.

Furthermore, in an amount of 100 mg / l, the compound (I
When I.1) was added to the developer with an anionic alkylphenoxypolyalkyleneoxyphosphate ester surfactant, this developer was designated as HFDEVPHOS.

In Table 2 below, the material No. No. exposed as described above. The combinations of the developing solution and the fixing solution in which 1 and 2 were sent were tabulated.

In order to mimic the harsh real-life situation of dust onset on the surface of the film after treatment of the material, the following method was carried out:

After processing a quantity of film was exposed to the extent that it had a medium density corresponding to the average density actually obtained for the real sample. The above amount of film was fed through the processor to cause replenishment of the processing solution so that it was completely regenerated. Actually about 10 per day
m ² was sent through the processing solution and the regeneration applied was 900 ml / m ² for developer, 1200 for fixer
It was ml / m ² . For each experimental combination of film and treatment solution as tabulated in Table 2, the method was restarted until a good working condition was reached in which the appearance of dust on the surface could be evaluated.

Therefore, after reaching the working conditions, non-exposed sheets of different materials were fed through the processor. Initially 10 sheets of each material were tested in piles to allow the desired evaluation.

For the appearance of dust on the film surface after treatment,
An index of 0-3 was given with the following significance:

3 or 2: Dust level that is acceptable to users who do not have strict regulation 1: Dust level that is acceptable to users who have strict regulation 0: No dust that can be visually detected

In Table 2, these numbers correspond to the above notes.

[0101]

As can be seen from Table 2, even with the hardener-free chemicals, the dust level on the film surface after treatment fell to an acceptable level, especially with the hardener-free treatment solution. This is the case when the material contains at least one polyoxyalkylene compound as a surfactant in the protective coating. Experiment No. Further improvement is obtained by the presence of the anionic alkylphenoxypolyalkyleneoxyphosphate ester surfactant in the hardener-free developer, as is clearly demonstrated by No. 4.

Front page continued (72) Inventor Joseph Clemant Septerrato, Mortzeer, Belgium 27 Agfa Gewert Naamrose, inside Ben Benchatchap (72) Inventor Pieté Perdue, Septerrat, Belgium 27 Agfa Gewert Namur Ze Bennault Chap

Claims (10)

[Claims] 1. A process of exposing a silver halide industrial X-ray photographic material, said material being processed in an automatic processor in a hardener-free developing solution and a hardener-free fixing solution, followed by washing. In a method of imaging by drying with infrared drying means at a film drying station, the material comprises a support and at least one gelatin silver halide emulsion layer and at least one non-photosensitive protective stress on at least one side thereof. Containing a protective coating, the total amount of silver halide per side being 1 m ² corresponds to 6 to 20 g of silver nitrate, said material being hardened with at least one vinyl sulfone compound, whereby it is ready for drying. A method characterized in that the water uptake of the treated film is reduced to less than 2.5 g water per gram coated gelatin. 2. The vinyl sulfone curing agent is di- (vinyl-sulfonyl) -methane or ethylene-di- (vinyl-).
2. The method of claim 1, wherein the method is sulfone). 3. The method according to claim 1, wherein in said material, at least one polyoxyalkylene compound is present as a surfactant in at least one of its hydrophilic layers. 4. The at least one polyoxyalkylene compound is 10 to 20 on one side of the film support.
4. It is present in an amount of 0 mg / m ^2.
the method of. 5. The at least one polyoxyalkylene compound is 20 to 10 on one side of the film support.
4. It is present in an amount of 0 mg / m ^2.
the method of. 6. The method according to claim 3, wherein the at least one polyoxyalkylene compound is a condensation product of castor oil and polyethylene oxide having 40 repeating units. 7. The method according to claim 3, wherein the polyoxyalkylene compound is present in a protective antistress coating on both sides of the film support. 8. A curing agent-free developing solution comprising at least one anionic alkylphenoxy and / or alkoxypolyalkyleneoxyphosphate ester, sulphate ester, alkylcarboxylic acid, sulphonic acid or phosphonic acid and / or as a surfactant. Or the salt thereof is contained, The method of any one of Claims 1-7 characterized by the above-mentioned. 9. The anionic alkylphenoxypolyalkyleneoxyphosphate ester surfactant,
Alkylphenoxy- (ethyleneoxy) _{n in} salt form
Phosphoric acid mono- or diester compounds (n is at least 4 positive integer, the alkyl group is C ₈ -C ₂₀ alkyl group) The method of claim 8, characterized in that a. 10. The method according to claim 8, wherein the anionic surfactant is present in the developer in an amount of 25 to 200 mg / l.