DE1290042B - Gelatin-silver halide photographic emulsion - Google Patents

Description

The invention relates to a gelatin silver halide photographic emulsion containing N-substituted polymeric amides.

It is known that exposed photographic silver halide emulsions suffer a loss of density on drying, that is to say that the /> _m , (. _R values are lower after drying than before drying. This effect is described, for example, in a publication by the Technical Association of the Graphic Arts: Fourteenth Annual Meeting, June 11-13, 1962 ", pp. 13 to 28. Satisfactory solutions to this problem, for example by adding certain compounds which reduce the density loss to the emulsion, have not yet become known, namely apparently because no compounds could be found which meet the multitude of requirements, ie are compatible with the emulsion, do not interfere with the development process and do not exert any adverse effects on the sensitometric properties of the emulsion.

From British patents 875 100 and 978 880 it is known that by addition from dextran or lactose to gelatin-silver halide emulsions can improve the opacity of the silver, but the addition of these compounds dissolves the emulsions do not have the problem of density loss on drying.

The invention is based on the surprising finding that the density loss described Can be largely avoided if a gelatin-silver halide emulsion is used which is the reaction product of an α-amino acid ester with certain anhydride groups Contains polymers.

The invention therefore provides a photographic gelatin-silver halide emulsion with a content of N-substituted polymeric amides, which is characterized in that it is a reaction product of an α-amino acid ester with

1. polyacrylic anhydride,

2. Polymethacrylic anhydride.

3. a copolymer of the two components alkyl vinyl ether, its alkyl group Has 2 to 4 carbon atoms, and maleic anhydride or

4. a copolymer of the three components alkyl vinyl ether, its alkyl group Has 2 to 4 carbon atoms, ethyl acrylate and maleic anhydride

contains.

Α-Amino acid esters which are particularly suitable for the preparation of the reaction products have the formula or

and H
ι - OCH; 3 - OCH ₂ CH ₃ R ₂ I.
- Ν O
Μ or v-il ₂ ! I
C- Q-CH ₃ H
) I.
- Ν O
H CH ₂ Il
C- -Q-CH ₂ CH ₃

HO

C ^

IVj

NH ₂
in which means: Ri H -CH ₃

O
- CH ₂ CH ₂ - C - O - CH ₂ CH ₂ CH ₃

Particularly suitable copolymers of alkyl vinyl ethers with maleic anhydride are those • in which the monomer residues in the polymer Alternate chains. The exact structure of the copolymers from alkyl vinyl ethers, ethyl acrylate and Maleic anhydride is not yet known. In the production of these copolymers can the molar ratios of the monomeric starting compounds which are subjected to the polymerization will be very different. A particularly advantageous molar ratio is about 0.85: 0.625: 1 or, expressed in parts by weight, 12.5: 12.5: 20. Never preferably have alkyl groups of the alkyl vinyl ethers 2 carbon atoms.

The one used in the preparation of the reaction products from α-amino acid esters and polymer Molar ratio can be very different. The α-amino acid ester is preferably used in a molar Excess, based on the anhydride groups present, is used. Have to be particularly beneficial molar ratios of 1.5 to 2 mol of amino acid ester per anhydride group of the polymer have been found. The molecular weights of the polymers that are reacted with the α-amino acid esters can be very different. Those polymers are preferably used which are in the form of a 5 weight percent Solution in acetone at 25 ° C has a viscosity of 0.8 to 2.2 cSt, preferably 1.3 to 1.8 cSt, own.

The ratio of the polymers to the gelatin of the gelatin-silver halide emulsion can advantageously be 1 to 4 parts by weight of polymer per 9 parts by weight of gelatin. A ratio of 1 / s to 2 ² Aj parts by weight of polymer per 9 parts by weight of gelatin has proven to be particularly advantageous.

The following describes the preparation of some reaction products of α-amino acid esters which are suitable according to the invention with certain polymeric acid anhydrides. That from alanine ethyl ester and polyacrylic anhydride obtained reaction product is particularly suitable according to the invention.

Manufacturing examples

A. Reaction product from polyacrylic anhydride

with alanine ethyl ester

A solution consisting of 12.6 g of polyacrylic anhydride in 125 cm ^{3 of} dry dimethylformamide was added to a solution of 16 g of alanine ethyl ester in 50 cm ^{3 of} dry dimethylformamide with stirring and heating in a steam bath. The solution was heated on the steam bath with stirring for 18 hours. Then she was

Allowed to cool, whereupon the reaction product obtained by pouring the solution into 3 l of anhydrous Ether has precipitated. The precipitated reaction product was then washed several times with ether washed and dried in vacuo. 15 g of reaction product were obtained.

B. Reaction product of polyacrylic anhydride
with glycylglycine ethyl ester

This reaction product was prepared by the method described under A., starting from 8 g of glycylglycine ethyl ester and 6.3 g of polyacrylic anhydride. There were 8 g of an almost colorless water-soluble Powder received.

C. Reaction product of polymethacrylic anhydride with glycine ethyl ester

15th

A solution of 15.4 g of poly (methacrylic anhydride) in 250 cm ^{3 of} dimethylformamide was reacted with 15 g of freshly prepared glycine ethyl ester in 50 cm ^{3 of} dimethylformamide by the method described under A. 18 g of a pale cream-colored powder were obtained.

D. Reaction product of polymethacrylic anhydride with alanine ethyl ester

15.4 g of polymethacrylic anhydride were dissolved in 250 cm ^{3 of} dimethylformamide and 18 g of alanine ethyl ester in 50 cm ^{3 of} dimethylformamide, whereupon the two solutions were combined and reacted according to the method described under A. 16 g of a hygroscopic powder were obtained.

35

E. Reaction product from the copolymer

from ethyl vinyl ether, ethyl acrylate and
Maleic anhydride with alanine ethyl ester

The copolymer was first prepared by dissolving 12.5 g of ethyl vinyl ether, 12.5 g of ethyl acrylate and 20 g of maleic anhydride and 0.2 g of benzoyl peroxide in 200 cm ^{3 of} acetone. The dissolution took place in a pressure vessel. The solution was bubbled with nitrogen. Finally, 0.8 g of azodiisobutyronitrile were added as a catalyst. The vessel was then closed with a lid with a rubber seal and placed in a thermostat ^{filled with water at 50 °} C. for 7 days. The solution became viscous and the polymer formed could be precipitated by adding ether. The polymer was then washed thoroughly with ether. 15 g of polymer were obtained, which were then dissolved in 150 ml of dimethylformamide and added with stirring to a solution of 18 g of ethyl alanine in 50 ml of dimethylformamide. The obtained solution was heated ^2] / 2 hours on a steam bath, was being thoroughly stirred. Subsequently, after cooling, the reaction product was precipitated by pouring it into ether. It was washed 3 times with ether and dried in vacuo. The yield was 17 g.

F. Reaction product from the copolymer
of ethyl vinyl ether and maleic anhydride

with glycine ethyl ester

40 g of ethyl vinyl ether, which was washed with water, was then distilled dried over solid Raliumhydroxyd and which consisted of a colorless liquid, and had a boiling point of 36 C were dissolved together with 40 g of maleic anhydride in 400 cm ^a acetone in a glass pressure vessel. The solution was bubbled with nitrogen. In addition, 0.8 g of azodiisobutyronitrile was added. The vessel was then closed with a cover having a rubber seal and placed in a thermostat which ^{contained water at 50 °} C. for 5 days. The solution became viscous. The polymer formed was precipitated by pouring it into petroleum ether with rapid stirring. After stirring for a further 15 minutes, the polymer was allowed to settle. The supernatant liquid was decanted off and replaced with 3 liters of fresh petroleum ether, whereupon the mixture was stirred for a further 15 hours. This washing process was repeated. The obtained fibrous polymeric material was then separated and air dried. 60 g of polymer were obtained. This polymer had a viscosity of 6.0 cSt in a 5 percent strength by weight acetone solution. 10 g of the polymer were dissolved in 100 ml of dimethylformamide, whereupon the solution was added with stirring to a solution of 9 g of glycine ethyl ester in 30 ml of dimethylformamide. The solution was heated with stirring for 2 hours ¹ Ii on a steam bath and then allowed to cool. The reaction product was then precipitated with ether. The yield was 14 g.

G. Reaction product from the copolymer

from ethyl vinyl ether, ethyl acrylate and
Maleic anhydride with glycine ethyl ester

The copolymer was prepared as described under E. 15 g of the copolymer were then reacted with 14 g of glycine ethyl ester according to the method described under E. It 16.5 g of the α-amino acid ester derivative were obtained.

H. Reaction product of polymethacrylic anhydride with methionine ethyl ester

The reaction product was prepared as described under D., with the exception that an Instead of the alanine ethyl ester, 26.5 g methionine ethyl ester were used.

I. Reaction product from polyacrylic anhydride
with methionine ethyl ester

The reaction product was prepared as described under A., with the exception that an Instead of alanine ethyl ester, 26.5 g methionine ethyl ester were used.

J. Reaction product from the copolymer

from ethyl vinyl ether and maleic anhydride

with methionine ethyl ester

This reaction product was prepared as described under F., with the exception that the Glycine ethyl ester was replaced by 26.5 g methionine ethyl ester.

K. Reaction product from the copolymer

from ethyl vinyl ether, ethyl acrylate and
Maleic anhydride with methionine ethyl ester

The reaction product was prepared as described under E., with the exception that an

Place of alanine ethyl ester 26 g methionine ethyl ester p-methylaminophenol sulfate 2.2 g

were used. Hydroquinone 8.8 g

, j

The reaction product was filled up to the liter with water as under D.

wrote made, with the exception that at

Place of alanine ethyl ester 28 g of ethyl glutamate then the film strips were in a known manner

were applied. fixed and washed. Now density

The following exemplary embodiments are intended to carry out the measurements using film strips under the invention illustrate in more detail. were searched for that were still damp and that were in

Air at 49 ° C and a relative humidity

Example 1 ^{were dried by} 20%. From the damp and

curves were applied to dry film strips

The reaction produced as described under A. and the density differences during drying with

tion product was dissolved in water, whereupon the correct densities were determined. The sensitivity

Solution was adjusted to a pH of 6.5. was measured as the rel. log. (10 / .E), where E is the

The solution was then presented in amounts of 30 g of react exposure sufficient to produce a

tion product per mole of silver of a coarse grain density of 0.85 above the haze was required.

Silver bromide iodide emulsion added, the 135 g of gel 20 Two gradation values were determined, and

tine per mole of silver halide. This emulsion is the tangent of a straight line, the two

was then applied to a film support. By connecting points of the curve together, the densities

Test strips of 0.25 and 2.0 as well as 1.0 and 2.5 above the were cut from the film obtained

ten that have haze for Vm second in a sensitometer. Furthermore, the sensations

were exposed with an intensity scale. Gluteness, the veil and the maximum density

Finally, the film strips were determined for 3 minutes (dry) with the same amount of silver salt applied,

at 20 ^° C. in a developer of the following composition. The results obtained are as follows

Composition developed: Table reproduced:

Relative sensitivity

gradation

veil

dry

Loss of density in densities

1.5

2.5

Comparative sample

2 parts of reaction product to 9 parts of gelatin ...

286 292

2.56 2.82

2.94 3.74

0.10
0.13

3.3
4.3

0.13
0.02

0.40
0.06

0.69 0.20

Example 2

When using the reaction products B. to D. according to the method described in Example 1 were get the following results:

Reaction product B

Relative sensitivity

gradation

veil

β. ,,
dry

Loss of density at the densities 1.5 2.5 3.5

Comparative sample

2 parts of reaction product to 9 parts of gelatin ...

286 290

2.74 2.66

3.5 4.0

0.08
0.09

3.60
4.0

0.11
0.06

0.26
0.18

.0.46 0.24

Reaction product C

Relative .sensitivity

gradation

veil

dry

Loss of density at the densities 1.5 ■ 2.5 3.5

Comparative sample

2 parts of reaction product to 9 parts of gelatin ...

286 291

2.74 2.92

3.5 4.3

0.08
0.11

3.60
4.0

0.11
0.04

0.26

0.46 0.12

Reaction product D

Relative sensitivity

gradation

veil

dry

Loss of density in densities

1.5

2.5

3.5

Comparative sample

2 parts of reaction product to 9 parts of gelatin ...

286 283

2.74 2.98

3.5 4.3

0.08
0.07

3.6
4.1

0.11
0.08

0.26
0.06

0.46 0.24

Example 3

When using the reaction products E. to L. according to the method described in Example 1 were get the following results:

Reaction product E

Relative sensitivity

gradation

veil

dry

Loss of density in densities

1.5

2.5

3.5

Comparative sample

Parts of reaction product to 9 parts of gelatin ...

298

293

2.66
2.70

3.36
3.58

0.09 0.07

3.45
3.80

0.14
0.04

0.26 0.18

0.42 0.22

Reaction product F

Relative sensitivity

gradation

1 2

veil

dry

Loss of density in densities

1.5

2.5

3.5

Comparative sample

Parts of reaction product to 9 parts of gelatin ...

298

296

2.66
2.80

3.36
3.94

0.09 0.09

3.45
4.00

0.14

0.26
0.06

0.42 0.04

Reaction product G

Relative sensitivity

gradation 1 2

veil

J) ₁₁₁ dry

Loss of density at the densities 1.5 2.5 3.5

Comparative sample

Parts of reaction product to 9 parts of gelatin ...

298

295

2.54
2.88

2.88
4.10

0.07 0.07

3.2
3.9

0.20
0.08

0.30

0.45

Reaction product H

Relative sensitivity

gradation

veil

P- « dry

Loss of density in densities

1.5

2.5

3.5

Comparative sample

Parts of reaction product to 9 parts of gelatin ...

284

286

3.16

3.74

0.07 0.10

3.35
4.10

0.12
0.06

0.26
0.06

0.46 0.16

Reaction product I.

Relative sensitivity

gradation 1 2

veil

Α. «
dry

Loss of density in densities

1.5

2.5

3.5

Comparative sample

Parts of reaction product to 9 parts of gelatin ...

284

284

3.16
4.60

0.07 0.16

3.35
3.80

0.12
0.10

0.26

0.46 0.14

Reaction product J

Relative sensitivity

gradation 1 2

veil

dry

Loss of density at the densities 1.5 2.5 3.5

Comparative sample

Parts of reaction product to 9 parts of gelatin ...

281

283

2.90
3.60

0.10 0.11

3.25
3.80

0.13
0.11

0.27
0.18

0.47 0.18

Reaction product K

Relative sensitivity

gradation

veil

dry

Loss of density in densities

1.5

2.5

3.5

Comparative sample

Parts of reaction product to 9 parts of gelatin ...

281

271

2.90
3.56

0.10 0.10

3.25
3.85

0.13
0.16

0.27
0.23

0.47

0.36 909 509/826

Reaction product L

10

Relative sensitivity

Gradation 1

Veil dry

Loss of density at the densities 1.5 2.5 3.5

Comparative sample

Parts of reaction product
on 9 parts gelatine ...

281 290

2.6 2.8

3.56 4.20

3.56
3.80

0.24
0.12

0.40 0.24

The following comparative examples A 'and B' show that with reaction products that according to the invention used are very close, the effects achieved according to the invention can not be achieved.

Comparative example A '

A copolymer of methyl vinyl ether and maleic anhydride with a specific viscosity from 0.1 to 0.5 was reacted with glycine ethyl ester in the manner described under G. and as in Example 1 described tested. The following results were obtained:

Relative gradation 1 2 veil dry Loss of density in densities 2.5 3.5 sensitivity 2.80 3.6 0.07 3.58 1.5 0.34 0.60 290 2.76 4.0 0.08 4.00 0.20 0.40 0.64 295 0.20

Comparative sample

Parts of reaction product
on 9 parts gelatine ...

Comparative example B '

A copolymer of ethylene and maleic anhydride was reacted with ethyl alanine and tested as described in example 1. The following results were obtained:

Relative gradation 1 2 veil o _max Loss of density in the 2.5 sensitivity 3.16 3.78 0.07 dry 1.5 0.44 287 2.96 4.10 0.07 3.76 0.26 0.36 286 3.90 0.16

3.5

Comparative sample

Parts of reaction product
on 9 parts gelatine ...

0.62 0.48

Claims (5)

Claims: 40 1. Gelatin silver halide photographic emulsion containing N-substituted polymeric amides, characterized in that that they are a reaction product of an α-amino acid ester with 1. polyacrylic anhydride, 2. polymethacrylic anhydride, 3. a copolymer of the two components alkyl vinyl ether, its alkyl group Has 2 to 4 carbon atoms, and maleic anhydride or 4. a copolymer of the three components alkyl vinyl ether, its alkyl group Has 2 to 4 carbon atoms, ethyl acrylate and maleic anhydride contains. 2. Photographic gelatin silver halide emulsion according to claim 1, characterized in that the _{α-amino acid ester is a compound of the following formula} HO NH ₂ ■ 65 is used, in which R _{1 is} H - CH ₃ O - CH ₂ CH ₂ - C - O - CH ₂ - CH ₂ CH ₃ or -CH ₂ CH ₂ -S-CH ₃ R ₂ - OCH ₃ - OCH ₂ CH ₃ HO I Ii ■ -N-CH ₂ -CO-CH ₃ or HO I Il -N-CH ₂ -CO-CH ₂ CH ₃ 3. Photographic gelatin-silver halide emulsion according to Claim 1, characterized in that that a compound is used as a copolymer consisting of two components 11 12 in which the monomeric residues in the polymer 5. Gelatin silver halide photographic alternate the chain. emulsion according to claim 1 to 4, characterized 4. Photographic gelatin silver halide records that they are based on 9 parts by weight of gelatin Emulsion according to claim 1, characterized in 1 to 4, preferably 1 '/ a to 2 ² / :) parts by weight net that they are a reaction product of polyacrylic 5 of the reaction product of a-amino acid ester contains acid anhydride and alanine ethyl ester. and the polymeric compound.