DE2455002A1 - PHOTOGRAPHIC DEVELOPMENT PROCESS - Google Patents

Description

PATENT ADVOCATES A. GRÜNECKER

DIPL.-ΙΝΘ.

H. KlNKELDEY

ΟΊ -Τ · 'β.

W. STOCKMAIR

DR.-ING. ■ AOE (CALTECH)

2455 00 2 ^Κ SCHUMANN

^ DR. RER. NAT. ■ DIPL.-PHYS.

P. H. JAKOB

DIPL.-ING.

G. BEZOLD

DR. RER. NAT. · DIPL.-CHEM.

MUNICH

E. K. WEIL

DR. RER. OEC. INQ.

LINDAU

8 MUNICH 22

MAXIMILIANSTRASSE 43

20. Έον. 1974 P 8671

Photo EiIm Co., Ltd.
No. 210, Nakanuma, Minami Ashigara-Shi, Kanagawa, Japan

Photographic development process

The invention relates to a method for photographic development, in particular, a method of photographic development using a developer using one Contains dialdehyde.

During processing of exposed photographic material, the halide silver emulsion layer is easily damaged or destruction, since the layer swells extraordinarily. Dialdehydes are therefore added to the developer (Compare US-PS 3,232,761 and GB-PS 1,040,081 and 1,269,268). Furthermore, antifoggants (for example, anthraquinone compounds or nitrogen-containing heterocyclic Compounds such as 5-nitroimidazole or benzotriazoles

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TELEPHONE (Ο8θ) 22 2662 TELEX Ο6-2β38Ο TELEQRAMME MONAPAT

added to prevent the formation of fog caused by the dialdehydes to inhibit.

However, if the photographic material is used for a long time developed a developer containing a known antifoggant and a dialdehyde, the Fogging gradually increases, and as the application time increases, there is an increase in density in the low-density areas easily to a larger increase than in the high-density areas (that is, the contrast is decreased). These appearances are not observed at all if the dialdehyde is not present in the developer. Accordingly, it is desirable maintain the photographic properties of the developer containing a dialdehyde.

An object of the invention is therefore to provide a method for photographic processing in which fogging is inhibited and a decrease in contrast is prevented.

Another object of the invention is to provide a high temperature and high speed developing process to be made available in which a developer with a dialdehyde is used.

Investigations have shown that the aforementioned phenomena occur even when the one containing a dialdehyde An antifoggant is added to the developer. However, it has been found that the aforementioned phenomena only occur when a dialdehyde and halogen ions are present in the developer, and that said phenomena with increasing Developing temperature occur more intensely. It was further found that those caused by dialdehydes and halogen ions Disadvantages increase in the order chlorine, bromine and iodine. It is believed that the formation of these halogen ions from the silver halide dissolved in the developer depends, and it has been found that the disadvantages are most pronounced with silver iodide.

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holding emulsions occur. The subject of the invention is thus a photographic development process characterized by is that the "exposed syrup photographic material subjected to development with a silver halide developer and an aqueous alkaline solution which contains a polyalkylene oxide compound having a molecular weight of about 300 to 20,000 and a dialdehyde.

In the case of the polyalkylene oxide compounds used according to the invention (hereinafter referred to as polyalkylene oxides) are, for example, nonionic, cationic or anionic Links. The polyalkylene oxides can be described as compounds containing an alkylene oxide radical, for example an ethylene oxide residue and / or a propylene oxide residue as the basic building block or structural unit included. You can also use polyalkylene copolymers, for example a block copolymer of polyethylene oxide and polypropylene oxide. ·

The polyalkylene oxides used according to the invention have molecular weights from about 300 to 20,000, preferably 1,000 to 9,000.

It is already known to increase the sensitivity by adding a polyethylene oxide to a photographic layer or to a To increase developer (see US Pat. No. 2,531,832). The invention however differs from this prior art in the presence of a dialdehyde and a polyalkylene oxide. It should also be noted that the sensitizing effect of the aforementioned prior art is not maintained at all If, according to the method of the invention, processing is carried out at high temperature and at high speed is carried out.

Examples of polyalkylene oxides suitable according to the invention are 1 · nonionic compounds, such as

Polyethylene glycols,.

for example Carbowax 1540, Carbowax 4OOO and Carbowax 1200

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(Prod., Union Carbide and Carbon Chemicals Corp.) "as Carbowax 1540 has, for example a degree of polymerization of about 35, a molecular weight of about 1300 to 1600, a specific gravity of about 1.15 and a solidifying point of about 43 to 46 ⁰ C. ,

Polyethylene glycol methyl phenyl ether,

for example those polyethylene glycol methyl phenyl ethers which a polyoxyethylene chain with a degree of polymerization of about 25 or 50 (manufactured by Nippon Emulsion Co., Ltd.), polyoxyethylene alkyl ether,

such as polyoxyethylene lauryl ether (HLB: 9.5j Manuf. Atlas Co.); Polyoxyethylene lauryl ether (with an oxyethylene chain with a degree of polymerization of about 20), polyoxyethylene oleyl ether (with a Oxyethylene chain with a degree of polymerization of about 50), and polyoxyethylene octyl ether (with an oxyethylene chain with a degree of polymerization about 50), Manuf. Nippon Emulsion Co., Ltd., polyoxyethylene nonylphenyl ether,

such as polyoxyethylene nonylphenyl ether with an oxyethylene chain with a degree of polymerization of about 30, 40 and 50 (Manufact. Nippon Emulsion Co., Ltd.),
Polyoxyethylene sorbitan ester,

like polyoxyethylene ens orbit anmono oil eat (HLB: 15.0) and polyoxy? - Ethylene sorbitan monostearate (HLB: 14.9), Herst. Atlas Co., USA, as well as polyoxyethylene sorbitan monolaurate (with an oxyethylene chain degree of polymerization about 30 or 50), Mfr. Nippon Emulsion Co., Ltd.,

Block polymers of polyoxyethylene and polyoxypropylene, such as Pluronic L-61, L-62, L-64, L-68 and L-75, Herst. Wyandotte Chemicals Corp.,
Polyoxyethylene alkyl ester,

such as polyoxyethylene monostearate (HLB: 17.9), Herst. Atlas Co., polyoxyethylene dilaurate (with an oxyethylene chain with a degree of polymerization of about 23), .Herst. Nippon Oils and Pats Co., Ltd., and polyoxyethylene monolaurate (having an oxyethylene chain of about 50 degree of polymerization), manufactured by Nippon Emulsion Co., Ltd .; 2. cation-active compounds, such as
Polyoxyethylene bis-pyridinium methanesulfonate of the formula

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i - (CHpCH O) _- CH CH - N

4 '' k

SO ₂ CH ₃ "

which is manufactured according to the process of US Pat. No. 2,950,970,

-r V) 2Cl "

3. anion-active compounds, such as
Polyethoxyethyl-bis-sulfuric acid of the formula

HSO ₃ -O- (CH ₂ CH ₂ O ^ -SO ₃ H

whose production is carried out according to the method of GB-PS 859 632,

NaO ₃ SO (C ₃ H ₆ O) ₁₃ SO ₃ Na

^C 9 ^H 19 ~

These compounds, which are used in numerous fields, are in U.S. Patents 2,400,532, 3,288,612, 3,294,540, 3 325 286, 3 345 175 and 3 516 83Ο.

Of the polyalkylene oxides, there are nonionic polyethylene oxides The most preferred compounds are. In particular, the polyethylene oxides of the general formulas I and II are preferred.

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In the general formula I.

₁₂₂ ^ -R ₂ (D

"R ₁ and R ₂ each represent a hydrogen atom or an organic radical with 1 to 16 carbon atoms (for example an alkyl radical such as a butyl or undecyl group, an aralkyl radical such as a benzyl group, an aryl radical such as a tolyl group, or an acyl radical), and η is an integer from about 5 "to 200.

In the general formula II

"a," b and c each represent a positive integer, where the Sum a + b + c is about 20 to 80, and b has a value of about 15 to 50. Preferably the ethylene oxide group comprises in about 10 to 50 percent by weight of the total molecule, and that before The average molecular weight of the polypropylene oxide radical added is about 800 to 3000.

Examples of compounds of the general formulas I and II are:

(1) HO - (CH ₂ CH ₂ O), ₀ H

(2) HO - (CH ₂ CH ₂ O) ₀ H

(3)

₉ O - (CH ₂ CH ₂ O) ₃₀ H

C ₁₁ H ₂₃ COO (CH ₂ CH ₂ O) ₉ OCC ₁₁ H ₂₃

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(.6) C ₃ H ₇ COO (CH ₂ CII ₂ O) ₁₅ H

(7) CH ₃ - (8)

CH ₃ -

O -

(9)

- (CH ₂ CH ₂ O) ₁₀ H

(10) C ₉ H ₁₉ COO (CH ₂ CH ₂ O) ₂₄ OCC ₉ H ₁₉

(12)

C ₉ H ₁₉ -

-O- (CH ₂ CH ₂ O) ₁₅ H

(13) CH ₃ O- (CH ₂ CH ₂ O) ₆ CH

HO (CH ₂ CIJI ₂ O) (CHCH ₂ O) ₁₅ (CH ₂ CH ₂ O) H CI

ΪΗ,

HO (CH ₂ CH ₂ O) ₃ (CHCH ₂ O) ₁₉ (CH ₂ CH ₂ O) H

(16)

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(17)

(ιδ)

ο ι

CH ₃

(19) HO (CH ₂ CH ₂ O) ₁₀ (CHCH ₂ O) ₃₀ (CH ₂ CH ₂ O) ₂₀ H

(20) HO (CH ₂ CH ₂ O) ₈₀ (CHCH ₂ O) ₃₀ (Ch ₂ CH ₂ O) ₈₀ H.

CH ₃

The polyalkylene oxide is used, for example, in amounts of about 0.0005 to 10 g / liter, preferably 0.01 to 5 g / liter, in the developer used.

The developer of the invention is an aqueous alkaline one Solution that contains a developer and a dialdehyde. Examples of suitable developer substances are the well-known dihydroxybenzenes (such as hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydroquinone, Methylhydroquinone, 2,3-dichlorohydroquinone or 2,5-dimethylhydroquinone); 3-pyrazolidones (such as 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, i-phenyl ^^ - dimethyl ^ -pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone or 1-phenyl-5-methyl-3-pyrazolidone); Aminophenols (such as o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, or 2,4-diaminophenol); Pyrogallol? Ascorbic acid; 1-aryl-3-pyrazoline (such as 1- (p-hydroxyphenyl) -3-aminopyrazoline, 1- (p-methylaminophenyl) -3-pyrazoline, 1- (p-aminophenyl) -3-aminopyrazoline or 1- (p-aminom-methylphenyl) -3-aminopyrazoline); or mixtures of the aforementioned compounds. In the method of the invention, a developer containing a hydroquinone is particularly preferred. The developer substance is generally in one in the developer Amount from about 0.01 to 2 moles / liter, preferably 0.05 to

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1 mole / liter, available. Suitable dialdehydes are both dialde « hyde, as well as their bisulfite adducts or hydrogen sulfite adducts (These are described in detail in U.S. Patents 26,601 (Reissue Patent) and 3,545,971) *

Examples of suitable dialdehydes are glutaraldehyde ,? L -methylglutaraldehyde, ß-methylglutaraldehyde, M8.1eindialdehyde, succinic dialdehyde, methoxy succinic dialdehyde, methyl succinic dialdehyde,. ^ - methoxy-ß-ethoxyglutaraldehyde, / -n-butoxyglutaraldehyde, • ^ -n-butoxyglutaraldehyde ß-ethoxyglutaraldehyde, qC »^ C -dimethoxy-succinic dialdehyde, ß-isopropyl-succinic dialdehyde, oc, oC -diethylbernsteindialdehyd, butylmaleindialdehyde, as well as the hydrogen sulfite adducts of the aforementioned dialdehydes. The dialdehydes are used in such amounts that there is no reduction in the sensitivity of the processed photographic layer and that the drying time is not appreciably increased. The dialdehydes are generally used in amounts of about 1 to 50 g, preferably 3 to 20 g, based in each case on 1 liter of the developer.

The developer may contain preservatives (such as Sulfites or hydrogen sulfites), buffers (such as carbonates, boric acid, borates or alkanolamines), alkaline substances (such as hydroxides or carbonates), solubilizers (such as polyethylene glycols or their esters), pH regulators (such as organic acids, e.g. acetic acid), sensitizers (such as quaternary ammonium salts), Contains development accelerators or surfactants (surface-active substances).

Furthermore, the developer can contain antifoggants (such as halides, for example potassium bromide or sodium bromide, benzothiazole, benzotriazole, tetrazole or thiazole), and chelating agents (such as Ethylenediaminetetraacetic acid or its salts, for example sodium or potassium salts, polyphosphates or nitriloacetatep) contain.·

The pH of the developed developer is adjusted to a value

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that is sufficient to ensure the desired density and contrast. Preferably the pH about 8.5 to about 11.5.

In a preferred embodiment in the use of the unwinder it is an activator processing, which is characterized in that a photographic material, which contains a developer substance (for example in an emulsion layer), developed using an aqueous-alkaline solution. With this processing, the objects of the invention can also be achieved.

The temperature and duration of development are closely related and are determined by the total processing time. In general, the development is carried out at about 10 to 60 ° C., preferably about 20 to 60 ^° C. and in particular 30 to 60 ^° C., for a period of about 10 seconds to 20 minutes, preferably 10 seconds to 2 minutes.

Following the development of the exposed silver halide photographic material, the developed photographic material is fixed. In the fixing solution is an aqueous solution containing thiosulfate and a water-soluble aluminum compound, and has a pH of about 3.8 to 5.0 (at 20 ⁰ C). Examples of suitable fixing substances are thiosulfates, such as ammonium thiοsulfate or sodium thiosulfate, or thiocyanates, such as sodium thiocyanate or potassium thiocyanate. Examples of suitable fixing substances are described in US Pat. No. 3,582,322. The amount of fixing substance used can vary accordingly; it is generally about 0.1 to 5 mol / liter of the fixing solution.

The water-soluble aluminum salt, which acts as a hardener in the fixing solution, is a compound that acts as a Hardener is known for acidic hardener-fixing solutions. Examples of such compounds are aluminum chloride and aluminum sulfate or potassium alum.

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A developing machine that uses transport rollers is described in U.S. Patents 3,025,779 and 3,545,971. wrote; this processing device is hereinafter referred to as Called transport roller developing machine. The processing using transport roller developing machines comprises four stages, namely developing, fixing, washing and Dry. The processing according to the invention includes other stages (like stopping) does not, however, preferably consists of the aforementioned four stages. The transport roll wrapping machine represents only a preferred embodiment; also other development machines (for example hanger type ", or non-contact type "as described in US Pat. No. 3,405,627) are suitable for practicing the method of the invention.

The silver halide photographic light-sensitive material which can be processed by the method of the invention contains a carrier. The supports are translucent or opaque plates or foils or layers made of glass, cellulose acetate, Polyethylene terephthalate, baryta paper, synthetic paper or waterproof paper. There is at least one halogen silver emulsion layer on the support. The halogen over emulsion layer can be applied not only to one surface of the carrier, but to both surfaces. Of course can be the halide silver photographic light-sensitive material optionally a backing layer, an antihalation layer, an intermediate layer and a top layer (for example a protective layer). The halogen silver emulsion can be prepared by using a silver halide such as silver chloride, silver iodide, silver bromide, silver bromochloride, Silver iodobromide or silver iodobromochloride (preferably a silver halide that is 0.1 to TO mole percent, preferably 0.3 to 8.0 mol percent and in particular 0.5 to 5.0 mol percent silver iodide) in a hydrophilic colloid (such as gelatin, modified gelatin, colloidal albumin, casein, carboxymethyl cellulose, hydroxyethyl cellulose, sodium alginate, Polyvinyl alcohol, polyvinylpyrrolidone or mixtures thereof). The halogen silver emulsions can by

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Mixing a water-soluble silver salt (for example silver nitrate) with a water-soluble halide (e.g. potassium bromide) in the presence of water and a hydrophilic one Colloids, using known methods (for example a single jet method, a double jet method or a controlled one Beam method), with physical ripening and chemical ripening, such as metal sensitization and / or sulfur sensitization can be performed. The silver halide emulsions can in the course of their preparation or immediately before coating, for example, spectral sensitizers (such as cyanine dyes, merocyanine dyes or mixtures thereof), stabilizers (such as 4-hydroxy-6-methyl-1,3 »3a, 7-tetrazaindene), Sensitizers (such as the compounds described in U.S. Patent 3,619,198), antifoggants (such as benzotriazole or 5-nitrobenzimidazole), polyethylene oxide, hardener (such as Formaldehyde, glyoxal, mucochloric acid or 2-hydroxy-4 »6-dichloro-triazine) or coating aids (such as saponin, sodium lauryl sulfate, Dodecylphenyol polyethylene oxide ether or hexadecyltrimethylammonium bromide) are incorporated. The so produced Halide silver emulsions can be applied to a support using a variety of methods. Suitable are for example dip coating, coating using a slot die, pearl coating (bead coating), extrusion using a doctor blade or double-sided surface coating.

In the foregoing silver halide photographic light-sensitive materials, the composition of the silver halide and the kinds of additives and the vehicle differ according to the use. The light-sensitive materials processed according to the method of the invention are, for example, black and white photographic material (for example X-ray films for medical or technical purposes, conventional photographic material or microfilm material).

As stated above, the characteristic is that

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Invention in the use of the developer containing a dialdehyde and a polyalkylene oxide. Accordingly, "the intended effect is hardly achieved if one of the two components, namely dialdehyde or polyalkylene oxide, is contained in the light-sensitive material and the other in the developer. If the dialdehyde is added to an emulsion coating solution, the coating solution immediately aggregates). since the dialdehyde has a strong hardening effect and the coating solution can no longer be used for coating If an emulsion containing the polyalkylene oxide is further used for coating, uneven coatings are obtained, even if every photographic material is developed with a developer containing the other component, therefore, the good results obtained in the present invention cannot be obtained, but when the polyalkylene oxide is added to the emulsion layer in a certain amount, some effect can sometimes be obtained However eNOXIDE can not be represented by a continuous range, although _S can be wifideigpgeben i _e by discontinuous points. It is therefore important in the present invention to incorporate the polyalkylene oxide into the developer.

According to the method of the invention there is no fogging, even if the developer is used for a long time, the contrast is kept at a certain level. Accordingly there is an advantage; of the invention in a developer, which is stable for constant long-term use; it is merely the addition of supplemental developer in conventional amounts necessary from time to time.

The examples illustrate the invention. All parts, percentages, Ratios and other information are based on weight, unless otherwise stated.

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example 1

A light-sensitive photographic material measuring 25 »4 x 30.5 cm made from a polyethylene terephthalate film support, a gelatin-iodobromide silver emulsion layer (1.5 mole percent silver iodide, gelatin amount 50 g / mole AgX) applied to one side of the Foil carrier in an amount of 40 mg silver (as silver halide) / 100 cm and 50 mg gelatin / 100 cm has been applied, and a protective gelatin layer on the other side of the Film has been applied in an amount of 20 mg gelatin / 100 cm, is exposed and then the subsequent processing using a transport roller developing machine.

Processing processing time temperature '( ⁰ C) (lake) 35 25th 34 25th 33 25th 50 15th

development
Fixation
Water
dry

The formulations of the developer and the fixing solution are as follows specified.

Developer A

Water 500 ml

Hydroxyethylethylenediamine triacetic acid 0.8 g

Sodium sulfite (anhydrous) 50.0 g

Potassium hydroxide 20.0 g

Hydroquinone 25.0 g

1-phenyl-3-pyrazolidone 1.5 g

Boric acid 10.0 g

Triethylene glycol 25.0 g

Glutaraldehyde 5.0 g

Glacial acetic acid 3.0 g

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Sodium hydrogen sulfite (anhydrous) 4 »5 g 5-nitro-imidazole 0.03 g

1-phenyl ~ 5-m.ercaptotetrazole. 0.005 g 5-ethylbenzotriazole 0.005 g

Potassium bromide 6.0 g ■

Water, supplemented to 1.0 liter

Developer B

This developer is prepared by adding 0.5 g of ■ Polyäthylenoxidverbindung (8) has to developer A. This developer has a pH of about 10.30 at 20 ⁰ C.

Fixing solution

Water 500 ml

Ammonium thio sulfate 200.0 g

Sodium sulfite (anhydrous) 20.0 g

Boric acid 8.0 g

Disodium ethylenediamine tetraacetate 0.1 g

Aluminum sulfate '15.0g

Sulfuric acid 2.0 g

Glacial acetic acid 22.0 g

Water, added to 1.0 liter

The pH of this fixing solution is about 4 »10 at 20 ⁰ C,

Developer A and B are in two transport roller development machines used. The same fixing solution is used in both developing machines. The exposure of the films will be like this carried out that about half of the coated silver halide is fully exposed.

Fresh developer is refilled after each development of the films, and you process films with the same area. After the aforementioned photosensitive materials have been exposed in stages using a step wedge,

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the development follows. Thereupon the properties of the developed Images determined using an optical densitometer. The developing machine is a automatic developing machine for X-ray films (Fuji RN); the total processing time is 90 seconds,

The properties of the photographic images are shown below. The last column is the sensitivity (speed) specified.

characteristic gradation B. sensitivity veil A. AWAY AWAY 2.60
2.61 number of
process
ten films 2.53
2.41 100 100
98 98 fresh
1000 0.06 0.06
0.08 0.06

2000 0.09 0.06 2.25 2.60 96 98

From the above results, it can be seen that as Number of processed films in developer A, the fog gradually increases and the gradation decreases, while this phenomenon is not observed in developer B. Regarding the speed is between developer A and developer B no difference observed.

Example 2

A photographic light-sensitive material measuring 25.4 x 30.5 cm made from a polyethylene terephthalate film support, a gelatin-iodobromide silver emulsion layer (10 mole percent silver iodide; 80 g gelatin / mole AgX) on one side of the film support in an amount of 80 mg silver (as silver halide) / 100 cm and 110 mg gelatin / 100 cm is, and a protective gelatin layer that is on the other side of the film support has been applied in an amount of 35 mg gelatin / 100 cm, is exposed and then used

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a transport roller developing machine, as indicated below, processed.

Processing Processing time temperature ( ⁰ O) (min) 31 1.5 28 1.5- 28 1.5 45 1

development
Fixation
Water
dry

The formulations of the developer and the fixing solution are shown below specified.

Developer C

Water 500 ml
Glycol ether diamine tetraacetic acid 0.5 g

Sodium hydrogen sulfite 50.0 g

Potassium hydroxide 36.0 g of hydroquinone 25, Og

1-phenyl-3-pyrazolidone 1.0 g

Diethylene glycol: 11: '0 g potassium carbonate' 10.0 g

Glutaraldehyde-sodium hydrogen sulfite adduct 25.0 g

Sodium bromide '8, Og 5-nitroimidazole' 0.02 g

Water, added to 1 liter

This developer has a pH of about 10.25 at 20 ^° C. Developer D

This developer is prepared by adding 0.25 g of the polyoxyethylene compound (19) to developer C; pH about 10.25 at 20 ⁰ C.

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It becomes the fixing solution of the same composition as in Example 1 used.

An automatic developing machine is used to develop the films used for technical X-ray films (Pakorol Super IX 17-1). The processing of the film is carried out using this Developing machine, in the same way as in example After the same number of films have been developed, the properties of the photographic images are compared with each other.

The properties of the photographic images obtained are shown in the table below.

characteristic D. gradation D. sensitivity T) veil C. 0 C. 0.04
0.04
0.04 2.80
2.82
2.80 100
98
95 number of
process
ten films 2.77
2.63
2.50 100
95
93 fresh
1000
2000 0.04
0.06
0.06

The above results show that the results obtained by the presence of the compound (19) are excellent.

Example 3

A 35 mm negative film with 36 exposures containing a gelatin-halosilver emulsion layer with 5 mole percent silver iodide and 95 mole percent silver bromide on a gelulose acetate film support is made using an automatic transport roller developing machine, processed as specified below.

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Processing processing time temperature

. (. ⁰ C) __ (min)

Development 30 1

Fixation 30 1.5

Soaking 30 1

Drying 45 1

The formulations of developers E and Έ are given below.

Developer E

Water 500 ml

Sodium sulfite (anhydrous) 80 g

Hydroquinone 5.0 g

1-phenyl-3-pyrazolidone 0.2 g Glut araldehyde-sodium hydrogen sulfite adduct 10.0g

Boric acid 10 g

5-nitroimidazole 0.02 g

Potassium bromide 1.0 g

Sodium carbonate (monohydrate) 15 g

Water supplemented to 1 »0 liters

This developer has a pH of 9 »0 at 20 ^° C. Developer F

This developer is made by adding 0.1 g of polyethylene oxide compound (2). The developer has a pH of about 9.0 at 20 ^° C.

A developer solution of the following composition is used:

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Water 600 ml

Sodium thiosulfate (pentanydrate) 300 g Sodium sulfate (anhydrous) 15.0g

Glacial acetic acid 120 ml sodium metaborate 12.0 g

Potassium alum 20.0 g

Water, added to "t, 0 liters

This fixing solution has a pH of about 5.0 at 20 ^° C.

Developers E and F are in the same transport roller developing machines used. The same fixing solution is used in both cases. The film is exposed in such a way that that about 1/3 of the coated silver halide is completely exposed.

Fresh developer is added after each exposure of the film. After films with the same area have been processed in the same manner as in Example 1, the photographic properties are determined. The properties thus obtained are given in the table below.

characteristic F. gamma F. sensitivity F. veil E. E. E. 0.02
0.02
0.02 0.63
0.62
0.63 99
96
97 number of
process
ten films 0.63
0.57
0.51 100
97
99 fresh
300
600 0.02
0.03
0.05

From the above results, it follows that the results due to the compound (2) are excellent.

Comparative example 1

The developer G becomes the same as the developer B

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of Example 1, but a polyethylene oxide with a molecular weight of 4x10, instead of the PolyäthylenoxidverMndung (8) is used. The development takes place according to Example 1, the properties obtained are as follows Table compiled.

characteristic * 0.06 0.06
0.08 0.08 gradation G 53
40 sensitivity veil A. A G A G 2,
2, number of
process
ten films 2.53
2.41 100 100
98 97 fresh
1000

2000 0.09 0.09 2.25 2.27 96 98

The above properties show that the compound used in Developer G, even though it is a polyethylene oxide leads to the same results as in the case v / o the developer does not contain polyethylene oxide,

Comparative example 2

It becomes a photographic light-sensitive material I of Dimensions 25.4 x 30.5 cm prepared by adding a gelatin-iodobromide silver emulsion layer (1.5 mole percent silver iodide; mean grain size of the silver halide crystals 1.2 u; 50 g gelatin / mol AgX) in an amount of 40 mg silver (as silver halide) / 100 cm, and 0.06 mg / 100 cm polyalkylene oxide compound (8), as well as a protective gelatin layer with 20 mg gelatin / 100 cm on both sides of a polyethylene terephthalate film backing brings up. '

This photographic light-sensitive material I is exposed so that about half of the silver halide is completely is exposed, and then using the developer A and the fixing solution used in Example 1 by means of a transport roller developing machine processed (overall processing

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2A55002

time 90 seconds). In this case, after each development of the photographic material developer supplemented.

On the other hand, the same Photographic Material II as in Example 1 is used in the same manner of the developer B and the fixing solution of Example 1 processed. The results are compiled in the table below.

characteristic gradation II sensitivity II veil I. I. I II 2.60
2.61 100
98 number of
process
ten films • 2.47
2.46 102
100 fresh
1000 0.08 0.06
0.08 0.06

2000 0.10 0.06 2.40 2.60 97 98

The above results show for the case where the photosensitive photographic material containing polyalkylene oxide, that the fog value is high, and it can be seen that the fog increases as the number of films processed increases increases. Furthermore, there is the disadvantage of flat gradation because of the large amount of fog that affects the gradation, It follows from all of the above that there are great advantages in incorporating the polyalkylene oxide into the developer.

Claims 509821/0999

Claims (5)

Claims * U Photographisehes development process, thereby characterized in that an exposed photographic Halide silver material developing with buckets of silver halide developers and an aqueous-alkaline one Subjects a solution containing a polyalkylene oxide compound having a molecular weight of about 300 to 20,000 and a Contains dialdehyde. 2. The method according to claim 1, characterized in that one as a polyalkylene oxide compound a non-ionic, cation-active or anion active compound is used. 3 * method according to at least one of claims 1 and 2, characterized characterized in that a nonionic compound is used as the polyalkylene oxide compound, 4. The method according to at least one of claims 1 to 3 _f, characterized in that a polyalkylene oxide compound ml * a molecular weight of 1000 to 9000 is used. 5. The method according to at least one of claims 2 to 4, characterized characterized in that the nonionic compound is PoöLyäthyl englykol, polyethylene glycol methylphenyl ether, Polyoxyethylene alkyl ether, polyoxyethylene nonylphenyl ether, Polyoxyethylene sorbitan ester, block copolymers of polyoxy-.ä% lylen and polyoxypropylene or polyoxyethylene alkyl esters are used. 6. The method according to at least one of claims 1 to 5, .da- • characterized in that one is used as a polyalkylene oxide compound etknown compound of the general formula I. the R. and Rp each represent a hydrogen atom or an organic one Mean a radical having 1 to 16 carbon atoms, and η is a 509821/0999 is an integer from about 5 to 200,
or the general formula II pO-M CHpCHpO -) - H (II) used in which a, b and c each have a positive whole Mean number, the sum a + b + c is about 22 to 80, and b has a value of about 15 to 50. 7. The method according to at least one of claims 1 to 6, characterized characterized in that the polyalkylene oxide compound used in an amount of about 0.0005 to 10 g per liter of the aqueous alkaline solution. 8. The method according to at least one of claims 1 to 7, characterized characterized in that a dihydroxybenzene, a 3-pyrazolidone, an aminophenol, ascorbic acid, a 1-aryl-3-pyrazoline or a mixture of the foregoing Developer used. 9. The method according to at least one of claims 1 to 8, characterized in that the developer in an amount from about 0.01 to 2 moles per liter of the aqueous alkaline solution is used. 10. The method according to at least one of claims 1 to 9, characterized in that the dialdehyde is glutaraldehyde, ot-methylglutaraldehyde, ß-methylglutaraldehyde, maleindialdehyde, succinic dialdehyde, methoxysuccinaldehyde, methylsuccinaldehyde, ot-methoxy-ß-ethglutaraldehyde, ^ -butaraldehyde , oC-Ethyl-ß-ethoxyglutaraldehyde, i) L ><L -dimethoxy succinic dialdehyde, ß-isopropyl succinic dialdehyde, <^ _ »^ -diethyl amberdialdehyde, butylmaleindialdehyde, the hydrogen sulfite adducts of the aforementioned di- ·· used hereof . 50982 1/0999 ti. Method according to at least one of Claims 1 to 10, characterized characterized in that the dialdehyde in an amount from about 1 to 50 g, per liter of the aqueous-alkaline solution, used. 12. The method according to at least one of claims 1 to 11, characterized in that in the aqueous ~ alkaline
Solution preservatives, buffers, basic substances, solubilizers, pH regulators, sensitizers, development accelerators, surfactants, antifoggants and / or chelating agents are used. 13 «The method according to at least one of claims 1 to 12, characterized characterized in that the aqueous-alkaline solution with a pH of about 8.5 to 11.5. used. 14 »Method according to at least one of claims 1 to 13» thereby characterized in that a black and white silver halide photographic material is used as the silver halide photographic material used. 15. The method according to at least one of claims 1 to 14 »thereby characterized in that the photographic halogen coating material fixed and watered after developing. 16. The method according to at least one of claims 1 to 15 »thereby characterized in that the silver halide developer is used in the aqueous-alkaline solution. 17 · The method according to at least one of claims 1 to 16, characterized characterized in that one uses the silver halide developer . Applies in the silver halide photographic material. 5 0 9821/0999