DE2357852A1 - PHOTOGRAPHIC MATERIAL - Google Patents

Description

A type of silver halide photographic material, which is gaining in importance because of its ease of processing, contains a silver halide developing agent in one layer. Photographic material of this type is usually processed by the exposed material with an activator solution, which a bath with a high. p ^ r value, and then with a Treated stabilizer solution that did not expose the

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Converts silver halide into a light-insensitive silver complex. This processing method becomes common carried out in an automatic processing plant, to which the exposed material can be fed and the developed and stabilized print material can be removed.

The usual developing agent incorporated in the photographic material is hydroquinone. However, it is sometimes necessary that the photographic material have a comparatively high sensitivity, and if so Material in the usual processing plant with activator solution / stabilizer solution is processed, you will not get satisfactory prints, especially with regard to the Contrast effect and shoulder sensitivity, as there is insufficient development time for this. But if you have the Increased development time sufficiently to eliminate these drawbacks will be the advantages of using an automatic Processing facility significantly reduced.

It is the object of the present invention to provide a5 To make photographic material available for processing in an automatic processing facility with activator solution / stabilizer solution is suitable, the disadvantages mentioned being largely eliminated.

The present invention therefore relates to photographic photography monochromatic silver halide emulsion material suitable for processing in an automatic processing plant

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system with activator solution / stabilizer solution is suitable, which is in at least one silver halide emulsion layer. or in a layer in effective contact therewith, 30 to 150 grams of silver present per gram atom in the emulsion of a hydroquinone derivative of the formula

contains, wherein E is a straight or branched alkyl group with 2 to 8, preferably 3 to 8 and in particular 3 to 3 carbon atoms and M is a hydrogen or alkali metal atom is.

The preferred compounds of formula I, which in the photo, Graphic material of the present invention find use are those in which R η-butyl, sec-butyl or n-hexyl is.

Preferably the compounds of formula I are in the silver halide emulsion layer or present in each silver halide emulsion layer if more than one such layer is present. However, the compounds of formula I can be present in any layer of the photographic material be on the same side of the support as the silver halide emulsion layer or layers

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find, whereby they can migrate out of this layer when they are treated with the activator solution. Such layers are referred to herein as layers in effective contact with a silver halide emulsion layer are located. Such layers can be a subbing layer, an intermediate layer or a top layer.

In a preferred embodiment, the present invention relates to a photographic material which is used for processing is suitable in an automatic processing plant with activator / stabilizer solution, which in of the silver halide emulsion layer or in a layer in effective contact therewith, per gram atom in the Emulsion present silver contains 30 to 150g of a hydroquinone derivative of the formula I together with hydroquinone, from the 30 to 150 grams of silver present per gram atom in the emulsion also in the silver halide emulsion layer or in a layer in effective contact therewith.

It was found that the material of the present Invention, in some cases, a hydroquinone derivative of the formula I alone or preferably together with hydroquinone itself contains, has increased developability. This shows up as increased shoulder sensitivity during development and an image with greater contrast.

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However, the Hydroohinonderivate of the formula I, wherein R is a methyl or a uonyl or higher alkyl group is not the same favorable results when in the photographicη material of the present Invention present. .

A silver halide photographic material with comparatively high sensitivity for processing in an automatic processing plant with activator / stabilizer solution is suitable, is the photographic material, as described in Example 2 of British Patent 1,287,978, it being stated that this material Contains hydroquinone in the emulsion layer .. With a similar material, but a hydroquinone derivative of the Formula I contains that completely or partially Replaced hydroquinone, a significantly improved material is obtained, as described in Example 1 below will.

In another aspect, the present invention relates to a method of processing a photographic material of the type described here, which contains a hydroquinone derivative of the formula I, including the photographic material exposed and it successively in an automatic processing plant with an activator solution and with a Treated stabilizer solution

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Any of the common activator solutions can be used will. Generally they contain a solution of sodium hydroxide normal in concentrations of 1 to 3.

Any of the usual stabilizer solutions can be used, but the preferred stabilizer is a water soluble one Rhodanide, for example ammonium rhodanide. The usual additives can be present in these two solutions be, for example hardeners, wetting agents, antifoams and image stabilizers.

In the examples (in Tables I to IV) the following parameters are given:

SO.7 corresponds (approximately) to the half-value sensitivity of the emulsion in the middle of the linear part of the curve of the exposure density (blackening curve)

Sl.2 is the sensitivity of the emulsion at the shoulder of the blackening curve in Example 1

Sl.7 is the sensitivity of the emulsion at the shoulder the blackening curve in example 3

D _m is the maximum density Bg is the shoulder density

is the contrast, derived from the average gradient of the blackening curve between 0.05 via fog to the point D _x , '

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log ES is the effective exposure area, where a lower number indicates higher contrast.

example 1

A silver halide gelatin emulsion was made in the manner produced that by the double nozzle method, a water-soluble halide and silver nitrate to form a Combined precipitate with the ratio Br: Cl equal to 67:33 in an aqueous gelatin solution and the emulsion with ammonia and an excess of chloride in the presence of sodium corrhodite and potassium ferric cyanide, as in the British Patent specification 1 287 978 described, allowed to ripen, whereby cubic grains with an average edge length of 0.8 / U. The emulsion then became a flocculate brought, dispersed in additional gelatin and ripened with sodium thiosulfate, then with a Tetraazainden stabilizer stabilized and finally, optically sensitized.

Either the amount of hydroquinone given in Tables I and II (HCh) and / or the amount of hydroquinone derivative of the formula I. The alkyl radical R is given in the second column of this table. In the sodium sulfonate salt was used in all cases.

The separated emulsion portions were put on paper strips

applied with a silver coating weight of 2 g / m 2

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and dried.

The strips were then flashed with a xenon flash for 10 seconds exposed and in an automatic processing facility processed, in which the material is first passed through an activator bath and then through a stabilizer bath will.

The activator solution used was a 2ii sodium hydroxide solution.

The stabilizer solution used contained 200 g of aluminum thodanide per 1 solution.

The results obtained are shown in Tables I to V.

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Table I.

Heh-crowd
g / gram atom
silver Derivative. ι ... - Amount of derivative
g / gram atom
silver SUN, 7 Sl, 2 De Y. log IT 133 ■ ψ * 3.27 3.P5 1.33 2.0 0.64 . -100 ■■ ■ ~. '' • ■ mm, * 3.24 2.93 '1.27' 1.8 0.6S dd ._ • Hexyl ", ·· · .. _t 33 '. [\ 3.31 3.14 1.47 2.2 0.65 ! S • ti ■ . "·. 67,, * ■. 3.34 3.20 1.62 2.5 0.66 67; * - - 3.22 2.74 "l.l7 1.7 0.66 ■ ■ is' ■ ; · Hexyl. _ ' 33 3.29 . 3.07 ' ^s 1.35 2.0 0.67 ti · ■: 67th. ; . 3 * 33 3.19 • 1.60 2.5 0.64 100 Butyl '. 3.28 3.12 1.48 2.3 0.63 » .; ' · "'' · • ■ · "67; 3.30. 3.17 1.54 2.4. 0.63 67 ■. ι » 33 3.29 3.10 1.40 2.1 Ό.66 η 67. 3 * 28 3.12 1.51 2.2 0.67
-j

Table II

O CO OO r \> NJ

O 00 cn

HchJ crowd
g / gram atom
silver derivative Amount of derivative
g / gram atom
silver SO. 7th Sl.2 De mm log IT 133 3.18 2.75 1.17 1.6 .0.70 67 Octyl • ■ 33 3.21 3.05 " 1.47 2.2 0.66 67 ir 67 ·. '"■ 3.14 3.03 1.61 2.7 0.53 67 - ■ ' 3.12 0.97 1.35 0.69 67 • butyl • ■, -33 3.18 2.98 ' 1.42 2.0 0.69 67, »» 67 3.18 3.04 1.50 2.3 0.66 ' 0 Il . . ¹ 53 3.17 3.04 1.61 2.6 0.64 '

Table III

CD CD OO K) NJ

O GO OT CD

Hch amount
g / gram atom
silver derivative Amount of derivative
g / gram atom
silver so.7 Sl.2 DE 2.2 log IT 133 - - 3.13 2.88 . 1.24 1.7 0.55 67 3.09 ' - 1.01 2.6 0.60 67 Butyl 67. ■ 3.14 3.Ö0 1.43 2.45 0.58 67 ■ Hexyl. . 67 3.18 3.03 1.45 '2.3 0.59 67 Octyl 67 3.12 2.88 1-.24 2.0 0.57 67 Decyl 67 '. 3.12 2.70 1.16 0.58

K) CvO

Table IV

σ co CX) ΓΌ KJ

CD OO cn OD

Hch amount
g / gram atom
silver ■ derivative Amount of derivative
g / gram atom
silver so. 7th DE Y log IT 133 - mm 3.24 1.03 1.57 0.63 67 M * ' 3 * 22 1.03 1.65 0.59 67 methyl 67 3 * 14 L ₁ IO 2.0 0.53 67. ethyl 67 3.28 1.18 2.1 0.56 67 Propyl 67 3.24 1.24 2.1 0.57 67 Butyl 3.24 1.32 2.35 0.54 67 " • hexyl 67 3.20 1.36 • 2.6 0.52 /. . 67 Octyl 67 3.25 1.32 0.54

cn

OO cn

Table V

Heh-crowd
g / gram atom
' Silver derivative ; Amount of derivative
g / gram atom
silver so.? Sl.2 DE Ϊ log IT 133 - 3.12 2.64 1.13 , 1.9 . 0.57 67 «MB 3.08 1.07 1.76 0.58 ■ 67 η-butyl 67 3.10 ■ .. 2.93 1.33 2.4 0.55 67 sec-butyl 67 3.13 3.00 1.39 2.6 0.52

The results in Tables I and II show that the Combination of hydroquinone and either the butyl or hexyl oetyl derivative a much greater shoulder sensitivity '(Sl.2) and contrast effect than hydroquinone alone delivers. Likewise, the butyl derivative, when used alone, gives a result that is similar to the best result that is achieved with a mixture of hydroquinone and the butyl derivative.

The results in Table III show that the octyl derivative has little beneficial effect on some layers while the decyl derivative has no beneficial effect. In addition, there are difficulties due to a large increase in viscosity that occurs when one adding the decyl derivative to the emulsion.

The results in Table IV show that the ethyl and Propyl derivatives, when present in the emulsion, have useful effects while the methyl derivative does not has a useful effect.

The results in Table V show that the sec-butylderi- ' vat, a compound having a branched alkyl group, also shows useful effects when added to the emulsion will. _

Example 2

A Silberhalogenidgelatineemulsion was placed in the manner ago · »that after the double-jet method from a lös"

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Halide and silver nitrate precipitate silver halide in aqueous gelatin solution with a BE: Gl ratio equal to 30:70. The emulsion was left with ammonia and an excess of chloride in the presence of i-sodium chloro-rhodite ripened, forming cubic crystals with a mean edge length of 0.5 / u. the Emulsion was then flocculated, in additional gelatin dispersed and ripened in the presence of sodium thiosulfate then stabilized with a tetraazaindene compound and visually sensitized.

For separate portions of the emulsion, nan gave those in the table III specified amount- hydroquinone and / or the amount of butyl- Sodium hydroquinone sulfonate of the formula I. The portions of öex emulsion were then applied to strips of paper with

ρ a silver coating weight of 1.5 g / m "* All strips were then exposed for 10 seconds and processed in an automatic processing system as in Example Ί.

The activator solution used was a 2N sodium hydroxide solution.

The stabilizer solution used contained 200 g of Aminoniunsr-hodanid per 1 solution.

The results obtained are given in Tables VI and VII below.

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Table VI

σ co απ

HOh-crowd
g / gram atom
Silver in the
Emulsions Hydroquinone
derivative
of formula I. Amount of derivative
g / gram atom
Silver in the
Emulsions SO.7 DM De V logES . 80
40 '
40
40 'Butyl . · "'33'
66 2.31
2.23
■ 2.32
2.39 • 2.03
1.85
2.03
2.12 1.83
1.51
1.80
1.97 1.68
1.30
1.58
1.85 1.15
• 1.19
1.20
1.13

Table VII

HCh amount
g / gram atom
silver derivative • Amount of derivative
g / gram atom
silver SO. 7th Dmax DE Ϊ log IT 80 - _r ■ 2.41 1.95 1.70 1.82 0.94 40 2.21 1.78 1.55. 1.02 1.45 40 Butyl 40 2.44 1.99 1.79 1.82 0.98 ' 40 'Hexyl 40 2.45 2.03 ■ 1.84 2.5 0.82 40 Decyl '. 40. 2.42 1.97 1.67 1.68 0.97

The results in Tables VI and VII show that the butyl and hexyl derivatives of hydroquinone provide a higher mean density sensitivity and shoulder density (D ₃₅ ) when used with hydroquinone than can be obtained with hydroquinone while the Decyl derivative does not bring any advantages.

Example 3

A silver halide gelatin emulsion was prepared by using the double nozzle method from a water-soluble bromine salt and silver nitrate precipitate forms in aqueous gelatin solution. The crystal were ripened in ammonia and in chloride ions, giving polyhedral grains with a mean diameter of 0.5 / U. The emulsion was flocculated, dispersed in additional gelatin, with sodium thiosulfate Let ripen and with a tetraazainden stabilizer stabilized and finally optically sensitized. The emulsion was then added to separate portions of the emulsion Table Viii below indicated hydroquinone amount or the specified hydroquinone and datf üiatriumsalz der 2 ~: butyl ~ hydroquinone-5-sulfonic acid.

The separated emulsion portions were put on paper strips applied with a silver coating of 15 g / m and dried. The coated strips were then exposed for 10 "^ seconds with a Χεηοη flash and in an automatic

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see processing plant as processed in example 1.

The activator solution used was a -1.5 N sodium hydroxide solution.

The stabilizer solution used contained 200 g of ammonium thiocyanate per liter of solution. .

The results obtained are shown in Table VIII below.

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Table VIII

CD CO OO

ro

CD CD crt co

ECh amount
g / gram atom
silver derivative . Amount of derivative
g / gram atom
silver so .7 Sl. 7th DM 96 DE 90 r 1 Io gES 133 ■ 2. 60 1 .86 1'. 51 1. 33 1. 76 1. 34 67 ■ - 2. 31 - • 1. 93 1. 75 0. 25th 1. 73 67 Butyl ' 67 2. 77 1 , 99 . 1" 1. 1.
* 1. 55

ro co cn

CO cn

The results show that the butyl derivatives together with hydroquinone provide higher SO.7 and Sl.7 sensitivities, than these can be obtained with hydroquinone alone "

Example 4

This example shows that when a hydroquinone derivative of formula I is added to a layer which is in effective contact with a silver halide emulsion layer, favorable effects can also be obtained.

A gelatin silver halide emulsion was prepared as indicated in Example 1.

The subsequent separate emulsion portions were then prepared.

Emulsion A - 133 grams of hydroquinone per gram atom of the emulsion added silver

B - 67 grams of hydroquinone added per gram atom of silver added to the emulsion

C - 67 g hydroquinone and 67 g hexyl derivative, both silver added per gram atom of emulsion -

D · - 67 g hydroquinone and 67 g hexyl derivative pro Gram atom of the silver added to the top layer, 'the over the silver halide emulsion' layer was applied.

After exposure and processing as in Example 1, the

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Results given in Table IX were achieved.

Emulsion so.7 Sl.2 DE X log IT A. 5.12 2.86 1.25 2.1 0.58 . B. 5.12 2.60 1.15 2.1 0.54 C. 5.15 5.04 1.47 2.7 0.55 D. 5.15 5.04 1.59 2.8 0.58

It follows that if you use the hexyl derivative of. Top layer of material admits, just as good results as if the hexyl derivative of the silver halide emulsion layer himself is admitted.

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Claims (5)

Claims :. Monochromatic silver halide photographic emulsion suitable for processing in an automatic processor mit-activator solution / stabilizer solution, characterized in that it is in at least a silver halide emulsion layer or in a layer in effective contact therewith, 30 to 150 grams of one per gram atom of silver present in "the" emulsion Hydrochinond derivative "of the formula OH OH where R is an alkyl group having 2 to 8 carbon atoms and M is a hydrogen or alkali metal atom. 2. Photographic material "according to claim 1, characterized in that R is n-eutyl, sec-butyl or n-hexyl-. 3. Photographic material according to claim 1 or 2, da characterized in that the hydroquinone derivative each silver halide emulsion layer -24- 409822/0856 of the photographic material are present. 4. Photographic material according to any one of claims 1 to 3, characterized in that in at least one silver halide emulsion layer or in a layer which is in effective contact therewith, per Gram atom of silver present in the emulsion contains 30 to 150 g of hydroquinone. 5. A method for processing photographic material according to any one of claims 1 to 4, characterized draws that the photographic material is exposed and then successively in an automatic processing plant treated with an activator solution and with a stabilizer solution. 409822/0856