DE2420414A1 - PHOTOGRAPHIC MATERIAL - Google Patents

Description

24204U

Photographic material

The invention relates to a photographic material with at least a hydrophilic colloid layer hardened by the addition of a hardening agent.

It is known that photographic materials using a hydrophilic colloid, e.g. gelatin, optionally made with synthetic polymers as binders have become ^ in the course of their development process of action different aqueous baths of different pH values and possibly elevated temperatures. Much Work has already been done on treating natural and synthetic polymers to improve their resilience to improve compared to water, so that no melting during the development process or the drying process and there is no undesired swelling of the polymers. A wide variety of compounds have already been used to particularly to treat photographic hydrophilic colloidal binders containing gelatin.

An overview of the hardening of hydrophilic colloids, e.g. Gelatin® , can be found, for example, in the book by G. F. Duffin, "Photographic Emulsion Chemistry", The Focal Press, 1966, pages 158-162.

It is known, for example, to harden hydrophilic colloids with metal salts, for example salts of chromium, aluminum and zirconium, to give v @ rw @ ad @ n «. The disadvantage of these salts is that they react with gelatine and that they harden gelatine very quickly. which are necessary - in order to achieve a sufficient® hardening ₉ that a © premature® coagulation of the gelatin solution takes place «

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Other known curing agents require heating in order to achieve a to achieve a sufficient degree of hardening. However, heating is, for example, in the case of silver halide photographic emulsions and emulsion layers are undesirable because such a heating process tends to lower the sensitivity the emulsion layer takes place and because there is also a risk of fogging.

The disadvantage of other organic hardeners is that they must have a comparatively high molecular weight, so that they do not become diffusing. It has also been shown that these hardeners also often increase serious adverse physical effects in the emulsion layers to lead. In addition, such hardeners generally have an undesirably low ratio of active curing groups to BaI load groups on «,

Many of the known hardening agents act slowly, so that a comparatively long period of time is required in order to achieve a sufficiently stabilized state of hardening. As a result, the development properties and sensitometric characteristics of a photographic emulsion layer with a content of such a hardening agent change in a way that cannot be controlled in a desired manner. This undesirable effect is called "post-hardening" and is therefore special disadvantageous because the Härtmigsprozeß the layers bsi storage of Aufzeiehnungs-Hiaterialion continues, and thereby the permeability to Eh twick lungs lös tangesa abaiiiiRi ₆ This leads zn problems and difficulties wlferead of Eatwickltmgsprog © ss @ s _B wherein the sensitivity of the photographic layers adversely affected will.

if

409846/0363

The object of the invention is to provide curing agents in whose use the problems associated with "post-curing" are eliminated or the known problems at least largely be eliminated.

The invention was based on the knowledge that photographic layers made of or with hydrophilic colloids can be hardened Certain mixtures of hardening agents are excellently suited and that certain mixtures are used when these are used in combination Curing agent synergistic effects can be observed, with the help of which the post-curing can be controlled. It has been found that when certain mixtures of chemical hardeners are used, improved "post-cure" is achieved can be compared to the degree of post-curing that is achieved when the individual components of the curing agent can be used alone.

The invention is based on the knowledge that for production hydrophilic colloids in an excellent manner mixtures of an acrylic hardener or acrylic hardener or formaldehyde plus bis (vinylsulfonylmethyl) ether or on the other hand diacrylamide plus 1,7-dichloro-3,3,5,5-tetraoxo-3,5-dithiaheptane suitable.

The invention thus provides a photographic material with at least one by adding a hardening agent hardened hydrophilic colloid layer, which is characterized in that the colloid layer consists of a hardening agent from a mixture of:

(a) diacrylamide and

(b) 1, 7-DiChIOr-S, 3,5,5-fetraoxo-3,5-dithiaheptane or

(c) an acrylic curing agent or formaldehyde and

(d) bis (vinylsulfonylmethyl) ether

at a weight ratio of (a) to (b) or (c) to (b) of about 5: 1 to about 1: 5 is hardened.

409846 / Ü863

Preferably the ratio used is from about 3: 1 to 1: 3.

under "acrylic hardeners" or hardeners Acrylic bases are to be understood as those with acrylic groups, e.g. those "acrylic hardeners" from GD-PS 1 234 S39 and US-PS 3 6 40 720 known type.

Typical acrylic hardeners or acrylic-based hardeners are diacrylamide, N-methacryloy] acrylaraid and N, N'-diacryloylurea.

The use of acrylic hardeners or hardeners based on acrylic is for example from GB-PS 1 234 S3D and US Pat U.S. Patent 3,640,720 is known. The use of bis (vinylsulfonyl) ether as a hardening agent is, for example, from US-PS 3,539,644 and 3,642,486 are known.

1,7-dichloro-3,3,5 ₉ 5-tetraoxo-3,5-dithiaheptane can, for example, from the; corresponding sulfide by the method described by II. S. Schultz and .Mitarbeitern in the journal "Journal of Organic Chemistry", 28, 1140 (1963) by oxidation with hydrogen peroxide. Formaldehyde is a well-known hardening agent for hardening hydrophilic colloids or wet ones containing hydrophilic colloids. The previously cited book by GF Duffin "Photographic Emulsions Chemistry" describes, for example, the use of formaldehyde to harden hydrophilic colloids.

With the hardening agent mixtures or hardening agent combinations described, the customary known hydrophilic colloids which are used for the production of photographic materials and which can be hardened by means of formaldehyde can be hardened. This means that it is possible with the described mixtures or combinations, for example, such hydrophilic colloids such as gelatin hardening, have melting points below about 65 ° C, preferably between about 27 ⁰ C and about 50 C. Examples of such hydrophilic colloids can be found in the cited patents.

The hardening agent mixtures described can be used to harden a wide variety of natural and synthetic polymers used as supports or binders in the manufacture of photographic materials or elements. Examples

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for hardenable hydrophilic colloids are gelatin, colloidal albumin, proteins, dispersed polymerized vinyl compounds, and in particular those which are able to increase the dimensional stability of photographic materials, for example Polymers made from alkyl acrylates and alkyl methacrylates, acrylic acid, sulfoalkyl acrylates or sulfoalkyl methacrylates and maleic acid with polymer chains with free amino groups, v.ie they z.ij. the end Column 7, lines 21-26 of U.S. Patent 3,702,249 are known.

The hardening agent mixtures described can be mixed with hardenable colloids in the most varied of ways, for example. in solution, emulsion or layer form. The mixtures can be used here in any suitable ilärtungskonzentration, which leads to an increase in the melting point of the or the curable hydrophilic colloids of at least about 5 ⁰ G including, for example concentrations of from about 0.5 to about 10 parts by weight o, based on the Dry weight of the curable colloid or colloids are required, preferably concentrations of about 0.7 to about 3 weight percent. The mixtures of hardening agents used according to the invention are particularly suitable for hardening hardenable photographic light-sensitive emulsion layers, specifically in particular for hardening emulsion layers which contain gelatin and a piotographic silver halide.

The hardening agent mixtures described can be used for hardening of a wide variety of photographic emulsions. For example, they are orthochromatic, panchromatic for hardening as well as infrared-sensitized limulsions, also for the hardening of oil emulsions and others not spectrally sensitized emulsions. The blends can be emulsions are incorporated before or after the addition of spectral sensitizing dyes, provided that such dyes are added. The hardening soil mixers described can also be used for example for hardening sensitized with sulfur and gold Use silver halide emulsions.

409846/0863
BATH ORIGINAL.

2420AH

The mixtures of hardening agents are advantageously used directly combined with the emulsion during its preparation, the components of the hardener mixture being added individually can be or the mixture as such. The emulsion treated with the two hardener components can then applied to a conventional support in a conventional manner and dried. The main hardening reaction (at which the hardeners react with the hydrophilic colloid in the coated layer) preferably runs during the drying level. The dried chemically hardened photographic layers obtained or the such Photographic materials having layers can be processed at comparatively higher temperatures, i. develop, fix and the like without physical degradation or destruction of the materials by the application higher temperatures takes place.

Hardening can also be achieved, for example, by the layer or layers of a photographic Material with a hardenable hydrophilic colloid with an aqueous solution of one of the hardener mixtures described bring into contact, for as long and at such a temperature, which is sufficient to the desired degree of hardening achieve, the hardening can optionally also take place during a subsequent hardening stage, provided that such a step is desirable.

The support of a photographic material according to the invention can consist of one of the customary known supports, as are normally used for the production of photographic materials, for example a film of cellulose nitrate, cellulose acetate, a polyvinyl acetal, polystyrene, methylene terephthalate or another polymeric material, as well made of glass, paper, mstall © by the HoIs. Auek lcaasi the substrate of a photographic material Haccording to the invention consist of a paper substrate which has been coated with an α-olefin polymer, in particular its polymer

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an α-olefin with 2 to 10 carbon atoms, e.g. polyethylene, Polypropylene or an ethylene-butene copolymer.

The photographic emulsions curable according to the invention can contain the usual known additives, e.g. spectral sensitizers, sensitivity enhancers and other hardeners, plasticizers, and the like.

The emulsions curable with the mixtures described can be used for the production of color photographic recording materials are used and thus contain color couplers. Finally, the hardener mixtures described are also suitable for Hardening of emulsions that are developed using solutions that contain color couplers or other color formers. Further the hardening agent mixtures described are also suitable for hardening emulsions of the so-called mixed package type.

In the case of hardening silver halide emulsions, the Emulsions contain the usual known light-sensitive silver halides, e.g. silver bromide, silver iodide, silver chloride, Silver chloride bromide and silver chloride iodide. The silver halides can for example consist of those which are latent Images for the most part depict on the surface of the silver halide grains or which latent images are inside of the silver halide grains.

Emulsions hardened with the hardening agent mixtures described Furthermore, they are excellent in the manufacture of photographic materials for the diffusion transfer process. One form of such a process is known to remove the undeveloped silver halide in the non-image areas of the negative is complexed to form a water-soluble compound which is incorporated into an image-receiving layer diffused, in which the compound is precipitated in the form of a positive metallic silver image. In the case of another Diffusion

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24204H

Transferring process, the final image is created by diffusion of the developing agent, oxidized developing agent, one Coupler or dye generated by diffusion from the exposed and developed photosensitive layer into a second layer.

It has proven to be particularly advantageous to use the hardener mixtures to be used when very little post-curing of the photographic material is advantageous.

The actual degree of "post cure" a photographic Material is or may be subject to, is not foreseeable, especially not with regard to the various Conditions such as temperature, pressure and humidity to which the photographic material is subjected can be.

However, a test procedure has been developed by which the relative degree of "post-cure" that can be determined by the most diverse chemical hardening agents is caused. Tests have also shown that approximate predictions can be made as to how high the degree of post-curing is. It has it has also been shown that the test results are well comparable with the results obtained in practice with the actual Use of photographic materials.

The test is a so-called. "7 Tage swelling test", the test is to incubate two samples and that a device under test for 7 days at a temperature of 49 ⁰ C and a relative humidity of 50% and the Anderei ^ specimen 7 days long at a temperature of 5 ° C and a relative humidity of 50 $. The degree of swelling or the swelling capacity is determined by determining the thickness of the layers applied to a layer substrate before and after immersing the test specimen for 5 minutes in distilled water at room temperature. In the ideal case, the percentage swelling in the 7-day swelling test described should be 0 or approximately 0. Such ideal values mean

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that there is very little or virtually no "post-curing" under the test conditions.

The following example is intended to illustrate the invention in more detail. example

First, three-layer photographic materials became produced by placing the following layers on a cellulose acetate support in a conventional manner were applied:

(1) a gelatin undercoat containing 1.62 grams of gelatin per square meter;

(2) a green-sensitive gelatin-silver bromide iodide emulsion containing 1.45 g of silver, 32.3 g of gelatin and 1.75 g of one purple dye-forming color coupler, each per 1 square meter of support area and

(3) a gelatin topcoat containing 32.3 grams of gelatin per square meter.

In addition to these recording materials produced for comparison purposes, which did not contain a hardener, other recording materials were made using chemical hardeners and combinations of chemical hardeners. The hardeners were contained in the corresponding gelatin Dispersions mixed in just before the dispersions were used for coating. After applying the layers the recording materials produced were quenched and dried in the usual way.

The recording materials described were then the same as the ones described Subjected to "7 days swelling test".

The following hardeners were used to carry out the tests:

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-ΙΟ Ι diacrylamide

II bis (vinylsulfonylmethyl) ether

III bis (vinylsulfonylethyl) ether

IV 1,7-DiChIOr-S, 3,5,5-tetraoxo-3,5-dithiaheptane

V N-methacryloylacrylamide

VI N.N'-diacryloylurea

VII formaldehyde

VIII Mucochloric Acid

The results obtained are shown in the table below. The test items that have a "+" are test items that have been mixed with a hardening agent used in accordance with the invention have been hardened.

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Test specimen hardening
No medium - - (mm / g Gel) % Source
7 days
at 5 ^° C
+ 501 right
lativer
Humidity
activity development after
7 days
at 49 ⁰ C
+ 5O ⁹ _{e right}
lativer
Humidity
activity ΔI source
lung
rise 1 I. II - 675 606 69 2 I. I. 0.040 292 314 -22 3 II I + II 0.080 238 249 -11 4th II I + II 0.044 250 235 15th 5 I + II I + II 0.088 192 172 20th ⁺ 6 I + II V 0.040
♦ o , 022 236 231 5 ⁺ 7 I ■ <■ II II + V 0.080
+ 0 , 044 192 182 10 ⁺ 8 9 formaldehyde VI 0.040
+ 0 , 044 198 190 8th 10 VI 0.334 175 200 -25 11 II ♦ VI - 589 492 97 12th II + VI 0.044 250 229 21 + 13 II + VI O "O67 276 313 -37 ⁺ 14 O ₉ O33
4- 0 , 022 303 274 29 * 15 0.033
+ 0 , 044 210 205 5 16 0.067
+ 0 , 044 210 210 0 * 17th 0.144 347 289 58 18th 0.044
+ 0 , 144 229 213 16 19th 0.030 279 342 -63 ⁺ 20 0.059 232 287 -55 21 0.022
+ 0 , 030 231 238 -7 22nd 0.044
+ 0 »030 203 210 -7 0.022
+ 0 , 059 187 215 -28

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24204U

Continuation from table

Δό 11 + VI 0.044 174 187 -13 + 0.059 495 292 203 24 III 0.020 438 226 212 25th III 0.039 26th I + III 0.033 365 251 114 + 0.020 27 I ♦ III 0.067 321 242 79 + 0.020 28 I + III 0.033 318 205 113 + 0.039 29 I + III 0.067 305 205 100 + 0.039 462 369 93 30th IV 0.019 31 I + IV 0.033 333 315 18th + 0.019 32 I + IV 0.067 318 305 13th + 0.019 170 227 -57 33 VII 0.333 34 II + VII 0.022 168 161 7+ + 0.333 35 II + VII 0.044 166 168 -Z ⁺ + 0.333 405 271 134 36 VIII 0.059 37 I + VIII 0.033 325 233 92 + 0.059 38 I + VIII 0.067 305 218 87 + 0.059

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409846 / U863

242Q4U

With the given in the table results comparable results were obtained when photographic Aufzeichnungsmateri alien of the type in the course of photographic processing as described, such as the Kodak Ektachrome ME-4 have been developed process (without pre-cure and neutralization step) at a temperature of 52 ⁰ C .

Furthermore, experiments have shown in which photographic recording materials exposed in a conventional Eastman 1B sensitometer and then developed in the conventional manner were that those used according to the invention, acting synergistically When used in the usual concentrations, hardeners did not exert any adverse effects on the recording materials.

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Claims (7)

PATENT CLAIMS 1. Photographic material with at least one hydrophilic colloid layer hardened by the addition of a hardening agent, characterized in that the colloid layer with a hardener consisting of a mixture of: (a) diacrylamide and (b) 1,7-DiChIOr-S, 3,5,5-tetraoxo-3,5-dithiaheptane or (c) an acrylic curing agent or formaldehyde and (d) bis (vinylsulfonylmethyl) ether at a weight ratio of (a) to (b) or (c) to (d) is hardened from 5: 1 to 1: 5. 2. Photographic material according to claim 1, characterized in that that the hydrophilic colloid of the hardened hydrophilic colloid layer consists of gelatin. 3. Photographic material according to claims 1 and 2, characterized in that the weight ratio of (a) to (b) or (c) to (d) is 3: 1 to 1: 3. 4. Photographic material according to Claims 1 to 3, characterized in that it contains at least one hardened silver halide emulsion layer having. 5. Photographic material according to claims 1 to 4, characterized in that the colloid layer, based on the dry weight of the hydrophilic colloid, contains 0.7 to 3 % by weight of the hardening agents * ..,. - 409846/0863 6. Photographic material according to Claims 1 to 5, characterized in that that the hydrophilic colloid layer with diacrylamide; N-methylacryloylacrylamide or N, N'-diacryloylurea as acrylic hardener is cured. 7. Photographic material according to Claims 1 to C, characterized in that that the hydrophilic colloid layer is based on 0.5 to 10% by weight of one of the specified hardening agent mixtures to the dry weight of the hydrophilic colloid. 409846/0863 _/ -