DE2002871C3 - Use of imidazole derivatives as development accelerators in the development of silver halide photographic materials - Google Patents

Description

In developing a silver halide photographic material it is expedient and desirable, the extent or the speed of the development to promote, in other words, to increase the sensitivity of the material. For this purpose it was known To use amine compounds as development accelerators. Typical examples are alkylamines (cf. USA. Patent 21 96 037), aralkylamines (see. US A. Patent 24 96 903, 25 15 147 and 25 41 889), phenoxyalkylamines (cf. USA. Patent 24 82 546), heterocyclic alkylamines (cf. USA. Patent 26 05 183), morpholine, piperidine or the like (U.S. Patent 23 04 025), xylylenediamine (cf. British Patent 10 86618) and imidiazole (see U.S. Patent 31 26 282).

However, these amines usually have a bad odor. In addition, their concentrations are often not kept constant in the treatment solutions due to their volatility. Although the extent or rate of development is accelerated by the amines, the extent or the speed does not increase sufficiently and it becomes an increase fogging and deterioration in the graininess of the developed silver were observed.

The object of the invention is to provide a development accelerator which can be used in a simple manner for the acceleration of the development extent or the development speed and for the increase of the effective sensitivity without increasing fog and without deteriorating the silver image can be.

For this purpose, according to the invention, compounds of the general below

where R 1, R ₂ , R3 and Ra each represent a hydrogen atom, a lower alkyl group (C- - C5), an allyl group or a vinyl group, where at least one of the radicals R 1 and Ra is not hydrogen, or one of the radicals Rt to A _{t represents} a hydroxylalkyl group (Cr - C5) and the remaining radicals are hydrogen, used as a development accelerator in the development of silver halide photographic materials.

Examples of compounds of the general formula given above, which according to the invention are used are:

2-methylimidazole, 4-methylimidazole,

2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-amylimidazole, 1-isoamyl-2-methylimidazole,

4,5-dimethylimidazole, 2-ethylimidazole, 1-methylimidazole, 2,4,5-trimethylimidazole, 4-hydroxymethyl-5-methylimidazole.

4- (2-HydroxyäthyI) -5-methylimidazole, 1 - allyl-2-methylimidazole,

1 - vinyl-2-methylimidazole.

These compounds are known. Procedures for their preparation are in “The Chemistry of Heterocyclic Compounds, Imidazole and Derivatives "([1953], Interscience Publishers Inc, New York). It was known from US Pat. No. 31 26 282 that imidazole of the first stage (black-and-white development) a color reversal treatment for the films in which couplers are incorporated. However, this compound is less effective compared with the alkylimidazole derivatives according to FIG Invention at. a development acceleration, as shown below with reference to comparative examples will be shown.

The compounds according to the invention can be applied to silver halide photographic materials in general as a development accelerator, especially for fine-grain materials with relatively low sensitivity, be applied. The addition of the known development accelerators to the developer leads to a deterioration in graininess and (image) resolution, which is particularly unfavorable for the materials, which are intended for high resolution is. In contrast it occurs when using the connections according to the invention does not exhibit such deterioration of the photographic image. In color reversal treatment increases the presence of the compound according to the invention in the black and white developer also the film speed or shortens the treatment time. The connections according to the Invention are more effective in terms of speed of development than those commonly used Thiocyanates and alkylamines, whereby they reduce the sensitivity and image sharpness of a photograph! -

/1

ichen bilcies increase. Moreover, the compounds iemäß de ^f the invention are not accompanied by an increase of development veils. The development of light can also be accelerated without deteriorating the dot quality. The compounds according to the invention can provide rapid treatment without increasing the development temperature, although the combination of imidazoles and temperature also enables a further reduction in the treatment time. ι ο

The developers to which the compounds according to the invention can be effectively applied are the commonly used photographic silver halide developers, ie an aqueous solution containing one or more of the compounds of hydroquinone, 1-phenyl-3-pyrazolidone and N- Methyl-p-aminophenol, which is antioxidant, e.g. B. sodium sulfite or ascorbic acid, salts such as sodium sulfate, pH regulator compounds or pH buffers, for example boric acid, borax, sodium hydroxide, sodium carbonate or trisodium phosphate, development inhibitors, e.g. Potassium iodide or potassium bromide, and organic fog retardants such as 6-nitrobenzimidazole or benzotriazole can be added. In some cases an aldehyde such as formaldehyde or glutaraldehyde can be added. . ,,, .. ₄ -

In addition to being added to the developer, the compounds according to the invention can also be added to a bath before development or _{incorporated into a 1C} halogen silver emulsion. In the case of adding it to the developer, the amount of the compound added is usually in the range of 0.01 to 100 g / 1000 ml of the developer, and preferably in the range of 0.05 to 10 g /. In the case of addition to a silver halide emulsion, the suitable amount can be in the range from 0.01 g to 50 g / l mol of silver halide and the addition can be made at any stage of the preparation of the emulsion, but preferably after the second ripening and before application as a coating or coating. are executed. Instead of incorporating the compound directly into an emulsion layer, it can also be incorporated into an adjacent layer, for example a protective layer, whereupon the compound penetrates through the emulsion layer. The invention can be applied to a silver chloride, silver bromide, silver chlorobromide, silver iodine, silver iodobromide, and silver chloride emulsion. The emulsion can be chemically sensitized with an unstable sulfur compound, a gold compound, or both. The emulsion can be spectrally sensitized with a cyanine dye or a merocyanine dye. The emulsion can be mixed with a heterocyclic compound, e.g. 4-hydroxy-6-methyll, 3,3a, 7-tetrazaindene or 1-phenyl-5-mercaptototrazole. In addition, the emulsion can be treated with a hardening agent, e.g. B. formalin or chloromuconic acid may be hardened or contain a surface-active agent to facilitate enrobing or coating.

The invention is explained in more detail below with the aid of examples.

example

A fine-grain positive film for motion picture cameras or cinema purposes, on which a fine-grain chlorobromosilver gelatin emulsion applied as a coating or overcoat was followed by development with a developer given composition at 27 ° C.

Developer A
water

N-methyl-p-aminophenol sulfate
Sodium sulfite
Hydroquinone

borax

Water, rest on

800 ml

20 g 100 g 5g 2g

nsuti, iwjiuu. 1000 ml

The standard development time for the above batch was 4 minutes; however, if the Compound according to the invention, namely 2-methylimidazole, was added, the development time was shortened as shown in Table I below. A development in 4 min with addition of the compound according to the invention resulted in high sensitivity,

as also indicated in Table 1.

The "relative sensitivity" given in Table 1 and in the examples below is by the relative value of the exposure amount (as a logarithmic value) corresponding to a density of

0.2 expressed via veil.

Also included in Table I are fog and graininess results. The specified Granularity values were given as the relative value of the physical granularity according to S e 1 w y η (cf. E. W. H. S e 1 w y η, Photo. Journ. 79, page 513 [1939]).

Table I.

Quantity (g / 1)

Development in 4 min

rel. Veil gamma sensitivity

Development time required to achieve relative sensitivity from 100

Graininess

control

2-methylimidazole

2-methylimidazole

0 1 4

100 220 430

Example!

1.35
1.35
1.40

4 min
2 min
1 min

100

95

100

A film of high sensitivity, comprising on a support a coating of a color-sensitized lodbromsilber gelatin emulsion, was subjected to development at 20 ⁰ C with a developer having the composition shown below.

Developer B
water

1-phenyl-3-pyrazolidone
Sodium sulfite
Hydroquinone
borax
Boric acid
Potassium bromide
Water, rest on

800 ml 0.2 g 100g 5g 2g 1g Ig 1000 ml

The standard development time for the batch given above was 8 minutes. But when the compound according to the invention, 2-methylimidazole, was added, the development time was shortened as shown in Table II below is shown.

In addition, good results were obtained in terms of fogging and graininess.

Table II

Additional quantity (g / l)

(Mol / l) development time

veil

Graininess

control

2-methylimidazole

2-methylimidazole

0.82

1.64

(IxIO- ² ) (2XlO- ² ) min
min
min

0.28
0.28
0.29

100
100
100

Example 3

A high resolution plate with a carrier and an ultra-fine grain iodobromide silver gelatin emulsion as a coating thereon was subjected to development at 20 ^° C. with a developer of the following composition:

Developer C
water

1-phenyl-3-pyrazolidone
Sodium sulfite
Hydroquinone
Sodium carbonate monohydrate

800 ml 0.5 g 50 g

12g 60g

Potassium bromide
Benzotriazole
Water, rest on

2.0 g
0.2 g
1000 ml

The standard development time for the batch given above was 6 minutes. But when

ίο the connection according to the invention, namely 2-methylimidazole was added, the development time was shortened as shown in FIG Table III is given. The development in 6 minutes with the addition of the compound according to the invention gave high sensitivity as shown in Table III. It also got good results in terms of Fogging and graininess achieved.

Table III

crowd

(g / l)

Development in 6 min

rel. veil

sensitivity

Development time required for the

Achieving a relative gamma

Sensitivity of 100

(min)

Graininess

control
2-methylimidazole
2-methylimidazole
2-methylimidazole

100 180 340 800

0.04 0.04 0.05 0.06 3.24
3.80
4.30
8.14

min 30 see

sec

100
95
95

100

Example 4

A fine-grain positive film for cinema use (motion picture camera) with a carrier and a fine-grain chlorobromo-silver gelatin emulsion as a coating thereon, development at 24 ° C. with a developer of subject to the following composition:

Developer C
water

N-methyl-p-amino-phenol sulfate

800 ml Ug

Sodium sulfate

Hydroquinone

borax

Boric acid

Potassium bromide

Water, rest on

50 g
4.4g 10g
5.0 g
0.5 g
1000 ml

The standard development time for the above formulation was 5 minutes. However, when χ 10 " ² mol / l of the compound according to the invention were added, the development time was shortened as shown in Table IV.

Table IV Example 5 20 02 as a coating crowd 25th 800 ml 871 y 8th veil : was 4 min Graininess • 4.00 Required Ent Graininess 7th at 20 ⁰ C with 0.04 100 4.10 development time for control a developer of the following composition 1.0 g 0.04 95 4.15 achieving a 2-methylimidazole Additional amount
(g / i) subject to: Development time 0.05 100 relative sens 2,4-dimethylimidazole 0 Developer E 5 min 0.04 95 chance of 100 2,4,5-trimethylimidazole 0.82 water (g / i) 3 min 10 see 0.04 100 (min) 2-ethylimidazole 0.96 N-methyl-p-aminophenol- Control 0 3 min 0.05 100 4th 100 1-methylimidazole 1.10 sulfate 2-methylimidazole 1 3 min 0.04 100 2 95 4-hydroxymethyl-5-methylimidazole 0.96 Table V 2-methylimidazo! 4th 3 min 20 see 0.04 100 1 100 2-methyl-4-butylimidazole 0.82 2 min 50 see 0.06 100 4-AHyl-2-methylimidazole 1.12 3 min 20 see 0.04 100 imidazole 1.38 3 min 20 see 75 g 1.22 2 min 40 see Hydroquinone
Sodium carbonate monohydrate 9.0 g
29 g 0.68 4 min 30 s Potassium bromide 6.0 g Sodium sulfite IVu ■ ■ VA ■ W IW I ^ S 111 4 * Λ
Water, rest on 1000 ml A microfilm with a carrier and a fine ^ _n komchlorobromosilver gelatin emulsion protruding tion on it became a development however the of the invention, 2-methylimidazole, The standard development time for the became the development time given approach abbreviated as shown in Table V below. Connection according to was admitted Development in 4 min rel. Veil gamma Sensation opportunity 100 0.19 160 0.19 330 0.20

The development in 4 minutes with the addition of the compound according to the invention was high Sensitivity as also shown in Table V above.

Example 6

A direct X-ray filiTi of high sensitivity with a carrier and a jogbrom silver gelatin emulsion

Sion as a coating thereon was subjected to rapid development at high temperature at 35 ° C with Developer C given in Example 3. Developer C usually required 100 seconds for development. However, when the compound of the invention was added, the development time was shortened as shown in Table VI below.

Table VI

control

2-methylimidazole

2-methylimidazole

2-methylimidazole

2,4-dimethylimidazole

2,4-dimethylimidazole

imidazole

Additional amount (Minor) ² ) (g / l) ² ) 0 (2.5x10- ² ) 2.1 (5.0x10- ^? ) 4.2 (2.5x10- ² ) 2.4 (2.5x10- ² ) 2.4 (5, Ox 10- 4.8 (2.5x10 1.07

Development ski length of time 100 see 55 see 0.16 45 see 0.16 45 see 0.17 45 see 0.17 40 see 0.18 70 see 0.16

Graininess

100
95

100
95

100

100

709 649/105

ίο

Example 7 A lithographic film for

_ -ο -, - photomechanical

Purposes with a carrier and a chlorobromide silver gelatin emulsion as a coating thereon, development at 20 ° C. with a developer of subject to the following composition:

Developer F

Water 500 ml

Sodium sulfite 30 g

Paraformaldehyde 7.5 g

Table VII

Potassium bisulfite
Boric acid
Hydroquinone
Potassium bromide
Water. Rest on

2.6 g

7.5 g 22.5 g

1.6 g 1000 ml

The standard development time for the above batch was 2 minutes, but if 2-methylimidazole was added according to the invention, the development time was shortened without the degrade pure dot quality as shown in Table VII below.

Additional amount

(g / l)

Development time veil

Graininess

control 0 2 min 0.07 100 2-methylimidazole 1 1 min 30 sec 0.07 95 2-methylimidazole 2 1 min 0.08 100

35

Example 8

A color photographic material with essentially

(a) a blue-sensitive halosilver gelatin emulsion layer containing a yellow color coupler which gives a yellow color by reaction with an oxidized developing agent forms,

(b) a yellow filter layer,

(c) a green sensitive halogen over gelatin emulsion layer with a magenta color coupler that forms a magenta color,

(d) a red sensitive silver halide gelatin emulsion layer containing a cyan color coupler which forms a cyan color, and

(e) a film carrier

was subjected to development at 20 ^° C. for 15 min with a developer of the composition given below:

Developer G

Water 800 ml N-methyl-p-aminophenol-

sulfate 3.0 g

Sodium sulfite 50 g

Hydroquinone 6.0 g

Sodium carbonate monohydrate 42 g

Potassium bromide 3.0 g

Water, rest to 1000 ml

The film was immersed in a solution of chrome alum for 3 minutes, then with white light from

Table VIII

irradiated on both sides and for 15 min with a color-forming developer of the following Composition developed:

Color forming developer:
water
Benzyl alcohol
Sodium sulfite
Trisodium phosphate 12 hydrate
Potassium bromide
Sodium hydroxide
Citrazinic acid
4-Amino-N-ethyl-N- (ß-methane-sulfonamide-ethyl) -m-toluidine-sesquisulfate monohydrate
Water, rest on

800 ml 6.0 ml 5.0 g

35 g 1.0 g 2.5 g 1.2 g

10g 1000 ml

45 The film was then washed for 5 minutes in a solution of acetic acid and sodium acetate introduced for 5 min, washed with water for 1 min, in a bleach solution containing g potassium ferricyanide and 15 g sodium bromide per ref desilvered and fixed with sodium thiosulfate.

The standard development time for the above composition was 15 minutes however, the compound according to the invention was added, the development time was shortened, like that; shown in Table VIII below. For comparison purposes, the well-known potassium thio was also used cyanate used.

additive
amount, g / l Develop
duration veil G B. Graininess G B. (1, OxIO- ² (1, -iin) R. R. Minor) 0.15 0.18 100 100 control 0 15th 0.15 0.10 0.12 100 95 100 2-methylimidazole 0.82 9 0.08 0.10 0.12 95 100 100 2,4-dimethylimidazole 0.96 9 0.08 0.10 0.11 95 100 100 1-methylimidazole 0.82 8th 0.08 0.09 0.10 95 100 100 1 -Allyl-2-methylimida / .ol 1.22 7th 0.08 0.12 0.13 100 110 110 Potassium thiocyanate 0.97 12th 0.10 0.13 0.15 105 105 105 Imidazole 0.64 11th 0.12 100

Example 9

A reversal color film, the couplers of which are incorporated with the developers, supported by a cellulose acetate film and a red-sensitive silver iodobromide gelatin emulsion, a green-sensitive silver iodobromide gelatin emulsion, a blue light absorbing yellow filter layer made of colloidal silver and a blue-sensitive iodobromide silver gelatin emulsion as a coating in the order given (D) 1-Allyl-2-methylimidazole

U22 g / l
(0.01 mol / l)

Then the film was washed with water for 2 minutes, a reverse exposure to red light subjected from the back and with a cyan color forming developer with the one below specified composition treated at 24 ° C for 5 min.

the carrier was at 24 ° C for 5 min with a 800 ml Cyan color forming developer 800 ml Black and white developers of the following composition water 5.0 g composition developed. 2.0 g Sodium sulfite 90 g 2-amino-5-diethylamino 0.6 g Developer H 8.0 g 15 toluene hydrochloride 15g water 52.5 g Sodium carbonate monohydrate 0.5 g N-methyl-p-aminophenol- 5.0 g Potassium bromide sulfate 1000 ml Potassium iodide 5.0 ml Sodium sulfite (0.1% aqueous solution) Hydroquinone 20 l, 5-dhydroxy-2,6-dibromo 1.2 g Sodium carbonate monohydrate naphthalene Potassium bromide Sodium hydroxide monobenzyl 2.0 g Water, rest on p-amine phenol hydrochloride 1000 ml Water, rest on

This developer was divided into 4 parts, and 3 parts became compounds according to the invention added as indicated below:

(A) control no addition (B) 2-methylimidazole 0.82 g / l (0.01 mol / l) (C) 1-methylimidazole 0.82 g / l (0.01 mol / l)

The film thus treated was then washed with water for 5 minutes with a bleach solution a content of 100 g Calciumferncyanid and 10 g sodium bromide per I desilvered and for 2 min fixed for 2 min with a solution of sodium thiosulfate. The characteristic values of the film, the Cyan reversal development is listed in Table IX below:

Table IX

Attempt no.

Additional amount, g / l Characteristic values

(0.01 mol / l)

rel. sensitivity

maximum
density

veil

Graininess

A control 0 100 3.32 0.17 100 B 2-methylimidazoi 0.82 270 3.25 0.08 95 C1-methylimidazole 0.82 320 3.13 0.07 95 D l -allyl-2-methylimidazole i, 22 560 3.03 0.07 100

Coating or coating applied to a film base, followed by drying. The sample film

.- ". ^", """U ^, _KC1 ., A _U uv, ~ - .. ,, ■■ was at 24 ° C for 5 min with the developer D

In the form of an aqueous solution of an iodobromosilver Ge 50 from Example 4 developed. The received .. · - .. · · ^. ι. - -> n »i_i n /" photographic characteristic values are in the

Example 10
2-methylimidazole according to the invention was in

latine emulsion containing 3.0 mol% silver iodide was added and the emulsion was used as

Table X

Table X below:

control

2-methylimidazole

2-methylimidazole

Additional amount of characteristic values

g / l mole of silver halide

relative veil

sensitivity

gamma

0.05
0.06
0.07

0.85
0.90
0.82

Graininess

100

95

100

Claims (1)

a formula Claim: Use of compounds of the general formula given below - ^s where R \, /? 2, /? 3 and Ra each represent a hydrogen atom, an alkyl group (Ci - C ₅ ), an allyl group or a vinyl group, with at least one of the radicals R \ and R * not being hydrogen, or one of the radicals R 1 to Ra represents a hydroxyalkyl group (Ci-C ₅ ) and the remaining radicals represent hydrogen, as a development accelerator in the development of photographic silver halide recording materials. 25th