DE2049502A1 - Photographic development process and developer solution suitable therefor - Google Patents

Description

The favorable properties in the treatment process for photographic black and white silver halide materials lie in increased speed indi ^ ksit, high Extent of development and a fine-grained silver image. The well-known development accelerators are ikmin compounds, like Alkyiamine (US-Fatentschrift 2 196 037), Aralkylamines (U.S. Patents 2,496,903, 2,515,147, 2,541,809), phenoxyalkylamines (US Pat. No. 2,482,546), heterocyclic alkyl amines (US Pat 2,605,183), morpholine and piperidine (U.S. Patent 1 086 681). However, these amines are poisonous, have a pungent smell, and are volatile. Therefore is careful Handling the Amines Required Their concentration in the developer solution is often difficult to keep constant keep"

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An increase in the extent of development will to some extent is observed when these compounds are added to the developing solution, but this effect becomes Frequently canceled by the increase in fog formation and furthermore, a deterioration in the grain size will frequently occur of the developed silver.

A main object of the invention is therefore to provide an improved accelerator for the developer solution, which is easy to handle, gives an increase in the amount of development and the effective speed of the photographic material without an unfavorable increase in fog and without deterioration the grain of the developed silver increases.

In particular, it is an object of the invention to provide a method for accelerating the development of fine grains photographic materials without damaging the grain of the developed silver.

The developer solution according to the invention is used for black-and-white photographic materials, particularly to silver halide photographic materials of low sensitivity which have a fine Grain required and it is generally used for office work, documentation work, industrial work or reprographic work applied.

The present invention can be applied to telephotographic Materials, lithographic materials (used to create spots), phototype materials, Microfilms, microplates, facsimile materials, halftone printing materials, materials for the production of integral circuit master images and photographic materials for astronomical sub. Bookings will be applied. This photographic

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Materials are made up of extremely fine-grained silver halide and contain little or no Amounts of silver halide. Therefore, the two characteristics of the photographic materials make different Ways of development versus those of ordinary photographic materials.

With these materials, the grain of the developed silver image must be sufficiently low during the Development in the development of, for example, fine-grain silver halide emulsions, as in development acceleration be according to the invention. For this purpose, the present invention provides a method for the treatment of photographic materials, the materials with a developer, the imidazole and hydroquinones keeps being developed, so that the rate of development or the abbreviation of the Development time is increased, leverage is inhibited, and effective sensitivity is increased the developed silver parts become fine.

From US Pat. No. 3,126,282 it is already known to use imidazole as the first developer for a Add reversal color film, the emulsion of which is a non-diffusing Contains color couplers, and to increase the speed or sensitivity of the film.

However, the increase in the speed or sensitivity of black-and-white photographic material to which the present invention is applied is far higher than that of the reverse color film by the imidazole according to the US patent, According to the examples is the reverse color film of the US patent from an emulsion of coarse silver iodobromide particles built up while the emulsions of the photographic.

1 0 9 8 1 6/1 G 1 9 BAD OWGHNAL

black-and-white materials used in the context of the invention contains fine silver halide particles.

The process for developing photographic materials containing fine silver halide grains is based according to the invention on the position that the increase in sensitivity by the imidazole depends on the size of the silver halide grains.

The fact that the development of the photographic material with fine grain silver halides by the addition of imidazole to the developer solution to the extent indicated in the examples accelerated becomes and the developed silver grains are fine and uniform, was previously unknown and results from not with the state of the art.

The developing solution which exhibits the above advantageous effects when the imidazole is added contains at least hydroquinone as the main developing agent and in many cases also 1-phenyl-3-pyrazolidone or K-methyl-p-aminophenol. If necessary, can Oxidation inhibitors such as sodium sulfite or ascorbic acid, suitable pH buffers such as boric acid, sodium hydroxide, Sodium carbonate or sodium phosphate, development inhibitors such as potassium iodide or potassium bromide, organic Fog inhibitors, such as 6-nitro-benzimidazole or benzotriazole, and aldehydes, such as formaldehyde or glutaraldehyde, can be added to the developer solution. The pH of the developer solution can be in a range between 8.5 and 12.0 can be set. The amount of imidazole added to the developer solution changes however, it is favorable with the kind of photographic materials and the pH of the developing solution in the range between 0.5 g / l and 10 g / l,

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2 (J Λ 9 "O

The following examples serve for further explanation of the invention without limiting it.

The eight fol ^ imden Ar ton / on υη.> Tugriu hi s
Films (I) to (VITI) were sent to LLoht iidtt ^ lG an
exposed to iiensitometers and subjected to the method according to the invention: (I) commercial direct x-ray film, (II) highly sensitive black and white negative film (ASA 100) for amateur purposes, (III) reverse color film (ASA 100) for amateur purposes, (IV) color negative film (A3A 100) for amateur purposes (V), fine-grain black and white positive film for cinematography, (VI) resographic film for photomechanical use, (VII) telephotographic film, (VIII) microfilm.

The method of the invention was with the films (I) to (IV) ineffective, but the test results are for comparison with those of the films (V) to (VIII) indicated. The mean diameters of the silver halide grains in each photographic film were the following:

Photographic film

Mean diameter of the silver particles

I. M. micron II 0.8 Il III 0.9 Il IV 1.0 ♦ I V 0.1 5 " VI 0.2 H VIl 0.2 Il VIII 0.2 Ii

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BAD OWGfNAt

Every photograph! tic he film (I) to (VIII) became the Development treatment with those given below subjected to suitable development solutions:

(a) Developer solution for the photographic film (I): Hendol development solution (product of Fuji Photo Film Go. Ltd.)

(b) Photographic film developing solution (II): D-76 developing solution (product of Eastman Kodak Co. Ltd.)

(c) Developer solution for the photographic film (III) (inherited developer for the reversal color film):

N-methyl-p-aminophenol 5.0 g Sodium sulfite 70.0 g Hydroquinone 2.0 g Sodium carbonate monohydrate 41.0 g Potassium bromide 4.0 g

Potassium thiocyanate 1.6 g potassium iodide (0.1 # strength aqueous solution) 10.0 ecm

Water to 11

(d) Developer solution for photographic film (IV) (developer for color negative film):

Sodium hexaraetaphosphate 1.4 g

Benzil alcohol 5.0 ml Sodium sulfite 3.0 g Sodium carbonate 41.0 g

Sodium hydroxide 1.0 g

4-Amino-3-methyl-N-ethyl-N-methane sulfate, 5.0 g

Potassium bromide 0.5 g

Water to 11

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BAD ORKMNAL

(e) developer solution for photograph! see films (V)

to (VIII):

D-16 developer solution for black and white posifilm (Eastman Kodak).

This developer D-16 was also used in the films (I) and (II) were applied although they were also dealt with by developers (a) and (b). In the first row became the developer solutions (a) to (b) imidazole not added and in the second row 2.0 g / l were added.

The test results are in the following table contain.

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Tabel

Development
conditions
(Developer,
Temperature, time) Addition of the
Imidazoles Relative
Sensitive
speed
(logarithmi
cal sensation
possibility) annotation I. photo
graphic
Movies Rendol, 24 ⁰ C
5 min. 0 g / l 2.60 00
I. I. π 2.0 2.65 Increase in fog formation,
Deterioration of the
Silver picture If D-76, 24 ⁰ C
6 min. 0 2.20 II It 2.0 2.30 Deterioration of the
Silver picture Il (c), 24 ^° C
6 min. 0 2.35 III Il 2.0 2.50 Deterioration of the
Silver picture Il (c) ^x , 24 ⁰ C
6 min. 2.0 2.45 Il (d), 24 ^° C
10 min. 0 2.05 IV It 2.0 2.10 It

CQ CTI CD

Table (port setting)

Photographic
Movies

Development conditions (developer, temperature, time)

Addition of the
Imidazoles

Relative sensitivity

(logarithmic sensitivity

annotation

, 860 II
ti V OT
CD η
VI
ti VII η VIII ti

D-16,
5 min.

24 ⁰ C

O
2.0

0
2.0

2.0

2.0

2.0

2.0

2.45 2.50

2.35 2.45

0.25 1.00 1.05 1.45 1.20 1.60 0.15 1.05

Increase in the fog, deterioration of the silver image

Deterioration of the silver image

(c) ^x is the same developer solution as (c), except that it lacks potassium thiocyanate.

It can be seen from this table that the addition of iraidazole for emulsions of fine-grain silver halide is very effective.

Example 2

A commercially available fine-grain positive film for cinematography, which was built up from a fine-grain silver bromochloride gelatin emulsion, was subjected to development with a solution of the following composition at 27 ^° C.

Developer solution A:

Water 800 ml of N-methyl-p-aminophenol sulfate 2.0 g

Sodium sulfite 100 g

Hydroquinone 5 g

Borax 2 g

Water to 11

This developer solution took 4 minutes to develop the positive film, but it was possible by adding the development time of imidazole can be greatly shortened. On the other hand, development treatment increased during 4 minutes when imidazole is added to the developer solution, a high sensitivity, as can be seen from the following table I results.

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Table I.

Trains
sat at 4 minutes Ent
winding fog 1
1
1 3 r required
development time Development
to he amounts
(g / l) re
lative
Sensation
opportunity 0.04
. 0.04
0.05 , 30
, 33
, 36 aiming a rela
tive sensitive
speed of 100 (min.) comparison
Imidazole
Imidazole O
1
4th 100
180
300 example 4th
2.5
1.5

A plate with high resolution, which consisted of a carrier with an ultrafine-grain silver iodobromide gelatin emulsion drawn thereon, was ^{treated at 20 °} C. with a developer solution of the following composition:

Developer solution 0:

water

1-phenyl-3-pyrazolidone

Sodium sulfite

Hydroquinone

Sodium carbonate (NapCO ^,

Potassium bromide

Benzotriazole

Water too

800 ml 0.5 g 50 g 12 g 60 g 2.0 g 0.2 g 1 1

This developer solution took 6 minutes to develop the dry plate, but when imidazole was added the developing time of the developing solution was shortened as shown in Table II. On the other hand it showed

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when developing for 6 minutes with the imidazole containing developer solution has a high sensitivity of the dry plate.

Table II

trains development during

sat 4 minutes

lot

relative

Sensitive
speed

fog

Development time required (min.) to achieve relative sensitivity from 100

Compare 0 100
Imidazole 1 150
Imidazo! 2 280

0.04 5.24 0.04 3.40 0.05 3.75

6 4 2.5

Example 4

A commercially available microfilm consisting of a carrier with a fine-grained silver chlorobromide gelatin emulsion was developed at 20 ^° C. with a developer solution of the following composition:

Developer solution E:

Water 800 ml

N-methyl-p-aminophenol sulfate 1.0 g

Sodium sulfite 75 g

Hydroquinone 9.0 g

Sodium carbonate (Na ₂ CO, .H ₂ O) 29 g

Potassium bromide 6.0 g

Water to 11

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However, this developer solution (E) required 4 minutes to develop the microfilm by adding the imidazole to the developer solution, the development time, as can be seen from Table III, abbreviated. On the other hand, development for 4 minutes with the imidazole-added developing solution resulted obtain a high sensitivity of the microfilm. In addition, the developed were silver grains favorably fine and uniform in the image when using the method of the present invention the developer solution containing the imidazole.

Table III

tensile at 4 minutes shocked winding amount relative (g / l) tive

el

0 Sensation 0.19 4.00 1 opportunity 0.20 4.06 comparison 4th 100 0.21 4.08 Imidazole 140 Imidazole 250

required development time (min.) for relative sensitivity from 100

4 3 2

The invention has been explained above in particular with the aid of a few examples, but is not based on this limited.

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Claims (10)

Claims Developing solution for black-and-white photographic material, which contains fine-grain silver halide, characterized by a content of hydroquinone and at least 0.5 g imidazole per liter of developer solution. 2. A method for developing a black-and-white silver halide photographic material, the silver halide grains of which are less than 0.3 M , characterized in that the photographic material with a developer solution containing at least hydroquinone as the main developing agent and at least 0.5 g of imidazole to a Liters of the developer solution is developed. 3. The method according to claim 2, characterized in that a silver halide which contains fine-grain silver chlorobromide and less than 1 $ silver iodide, the particle size of the silver halide being less than 0.2 ix, is developed. 4. The method according to claim 2, characterized in that a photographic material for reprographic Purposes is developed. 5. The method according to claim 2, characterized in that a photographic material for lithographic Footage is developed. 6. The method according to claim 2, characterized in that that a photographic material is developed for printing halftone spots. 7. The method according to claim 2, characterized in that a photographic material developed for facsimile will. 8. The method according to claim 2, characterized in that a photographic material for integral circuits is being developed. 109816/1619 9. The method according to claim 2, characterized in that developed a photographic material for microfilms will. 10. The method according to claim 2, characterized in that a photographic material is developed for the phototypesetting . 109816/1619