DE1211070B - Light-sensitive, photographic silver halide emulsion containing a hardener - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

G03c

German class: 57 b-8/02

Number: 1211070

File number: E 26285IX a / 57 b

Filing date: January 24, 1964

Display day: 1.7. February 1966

R ₂ N POX ₂
(R ₂ N) ₂ POX

It is known to add gelatin hardeners to photosensitive emulsions. Have the known hardeners however, they have the disadvantage that, in addition to the hardening properties, they have a number of disadvantageous side effects cause that limit their usability.

For example, formaldehyde and mucochloric acid have excellent curing properties, but they form strong veils. Storage veils also call the 2,3-dihydroxydioxanes known as hardeners and polyethylene glycol acetates. The nitroaldehydes described in the literature as being particularly advantageous have the particular disadvantage that they reduce the sensitivity of the emulsions on prolonged storage greatly decrease. The ketones known as hardeners, e.g. B. divinyl ketone have these disadvantages. Immediately after adding them to the emulsion, they cause a considerable loss of sensitivity.

The invention was therefore based on the object of providing a hardener for photosensitive, photographic To find silver halide emulsions whose binder consists at least partially of gelatin, which does not adversely affect the photosensitive properties of the silver halide of the emulsion.

It has been found that certain aminophosphoryl halides are hardeners which provide the desired Possess properties. Accordingly, the photosensitive photographic silver halide emulsions are of the invention characterized in that it contains an aminophosphoryl halide in a hardening amount of the formulas

contain, wherein R has the meaning of a lower alkyl group and X is a halogen atom.

The amount of aminophosphoryl halide should preferably be about 0.3 to 6% of the amount of gelatin. It has been found that by incorporating the aminophosphoryl halides the resistance the emulsion layer is increased compared to hot water while at the same time having a small effect on the Contrast and a certain anti-fogging effect is exerted.

In the formulas given, R can be a lower alkyl group, such as a methyl or ethyl group, etc., and X can be a halogen atom, in particular a chlorine, fluorine or bromine atom. The emulsion layer containing the hardener can after coating on a support, and after a 18 hour drying at 15 ° C a melting point of the order of at least about 37.8 ⁰ C Photosensitive photographic
Silver halide emulsion containing a hardener

Applicant:

Eastman Kodak Company,

Rochester, N. Y. (V. St. A.)

Representative:

Dr.-Ing. W. Wolff, H. Bartels and Dr. J. Brandes, Patent Attorneys, Munich 22, Thierschstr. 8th

Named as inventor:

Roy Arthur Jeffreys Harrow,

Middlesex (UK)

own. The aminophosphoryl halides produce gelatin-silver halide emulsions which form layers lead, which after drying has an excellent resistance to water and damp or have aqueous conditions at elevated temperature.

Although the aminophosphoryl halides are advantageously used in concentrations of 0.3 to 6 parts are applied to 100 parts of gelatin, they can also be used in lesser or greater concentrations will. In addition to the excellent resistance to water and aqueous conditions at elevated temperatures have those using the new aminophosphoryl halides produced layers generally have good resistance to high temperatures. the Aminophosphoryl halides which can be used according to the invention consist either of dialkylaminophosphoryl dihalides or bis-dialkylaminophosphoryl halides. Since gelatin normally used for photographic purposes has high gelling power should have, d. H. Should have a "Bloom value" of at least 250 g, the aminophosphoryl halides are suitable in particular for the hardening of light-sensitive emulsion layers, for their production Gelatin of high gelling power is used as a binder for the silver halide.

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

example 1

Samples of fine grain gelatin-silver bromoiodide emulsion of negative type containing

609 508/213

6 to 7% gelatin were made with various amounts of dimethylaminophosphoryl dichloride and bisdimethylaminophosphoryl chloride offset. These samples were coated onto cellulose triacetate backing. The specimens obtained were then subjected to a series of test conditions. The test slopes were examined for sensitivity, fog, contrast and melting point, with the the latter determination was made after the emulsion was immersed in water and the temperature increased from room temperature to the boiling point of water. According to test condition (a) was tested 1 week after the coating, and the test condition (b) became 1 week after storage The test slope was tested at a relative humidity of 42% and a temperature of 48.9 ° C. The results obtained are shown in Table I below:

Table I

Relative veil sensitivity

contrast

Mp. ⁰ C

a) 1 week after coating

Comparative sample (V.P.)

V. P. + Compound I; (R = methyl, 0.3 g / l)

V. P. + Compound I; (R = methyl, 1.0 g / l)

V. P. + Compound II; (R = methyl, 0.3 g / l)

V. P. + Compound II; (R = methyl, 1.0 g / l)

b) 1 week after storage be

Comparison sample (VP)
VP + compound I; (R = methyl, 0.3 g / l) VP + compound I; (R = methyl, 1.0 g / l) VP + compound II ;. (R = methyl, 0.3 g / l) VP + compound II; - (R = methyl, 1.0 g / l)

In a further series of tests, the test slopes were tested 3 months after coating. Here

4.30 0.19 0.96 32.2 34.4 4.40 0.16 0.96 34.4 • 39.4 4.34 0.13 0.93 60.0 82.2 4.40 0.14 0.98 38.3 65.5 4.36 0.15 0.89 > 93.3 > 93.3 more active ι humidity C. 4.30 4.32 4.24 4.33 4.14 of 42% at 48.9 ° 0.24 0.21 1.6 0.19 0.20 0.89 0.86 0.87 0.85 0.83

were those given in the following tables Get results:

Table II veil contrast Mp ° C 3 months after coating Relative
sensitivity 0.17
0.11
0.13
0.12 0.97
0.95
0.93
0.87 35.6
76.7
40.6
> 93.2 Comparison sample (VP)
VP + compound I; (R = methyl, 1.0 g / l)
V. P, + Compound II; (R = methyl, 0.3 g / l)
VP + compound II; (R = methyl, 1.0 g / l) 4.34
4.24
4.29
4.30

In a further series of experiments, other specimens were tested after they had been stored for 6 months had been. The following results, shown in Table III, were obtained:

Table III

6 months after coating Relative
sensitivity veil contrast Mp. ⁰ C Comparison sample (VP)
VP + compound I; (R = methyl, 1.0 g / l)
VP + compound II; (R = methyl, 0.3 g / l)
VP + connection Π; (R = methyl, 1.0 g / l) 4.30
4.21
4.30
4.15 0.19
0.13
0.17
0.14 0.94
0.88
0.92
0.88 33.3
92.2
40.6
68.3

Example 2

6o

Example 1 was repeated with the exception that in control of the chlorides used in Example 1 the corresponding fluoride, namely dimethylaminophosphoryl difluoride and bisdimethylphosphoryl fluoride were used. With the fluorides were im Achieved essentially the same effects as with the chlorides of Example 1.

Example 3

In this example hardeners "of the following formulas were investigated:

(C ₂ Hs) ₂ NPOCl ₂
(C ₂ Hs) ₂ N) ₂ POCl and
(C ₂ Hs) ₂ N) ₂ POF

(IV)

(VI)

These hardeners were made into a gelatin-silver halide photographic emulsion and layers shed. The test results obtained with these layers are summarized in Table IV below:

Table IV

Relative sensitivity

veil

contrast

Mp. ⁰ C

Comparison sample (VP)
VP + compound IV, 1.0 g / l
VP + compound IV, 3.0 g / l
VP + compound V, 1.0 g / l

Comparative sample (V.P.)

V. P. + Compound IV, 1.0 g / l

V. P. + Compound IV, 3.0 g / l

V. P. + Compound V, 1.0 g / l

Comparison sample (VP)
VP + compound IV, 1.0 g / l
VP + compound IV, 3.0 g / l
VP + compound V, 1.0 g / l

a) 1 week after coating

4.37 4.31 4.21 4.32

4.26 4.12 3.84 3.97

c) 3 months after coating

4.30 4.29 4.22 4.27

The compound (VI), namely bisdiethylaminophosphoryl fluoride acted as a hardener in a similar way to the corresponding chloride.

The aminophosphoryl halide hardeners are not only suitable as hardeners for photographic silver halide emulsions, in which the binder for the silver halide consists of gelatin, but these Compounds are also suitable as an additive to emulsions in which the binder for the silver halide consists of a mixture of gelatin and other polymeric compounds. For example, can the silver halide emulsions contain except gelatine: butyl acrylate-acrylic acid copolymers and / or ethyl acrylate-acrylic acid copolymers. Gelatin can be the main ingredient in such emulsions of the binder or represent only a small proportion of the binder. The following Examples illustrate this.

Example 4

A silver halide photographic emulsion was prepared whose binder was 1 part of gelatin and 3 parts (dry weight) of the sodium salt of an ethyl acrylate-acrylic acid copolymer of 80 percent by weight ethyl acrylate and 20 percent by weight acrylic acid. To different The proportions were 5 g each of dimethylaminophosphoryl chloride or di (dimethylamino) phosphoryl chloride added per 100 g of binder. The emulsions were then coated on a support. The percentage swelling in water was determined from the tests obtained. It turned out that the Emulsion layers with a content of a hardener had a swelling of 240 and 200%, while a comparative test specimen without hardener had a swelling of 340%.

0.20 0.98 32.8 0.16 0.98 35.0 0.12 0.98 37.8 0.17 1.00 35.6 42 ° / from 48, 0.26 33.9 0.20 36.7 0.27 43.3 0.30 Ό and a temperature 36.7 mg
0.21 32.2 0.16 41.1 0.12 > 93.3 0.16 > 93.3 0.99 0.95 0.87 0.90 1.03 0.87 0.89 0.90 Example 5

A silver halide photographic emulsion was prepared whose binder was 3 parts. Gelatin and 1 part (dry weight) of an ethyl acrylate-acrylic acid copolymer existed, as described in Example 4. 5 g of dimethylaminophosphoryl dichloride or di (dimethylamino) phosphoryl chloride per 100 g of binder were added to various proportions of the emulsion. The emulsions were then coated onto a support. The swelling in water was 250 ° / ₀ for the layers which contained a hardener , while a swelling of the emulsion layer in water of 530% was found for a comparative sample which had been produced without hardener.

Comparison example

The advantages of the aminophosphoryl halide hardeners used according to the invention over known ones Hardeners, such as nitropropandial and divinyl ketone, result from the results of the following comparative tests :

Different proportions of the same silver halide emulsion were added as a hardener: Nitropropandial, Divinyl ketone and bis (dimethylamino) phosphoryl chloride and dimethylaminophosphoryl dichloride. The emulsions were coated on a photographic support. From the received Films were used for speed, y value and fog shortly after and after coating 1 or 2 weeks storage at a temperature of 49 ° C with a relative humidity of 50%. The following results were obtained:

7th Freshly made film y value veil Storage time
(Weeks) 8th y value veil relative
Sensation
opportunity 1.14 0.13 1 0.88 0.41 g hardener / mole silver 100 1.15 0.10 1 Stored film 0.45 0.78 - (comparative sample) 85 1.27 0.16 2 relative
Sensation
opportunity 0.69 0.96 3.6 g nitropropandial 100 60 - (comparative sample) 7.4 7.2 g bis (dimethyl 1.32 0.11 2 37 0.93 0.11 amino) phos- 85 1.17 0.09 2 0.66 0.56 phoryl chloride 100 - (comparative sample) 57 2.4 g dimethylamino 1.17 0.06 2 29 1.05 0.07 phosphoryldi- 87 1.44 0.13 1 1.00 0.24 chloride 100 1.10 0.08 1 0.88 0.10 - (comparative sample) 67 83 1.2 g divinyl ketone 83 74

From the results obtained, it can be seen that the relative sensitivity of nitropropandial containing Emulsions decrease extremely sharply after storage. The addition of divinyl ketone leads a considerable decrease in the relative sensitivity even with fresh samples.

The advantages of the aminophosphoryl halide hardeners used according to the invention over known ones Hardeners such as formaldehyde and mucochloric acid result from the results of the following comparative tests:

Different proportions of a highly sensitive silver bromoiodide emulsion made with the aid of a cyanine dye After panchromatic sensitization, formaldehyde, mucochloric acid and aminophosphoryl halide were carriers added. The emulsions were coated on cellulose acetate supports. The films obtained were then placed in a sensitometer exposed, developed, fixed, washed and dried. The following results obtain:

Freshly made film y value veil relative ' Stored Filrr 1 veil g hardener / 100 g gelatin relative 1.30 0.16 Sensation
opportunity 0.42 Sensation
opportunity 80 y value - (comparative sample) 100 1.25 0.12 0.95 0.12 1.0 g dimethylaminophosphoryl 82 dichloride 89 1.28 0.10 1.10 0.07 3.0 g dimethylaminophosphoryl 65 dichloride 68 1.33 0.13 1.12 0.17 1.0 g di (dimethylamino) phospho- 80 phoryl chloride 94 1.32 0.11 1.03 0.09 3.0 g di (dimethylamino) phosphor 0.92 0.13 71 0.89 phoral chloride 85 1.12 0.13 10.2 1.03 0.24 0.5 g formaldehyde 78 57 0.38 0.5 g of mucochloric acid 83 0.83

Claims (3)

Patent claims: 1. Light-sensitive, photographic silver halide emulsion, the binder of which consists at least partially of gelatin and which contains a hardener, characterized in that it contains an aminophosphoryl halide of _{the formulas R 2 NPOX 2} and (R ₂ N) ₂ POX, in which R the Has a meaning of a lower alkyl group and X is a halogen atom. 2. Silver halide emulsion according to claim 1, characterized in that it is used as a hardener Dialkylamino) phosphoryl dichloride, a bis (dialkylamino) phosphoryl chloride or a bis (dialkylamino) phosphoryl chloride contains. 3. Silver halide emulsion according to claims 1 and 2, characterized in that it as hardener a diethylaminophosphoryl dichloride, a bis (diethylamino) phosphoryl chloride or a Contains bis (diethylamino) phosphoryl fluoride. Considered publications:
German Patent Nos. 872153, 935 706;
■ USA patents No. 2,372,873, 2,870,013,
2,732,303;
"Adhäsion" magazine, 1961, issue 5, pp. 228/229. 609 508/213 2.66 © Bundesdruckerei Berlin