DE2337412A1 - Bis-(vinyl-sulphonyl)alkanes as hardeners - for photographic gelatine-silver halide emulsions, preventing fog or abnormal hardening - Google Patents

Abstract

A bis-(vinylsulphonyl)-alkane (I) of formula CH2=CHSO2-(CH2)nSO2CH=CH2 (in which n = 1-8) is used as hardener for gelatino-Ag halide emulsion(s) of light-sensitive photographic recording material, esp. colour photographic material. Unlike hardeners such as K alum, Cr alum, HCHO and glyoxal, (I) does not cause fogging, desensitisation or abnormal hardening, even during prolonged storage.

Description

The invention relates to a hardening agent for gelatin containing light-sensitive photographic recording material, in particular a light-sensitive photographic Gelatin / silver halide recording material with a curing agent comprising two vinylsulfonyl radicals each directly connected to an alkyl radical.

Numerous measures for hardening gelatin layers of photographic recording materials are known in the photographic field. When such hardening is ineffective or insufficient, the gelatin film undergoes excessive swelling by water during treatment, whereby it can be easily damaged and in extreme cases it becomes detached from the substrate and goes into solution.

As hardening agents for photographic gelatin, inorganic compounds such as potassium alum and chrome alum are as well organic compounds such as formaldehyde and glyoxal are known.

However, the use of such compounds in photographic light-sensitive materials is common

Dr.f./ek. B09807 / 0945

'afflicted with certain disadvantages. This is how it happens, for example to a thickening of the coating liquid, to a post-curing of the coated one Films on storage as well as an increase in desensitization and fogging.

The invention was based on the object of providing a curing agent free from the disadvantages outlined for the gelatin of silver halide photographic light-sensitive recording materials.

In the case of light-sensitive photographic silver halide images drawing materials according to the invention Usable gelatin hardeners are compounds with vinylsulfonyl radicals of the general Formula:

H ₂ C = CHSO ₂ (CH ₂ ) _n S0 ₂ CH = CH ₂ where η is a number from 1 to 8.

Those used in silver halide photographic light-sensitive materials Gelatin hardeners which can be used according to the invention can be prepared as follows:

Production example 1

The compound 1,2-bis (vinylsulfonyl) ethane (with η = 2) can be produced by the following three-step process.

First, a solution of 4.6 g (0.2 mol) of metallic sodium in 100 ml of alcohol at a temperature of 18 ° C was prepared 15.6 g (0.2 mol) of 2-mercaptoethanol were added dropwise. After the addition was complete, the resulting reaction mixture became

509807/0945

Stirred for 50 minutes and then dropwise at a At a temperature of 18 ° to 24 ° C., 18.8 g (0.1 mol) of ethylene bromide were added over the course of 40 minutes. Then was the reaction mixture slowly heated to boiling temperature for 2 hours with stirring. Now that was educated Sodium bromide filtered off hot. The filter cake was washed with hot alcohol, whereupon the washing alcohol was combined with the piltrate. The whole thing then became evaporated to dryness under reduced pressure. This gave 15.7 g (86.3 # yield) of 1,2-bis (β-hydroxyethylthio) ethane in the form of a white solid with a melting point of 58 ° to 62 ° C as an intermediate of the first stage received.

An elementary analysis of the compound CgH ^ hOp ^ P ^er> S ^a ^ the following values:

Calculated C: 39.10 H: 7 * 66 S: 34.80 Found C: 38.94 H: 7.48 S: 35.12

15.7 g (0.09 mol) of the 1,2-bis (ß-hydroxyethylthio) ethane obtained were stirred into a mixture of 67.3 m (0.52 mol) of 30 # strength hydrogen peroxide and 67.3 ml of glacial acetic acid entered, whereupon the reaction mixture obtained was heated to boiling temperature for 1 hour. After completion of the implementation the solvent was removed as much as possible under reduced pressure, leaving the oily residue 200 ml of alcohol were added and the whole thing was then cooled.

The resulting precipitate was filtered off and removed from a mixed solvent of alcohol and pyridine recrystallized, leaving 13.8 g (65.4 # Lge yield)

- 4 509807/0945

1,2-bis (ß-hydroxyethylsulfonyl) ethane with a melting point of 78 ⁰ C were obtained as an intermediate product of the second stage.

An elemental analysis of ^{the compound c} 5 ^{H ijPgSp er} S ^aD
the following values:

Calculated C: 29.26 H: 5.73 S: 26.04 Found C: 29.08 H: 5.80 S: 25.32

10.0 g (0.04 mol) of the obtained l, 2-bis (ß-hydroxyethylsulfonyl) ethane were dissolved in 25.0 g of a 50 ⁰ C hot concentrated sulfuric acid was added, and the reaction mixture stirred for 3.5 hours at this temperature became.

The reaction mixture was then cooled, poured onto crushed ice and made weakly alkaline with 20% sodium hydroxide solution, the cooling being carried out in such a way that the reaction mixture was kept ^{at a temperature below 50 ° C. during the entire neutralization process.} The crystalline precipitate which precipitated out and was contaminated with sodium sulfate was filtered off and washed free of sodium sulfate with water. The white powder obtained in this way was recrystallized from methanol, 3.1 g (36.1% yield) of 1,2-bis (vinylsulfonyl) ethane having a melting point of 121 ° to 124 ° C. being obtained as the end product.

An elemental analysis of the compound ^c 6 ^H ] o ° 4 ^S 2
resulted in the following values:

Calculated C: 34.29 H: 4.80 S: 30.50 Found C: 34.12 H: 4.90 S: 30.26

509807/0945

Production example 2

1,5-bis (vinylsulfonyl) pentane (rait n = 5)

This compound was prepared as in Preparation Example 1, but starting from 1,5-bis (ß-hydroxyethylsulfonyl) pentane in a yield of 38 * 4 # and
had a melting point of 53 ° to 55 ° C.

An elemental analysis of the compound obtained
^C 9 ^H 16 ° 4 ^S 2 ^{resulted in the} following values:

Calculated C: 42.84 H: 6.39 S: 25.4L Found C: 42.38 H: 6.54 S: 25.04

The others, which have a different alkyl chain length Connections can be made in the same way *

Compounds of the formula given, in which η would mean a number of 9 or greater, have only a small number Hardening effect and hence are unsuitable for use in silver halide photographic light-sensitive materials according to the invention.

The hardening agents of the given formula can be used in any gelatin layers, e.g. protective layers, adhesive layers, Interlayers, backing layers and light-sensitive photographic emulsion layers will. In most cases it is sufficient to use a curing agent of the formula given to use alone. If necessary or when desired, the hardening agents may be of those specified Formula can also be used along with other curing agents.

- 6 S09807 / 0945

When a hardener of the formula given is incorporated into a photographic emulsion, this is done preferably in the form of a solution in methanol or another solvent in such an amount, that its concentration in the emulsion, based on the gelatin, expediently 0.1 to 10, preferably 0.2 to J5 &. The most suitable in each case The amount of hardening agent may be more suitable depending on the particular gelatin contained in the emulsion Way to be chosen. A hardening agent of the formula given is added to a silver halide emulsion after the same added second maturation. It can be used in combination with other photographic without any adverse effect Usual additives incorporated into emulsions after the second ripening, e.g. stabilizers, coating auxiliaries or sensitizing dyes can be used. A curing agent of the formula given can also emulsions are added which are chemically produced by the use of gold, sulfur, polyethylene oxide and the like were sensitized. It is also possible to use a curing agent of the formula given as coupler to add light-sensitive color photographic emulsions.

The addition of a curing agent of the formula given to one of the emulsions mentioned does not cause any In case of fogging or desensitization and even with prolonged storage of the Emulsions to no abnormal hardening (the same).

The support of light-sensitive silver halide photographic materials according to The invention can be formed from a conventional photographic support such as a triacetate film, a barite-coated one Paper, a polyester film, or a

509807/0945 "7 - ■

Polycarbonate film.

A gelatin, polyvinyl maleic acid and the like. As well An adhesive layer containing a curing agent of the formula shown has good adhesiveness to the Support. Finally, the hardening agents of the formula given have a beneficial effect on the With a view to stabilizing the fogging and sensitivity properties of photographic emulsions.

The following examples are intended to illustrate the invention in more detail.

example 1

A highly sensitive photographic silver iodobromide negative with 5 mol # silver iodide became a second Subjected to ripening and then loaded with a stabilizer and a coating aid. Then was divided the emulsion into 4 parts. A first part was made for the production of a comparison material (without any other additive) applied to a layer support. The remaining 3 parts were with 1,2-bis (vinylsulfonyl) ethane (test piece 1), 1,5-bis (vinylsulfonyl) pentane (test piece 2) or the outside vinylsulfonylalkyl radical-containing hardening agents N, N'-bis (2-vinylsulfonylethyl) piperazine which lie within the scope of the invention (Test item 3) and applied to the substrate for the production of corresponding recording materials.

The various film samples were stored for 3 days at a temperature of 55 ° C or 3 days at a temperature of 50 ⁰ C and a relative humidity of 80 #. The specimens stored in this way and fresh specimens, ie specimens immediately after

- 8 509807/0945

Application of the emulsions in question to the substrate, were examined individually to determine how long it takes until the pilm surface is immersed in an alkaline solution Solution begins to go. Furthermore, the individual test specimens were tested for their surface strength in a developer examined.

A 3 # strength sodium carbonate monohydrate solution was used as the alkaline solution used. The stored and the freshly prepared test specimens were in the 50 ° C warm solution immersed, whereby the for each test item up to the beginning of dissolution (the pilm surface) required immersion time has been determined.

The determination of the surface strength was carried out as follows: Each test piece was for 5 minutes in a developer dipped at 20 ° C., whereupon the swollen emulsion layer surface was weighed down with a or loaded pen (radius 1 mm) was scratched. The (film) surface strength is the minimum load at which the film surface has just been scratched with the pen.

In order to determine their photographic properties, the various samples were further tested according to the method JIS-7604 sensitometric examinations (regarding the Values for relative sensitivity and fog).

The results obtained in all tests are summarized in the following table I:

- 9 509807/0945 o «k3 * nal inspected

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50980 7/0945

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The values contained in Table I clearly show that the curing agents of the specified Formula develop a far better hardening effect than the hardening agent outside of the invention.

Example 2

The same photographic emulsion as in Example 1 was subjected to a second ripening and then with the purple coupler l- (2,4-dimethyl-6-chloropheny3 ^ - 3- ^ 5- [α- (3-pentadecylphenoxy) butylamide-cfjbenzamino ^ -5-pyrazolone in the form of a conventionally prepared protective dispersion based on oil.

The obtained emulsion was divided into 4 parts, from which one (without any further addition) was used to produce a comparative material. The remaining J3 parts were made with 1,3-bis (vinylsulfonyl) propane (Test item 4), 1,6-bis (vinylsulfonyl) hexane (test item 5) or the bis (vinylsulfonylmethyl) ether (test item 6) lying outside the invention and added to the preparation of the corresponding photographic light-sensitive materials applied to the substrate.

The specimens thus produced were used in Example 1 on their (film) surface strength examined. Furthermore, the test items were examined sensitometrically by using a diethyl-pphenylenediamine containing color developer developed and then bleached, fixed and in a conventional manner have been watered.

The results obtained in all tests are summarized in the following table II:

- 11 -

509807/0945 original inspected

Table II

Amount of photographic

'Test specimen hardening phische' - ■ —-— ■

by means of self-Up to the beginning of the in-solution pro 10 g stocks go in the alkaline solution

Hardening properties

Minimum load at which scratches were just formed

(mg) fcJ Ί Ιϋπϊίπτι
\ Comparison
material 200 0, ReI
fin nkeit ^Lj tables
Length at ei
ner tempe
rature from
■ 55 C gela
gert test
ling üBXü .. \ UlXlL / fresh
Test ·
ling 3 days,
at ei
ner tempe
rature from
55 C gela
gert test
ling 3 days for one
Temperature from
50 C and e? .Ner
relative humidity
activity of SC ", ^
stored prdf
■ things 4th 200 0, , 12 100 2 .3 11 14th 16 3 8 6 0 p 5 200 0, , 10 93 14th 24 3 days at ei
temperature
from 50 C and
a relative
Moisture from
80 ^ stored
Test items 110 165 240 ) 7/09 < 6th 0, , 10 95 10 18th 0.5 80 130 l80 he". 11 91 8th 15th 32 20th . 35 50 25th 20th

The values in Table II it can be seen that the Härtungsmfittel · the given formula without affecting: other, photographic Eigenschäften a \ excellent ^ HSrtungswirkung unfold * By using Häritungsmittel the given formula · nmxrden neither the couplers used terms affects its color development ability nor was the Occurrence of dye stain observed.

The hardening agent outside the invention had reasonably good resistance to solution in alkaline Solution, however, very poor scratch resistance.

Example 3

A highly sensitive silver iodobromide emulsion for X-ray films was subjected to a customary chemical ripening and then with, in each case based on 1 l of emulsion, 100 mg 4-Hydroxy-6-methyl-1,3 * 3a, 7-tetrazalinden as a stabilizer and 2 g of saponin added as a coating aid. The obtained emulsion was divided into 3 parts, of which one (without any further addition) for the production of a comparative material on a polyethylene terephthalate support was applied. The remaining two parts were individually compared to those used in Example 1 Hardening agents of the formula given and then added to the production of test items 7 and 8 (according to the invention) applied to polyethylene terephthalate support.

Each specimen was exposed in accordance with JIS-K7604 for 30 seconds using a containing l-phenyl-3-pyrazolidone and hydroquinone, strongly alkaline developer solution at a temperature developed from 35 ° C (high temperature fast) and then up examined their sensitivity and veil.

7/0945, - 13 -

OfiK & NAL INSPECTED

Furthermore, the test specimens were examined in the manner described in Example 1 for the hardening effect achieved The results obtained are summarized in the following table III:

509807/0945

Table III

Amount of photographic

Test specimen hardening phish

By means of your own up to the beginning of the in-solution per 10 g of shafts in the alkaline lo-

Gelatin solution required time (min)

(mg) ^;

Hardening properties

Minimum load at which scratches were just formed

CJI ■ comparison - ο material 100 co 7th 100 QO 8th σ ο ψ cn

Relatively fresh 3 days
veBnp-testing Gela in egg ■ boulders ner Tempelich- temperature of ^ness 55 ⁰ C

0.16 100 2
0.12 95 16
0.11 96 12

J> days at a fresh 3 days at a temperature test items at a temperature of 50 C and at a temperature

a relative
Moisture from

gerte test- 80 $ stored items test items 3 days at a temperature of 50 C una a relative humidity of

equipment test- 80 $ gelagerce

linge test items

rapur from C gela-

ιβ

30 25 11

130

80

14th

155 180

15th

220 I65

Claims (2)

Claims UK light-sensitive photographic silver halide recording material, consisting of a layer support and at least one gelatin layer which contains a hardening agent and which is or one of which contains the silver halide, characterized in that it contains a compound of the formula as hardening agent CH ₂ = CHSO ₂ (CH ₂ J ₁₁ SO ₂ CH = CH ₂ with η = a number from 1 to 8, contains, 2. Recording material according to claim 1, characterized in that that it contains a color photographic silver halide emulsions layer as gelatin layer. 509807 / 094.5 OB ^ AL .NSPECTED