DD124854B1 - METHOD FOR CURING GELATINE-CONTAINING LAYERS - Google Patents

Description

-2- 190 251

Apart from chromium-chlorides, the reaction can also be carried out with other chromium-III compounds, eg. As chromium-III acetate, take place.

It is an advantage of the invention that the use of the chromium compounds according to the invention in addition to the known photographic additives, such as filter dyes, sensitizers, wetting agents, Antikometenmittel, pH regulators, clear coaters, stabilizers, hydrophobic and / or hydrophilic color couplers, viscosity-increasing or viscosity-lowering compounds and mordants can be done without their effect is affected.

The use of the compounds according to the invention can be carried out in emulsions of various kinds with regard to the composition of the silver halides or the type of preparation, without limiting the applicability. A further advantage of the chromium compounds according to the invention is that, in addition to the improvement of the physico-mechanical properties of the gelatin layers, a marked improvement in the adhesion of the photographic layers to the substrate is effected, the carrier material e.g. Cellulose ester, polystyrene, polyethylene terephthalate or polyvinyl acetate.

With particular advantage, the compounds according to the invention are used in multilayer materials, since they allow the layers to be matched to the same swelling behavior given good resistance to oily substances and rapid curing. The application in photographic materials can also be done in combination with organic curing agents, wherein it has proven to be advantageous to apply the method of diffusion curing for the organic curing agent .

The use of the chromium compounds according to the invention is not limited to emulsion layers but can also be carried out in the conventional auxiliary photographic layers, e.g. in Barytagen, preparation layers, backing layers, interlayers or coatings, the purpose of the materials may be of different nature, such. B. for positive, negative, reversal, X-ray or Duplizierverfahren.

Another possible application also results from the use of the compounds according to the invention in the processing baths. During this process, the chromium compounds diffuse into the gelatin layers during processing and cause the hardening process.

Another important advantage of the compounds according to the invention is that they provide the possibility of latent curing. The compounds may e.g. the gelatin layers are added at pH values> 7.0, without a swelling depression is observed on the layers. By treatment in stopping or fixing baths or baths with pH values <7.0, the curing occurs, and the layers show a significant swelling reduction and melting point increase. This procedure allows optimal sensitometric data to be obtained during development. The reactions with K and / or sodium acetates are carried out in aqueous solution, but preferably in organic solvents, e.g. Methanol, advantageously at temperatures> 50 ° C performed. The reaction in methanol gives z. 3. in the use of chromium-III-chloride has the advantage that the forming alkali metal chloride can be sucked off after completion of the reaction and thus eliminates a burden of Geiatineschichten by the amounts of electrolyte. The reactions can also be carried out advantageously in the melt.

In the preparation of the compounds according to the invention, the choice of the chromium compound / acetate ratio is left to the user as it depends on the required viscosity stability of the gelatin solutions. The user is given the opportunity to produce a chromium compound for each system by choosing the quantitative ratio, which causes the desired viscosity behavior of the casting solutions.

In the case of using chromium-ill-chloride in the reaction, for gelatin solutions (gelatin prepared by the alkaline digestion method), a viscosity stability of pH5 to pH8 is achieved when the amount ratio (weight ratio) of e.g. 1: 1 to 1: 1.5. The structure of the new chromium compounds can z.Z. can not be specified exactly. It could be assumed that the significant differences between the new compounds and the previously known chromium hardeners are due to the formation of pclymeric chromium complexes. The invention will be explained in more detail below by Ausführungsbeispieien.

example 1

As a general rule for the production of the chromium-III compounds according to the invention, the following instructions are used. Thereafter, the reactions listed in Table 1 are carried out.

in 1GO ml Methanoi are dissolved 1.2 parts by weight of sodium acetate and added with stirring 1 part by weight of chloride chromium-IH-(20% Cr ³ "). Subsequently, the solution is heated and three hours at reflux (70 ⁰ C). After After the mixture has cooled, the sodium chloride is suctioned off from the methanolic solution, and the solution can be diluted to the desired chromium content after determination of the content.

Example 2

As comparison substances, solutions according to table 2 are used. The difference to Example 1 is that the solutions 12 to 15 are not heated, but are made only at room temperature.

3eispiei 3

To a 5% gelatin solution (isoicnic point 4.78), different amounts of the chromium III compounds are added and the sample solutions are adjusted to a pH of 6.3 with citric acid. Thereafter, the solutions are poured onto prepared glass plates. The queliung of the incubated gelatin layers is determined after two days storage at 50 ° C and 20% relative humidity by the known weighing method.

The values obtained in Table 3 show that the compounds according to the invention show equally good to better curing properties in comparison to the previously used chromium curing agents.

Example 4

To a 5% gelatin solution as in Example 3, wetting agents with enhanced wetting agent action are added to the preparation layer and blue staining is achieved by the addition of gelatin gels containing colloidal silver. After addition of the listed in Table 4 chromium solutions and pH adjustment to 6.8, the casting is carried out on a prepared Triacetatunteriage.

-z- 190 251

The viscosity of the casting solutions is adjusted to 8.2 cP in each case. The solutions are always shed after a standing time three hours ago. The standing temperature is 4O ⁰ C. The determined physical-mechanical values confirm the results of Example 3. In addition, it can be seen that allow only the chromium compounds of the invention, since in the hitherto used chromium compounds by viscosity increases of Geiatineiösungen required for the casting toughness these solutions can not be met. The results are summarized in Table 4.

Example 5

Casting solutions analogous to Example 4 are measured at the time intervals listed in Table 5 on an Ubbelohde viscometer and the cSt determined is converted into cP by multiplication with the densities.

Table 5 clearly shows the advantages of the new chromium curing agents since only gelatin solutions with chromium curing agents of the new type exhibit the viscosity stability required for the casting process of photographic materials.

The temperature during the standing time and the measurements is 40.5 ⁰ C.

Example 6

To justify the demands for elevated temperatures in the production of the new chromium compounds, the production is carried out at different temperatures. To rule out that the significant differences are due only to a change in the reaction rates due to the different temperatures, the same tests are repeated by the sample solutions after a longer standing time of the solutions. The gelatin system used was that of Example 4. Table 6 shows that the advantage according to the invention is achieved only by a chemical reaction which takes place only at elevated temperatures.

Example 7

60kg of a highly sensitive silver bromide iodide emulsion containing more than 1.5 mole% silver iodide and 98.5 mole% silver bromide at a gelatin content of 80g / kg emulsion and used for radiological purposes are made after maturation with the known organic sulfur compounds with a triazaindoicin stabilized and adjusted to a pH of 6.5.

After the division into 6 equal portions, these are, after the addition of the specified in Table 7 curing agents and the common casting aids, such as wetting agents and clear coat, cast on a 180μ Polyäthyienterephthalat underlay.

The material is cut open and exposed test strips behind a Stufenkeii. The development of the sample strips is fresh and after artificial storage in a developer of the following composition

0.6000 g 1-Pheny! Pyrazo! Idon- <3) 10.0000g Hydroquinone 55.0000g Sodium sulfate (anhydrous)

0.1500 g of ethylamino-β-hydroxypropyl

hydrazindioxalat

55,0000g sodium carbonate (anhydrous) 10.0000g potassium bromide

Fill 0.0075 g of 1-phenylmercaptotetrazole with water to 1 liter.

The results of Table 7 confirm the photographic safety of the compounds of the invention. Example 3

A color multilayer material for negative purposes is produced. For the bottom casting, a red-sensitized eromjodsiibererriulsion of the cooking type, with a gelatin content of 9.0% is used. In addition to the usual additives, such as StaOilisatoren, wetting agents, filter dyes, clear holders, a cyan coupler Ko686, according to BIOS 721.18 (1946), is used. On the underside a gelatin interlayer is potted. The medium casting consists of a gold-ripened green-sensitized bromide silver emulsion with a gelatin content of 9.1%. In addition to the additives already mentioned, a magenta coupler Z169, according to BIOS 721.21 (1946), is added.

Following the application of a gelatin interlayer, the unsensitized top-coat emulsion, a bromochloride emulsion having a gelatin content of 8.6%, with the addition of a yellow coupler F530, according to BIOS 721, 22 (1946), and the other casting additives is applied. The last step is the application of a gelatin coating. The evaluation of the material takes place after exposure of a wedge and measurement of the developed curves behind the corresponding color separation filters. From Table 8 it can be seen that only the novel chromium compounds of the invention can be added in sufficient quantity without disadvantages.

Example 9

To the gelatin solution of Example 3, the chromium compounds given in Table 9 are added at different pH values (+).

After storage for 10 days (5OX, 20% relative humidity), the swelling and the melting point of the materials are determined after a treatment:

a) 10min developer 20min watering

b) 5 min stop bath (pH 4.0) 25min watering.

The results of Table 9 confirm the latent hardening effect of the new chromium compounds. {+) (I = adjusted pH 7.5 Ii = adjusted pH 6.5!

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Table 1

Verb. output Weight Loss reaction Dilutes on No. chromver relationship medium % Cr 3+ binding Chromium salt: sodium acetate

Chromium-ill-chloride Chromium-lll-chloride Chromium-lll-chloride Chromium-lll-chloride C h m-lll-acetate

1: 1.0 1: 1.2 1: 1.2 1: 1.3 1: 1.2

Product 3 isolated and dissolved in water Product 4 isolated and dissolved in water

water 1 water 1 methanol 1 methanol 1 water 1 1 1

Table 2

verb

 No.

Exit chromium bond

Weight ratio of chromium salt: sodium acetate

reaction medium

Dilutes on

% Cr 3+

8th Chrome hi-su if at - 9 Chromium III chloride - 10 Chromium III chloride - 11 Chromium III acetate - 12 Chromium-III-sulphate 1: 1 13 Chromium III chloride 1: 1.2 14 Chrome lli chloride 1: 1.2 15 Chromium III acetate 1: 1.2

water 1 water 1 methanol 1 water 1 water 1 water methanol 1 water 1

Table 3

mg Cr ³⁺ ZIOOOmI 5% gelatin solution 100 verb 2 300 verb 2 500 verb 2 100 verb 3 300 verb 3 500 verb 3 100 verb 5 300 verb 5 500 verb 5 100 verb 6 300 Verb 6 500 verb 6 100 verb 8 300 verb 8 500 verb 8 100 verb 9 300 verb 9 500 verb 9 100 verb 11 300 verb 11 500 verb 11

Table 4

mgCr ³⁺ / 1 000 mi 5% gelatin solution 100 verb. 8 500 verb 8 100 verb 9 500 verb 9 100 verb 10 500 verb 10 100 verb 11 500 verb 11 100 verb 3 500 verb. 3 100 verb 5 500 verb 5 100 verb 2 500 verb 2

Swelling IgH ₂ GVg gelatin)

3.45

2.12

1.85

3.12

2.01

1.72

3.91

2.80

2.35

3.65

2.21

1.81

4.61

2.89

not pourable

3.14

nichtvergießbar

not pourable

3.65

2.65

2.29

Quench (gH ₂ O / cm ³ gelatin)

4.18

nichtvergießbar

nichtvergießbar

nichtvergießbar

nichtvergießbar

nichtvergießbar

3.71

nichtvergießbar

2.24

1.74

3.75

2.40

2.40

1.81

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Table 5

mg Cr ³⁺ Z

5% gelatin solution

0.5 hours

Viscosities (cP) after 3 hours

6 hours

100 verb 1 100 verb 3 100 verb 3 500 verb 3 800 verb 3 100 verb 4 300 verb 4 500 verb 4 800 verb 4 100 verb 5 300 verb 5 500 verb 5 800 verb 5 100 verb 8 300 verb 8 500 verb 8 100 verb 10 300 verb 10 500 verb 10 100 verb 11 300 verb 11 500 verb 11

8.1 8.8 8.1 8.2 8.2 8.2 8.5 8.1 8.4 8.2 8.1 8.1 8.0 8.2 11.3

8.1 8.3 3.1 8.3 8.4 3.2 8.5 8.1 8.1 4.2 8.2 8.2 8.2 8.2 8.6

8.7

8.4 9.7

8,2 8,3 8,2 8,3 3,5 8,2 8,5 8,2 8,4 8,3 8,2 8,3 8,4 11,2

10.2

9.1 12.6

* Not measured due to excessive viscosity increases. Table 6

mg Cr ³ Vi 500 1 H. I 6 hours Il 3 hours. to 1 H. Ill 6 hours reaction 5% Gela 8.5 8.5 Viscosities (cP) 8.6 8.1 8.2 temperature tinelösung 8.5 8.6 8.4 6 hours 8.3 8.5 ( ⁰ C) 8.5 3 hours. 8.9 1 H. 8.6 8.6 8.2 3 hours. 8.4 300 verb 3 8.1 8.5 8.1 8.6 8.5 8.4 8.5 8.2 3.5 ) 500 verbs 3 8.4 8.6 8.5 8.4 8.4 8.8 8.4 8.5 8.5 70 800 verb 3 8.4 8.6 8.6 8.6 8.5 8.5 8.1 8.2 8.4 ) 300 verb 5 8.1 8.5 8.4 8.5 ) 500 verb 5 - 8.4 - 8.3 - 8.6 - 8.4 - 70 800 verb 5 - 8.4 - 8.3 - - 8.2 - ) 300 verb. 14 8.4 15.6 12.6 - 8.0 14.8 ) 500 verb. 14 8.1 - - - 20.4 - 8.5 - - 20 800 verb. 14 - - - - - 17.3 - - - ) 300 verb. 15 16.3 8.6 - 10.1 ) 500 verb. 15 - 19.9 - 8.5 - - - 21.3 - 20 300 verb. 15 3.4 - - - 15.3 8.3 - - ) 500 verb. 14 - - - _ - - 800 verb. 14 - - - - - - - - - 500 verb. 15 - 16.9 - 8.1 - - - 17.6 - ) 800 verb. 15 8.1 - - - 14.1 - 8.6 - - ) - 500 verb. 14 - - - - - - - - ) 800 verb. 14 - - - - ) 500 verb. 15 15.3 8.0 - 16.9 »40 800 verb. 15 - - - ) °

I 24 hours after sales

II 8 days after sales

III 20 days after sales

Storage temperature of the solutions 24 ⁰ - = viscosity increase too high

rel. Sensitive k. 5TgHZ gradation 5TgHZ veil 5TgHZ -6- 190 251 32 Table 7 fresh fresh fresh > 70 mgCr ³⁺ / 1kg > 70 emulsion 89 2.6 0.09 enamel > 70 100 89 2.8 2.7 0.04 0.05 Point > 70 100 89 2.9 2.6 0.04 0.05 ⁰ C > 70 Type 100 87 2.8 2.5 12:03 0.04 > 70 300 verb 3 93.5 89 2.7 2.6 0.03 0.06 > 70 500 verbs 3 100 89 2.8 2.7 0.04 0.06 300 verb 3 100 87.5 2.8 2.5 0.05 0.05 300 verb 5 87 87 2.6 2.5 0.04 0.07 500 verb 5 93.5 2.6 0.04 3CO verb. 5 300 verb. 11

5 Tg HZ = 5 days Table 8 Storage at 50 ° Cund20% relative humidity Viscosities (cP) after swelling fp mg Cr ³⁺ / kg emulsion 0.1 hours 3 hours * (g H ₂ CVCm ³ gel) ³ C ** A B C A B C

300 300 300 verb. 2 100 100 100 21.9 800 800 300 verb. 2 100 100 93.5 22.6 300 300 300 verb 3 100 100 100 23.4 500 500 500 verbs 3 100 100 93.5 22.8 300 300 300 verb. 4 100 93.5 93.5 22.9 500 500 500 verb 4 93.5 93.5 93.5 22.6 300 300 300 verb 5 100 100 93.5 21.4 500 500 500 verb 5 100 93.5 93.5 22.7 300 300 300 verb. 8 - - - 22.6 300 300 300 verb. 9 - - - 23.1 300 300 300 verb. 10 - - - 26.4 300 300 300 verb. 11 - - - 22.0 150 150 150 verb. 11 93.7 93.7 87.0 22.1 Tyo Type Type 100 100 100 22.4

22.2 22.7 23.8 23.0 23.0 22.9 22.1 22.9

2.65 2.12 2.50 1.90 2.60. 2.00 2.65 2.18

4,22 8,35

> 70> 70> 70> 70> 70> 70> 70> 70

> 70 32

* The solutions were cast after 4 hours of standing, so that no solution could be poured out of the solutions previously used

Toughen chrome compounds.

** Determination of the values after 5 days storage of the material at 50 ^° C. and 20% rel. Humidity A = lower casting B = middle casting C = upper casting

Table 9

Q (gH ₂ O / cm ³ treatment after a Fp ⁰ C I 34 Il Q (gH Treatment according to b mg C ³⁺ / 1 000 ml 5% I Gel.) 36 > 70 I ₂ O / cm ³ GeU Fp ( ⁰ C) Gelatinelösg. 7.12 Il 34 > 70 2.12 ! 300 verb 3 5.60 2.00 37 > 70 1.91 > 70 500 verbs 3 9.44 1.72 34 > 70 2.80 > 70 300 verb. 4 5.94 2.90 34 > 70 2.27 > 70 500 verb 4 8.12 2.12 > 70 > 70 2.70 > 70 300 verb 5 6.34 2.80 > 70 > 70 2.18 > 70 500 verb 5 2.30 2.20 > 70 2.78 > 70 300 verb. 11 2.41 2.65 2.50 > 70 500 verb. 11 2:36 > 70

Claims (1)

-I- 190 251 Claim: Process for the hardening of gelatin-containing layers I _n silver halide materials with chromium-III compounds, characterized in that reaction products of chromium-l chloride or -acetate and potassium or sodium acetate or acetic acid obtained in water or organic solvents at temperatures of 50 to 70 ^° C be used. The invention relates to a method for curing gelatin-containing layers in silver halide materials. For the quality of the photographic material, the physico-mechanical properties of the gelarine layers, such as swelling, melting point and mechanical strength, are of crucial importance. Therefore, almost all photographic materials are treated with gelatin hardeners, which cause crosslinking of the gelatin molecules. The crosslinking is ^ _n the functional groups of gelatin, such as amino, or carboxyl groups Guadino- caused. So far, especially curing agents of the organic class have been used. In the literature, almost all substance classes that show or are expected to have sufficient reactivity towards nucieophilic groups have been described. As well as ethylenes, ketors , silicones, esters, halides, amides, anhydrides, tpaxydides, aziridines, carbodiimides, phosphonitrile chlorides, cyanuric chloride derivatives, ethers, quaternary salts, Bisulfitanlagerungsprodukte (eg. as the aldehydes), methylol compounds, isocyanates, Härtungsmitt ^ i _m jt mixed function (z. B. Mucohalogensäureni and compounds having reactive double bonds (eg, triacrylformal) can be mentioned. Most of these compounds, in addition to the disadvantages listed below, especially their toxicity as a major disadvantage own. Their preparation and use is harmful to health, so that their use is often not allowed. As an example, the carbodiimides, certain acid derivatives, epoxides and triacrylic called. In addition, the organic curing agents show further significant disadvantages with regard to the deterioration of the sensitometric characteristics. Thus, aldehydes and methylol compounds cause an unacceptable fog increase in the emulsions. Cyanuric chloride derivatives undergo rapid hydrolysis and cause a decrease in gradation and sensitivity. Epoxies show defects on storage and cause poor adhesion. Triacrylformai, like most organic curing agents, exhibits too long a post-cure period. As a result, the hardening state of the materials changes over Mcnate, whereby the sensitometric parameters are also subject to fluctuation. The described disadvantages made the substance class of the inorganic gelatin hardeners again increasingly in the interest of the users. In addition to the aluminum salts, it is the chromium III salts that are used for curing. Chromium-ill compounds are widely used because, in addition to their relative non-toxicity, their low influence on the sensory properties, their rapid rate of cure ^uri <i give their favorable influence on the horizontal swelling behavior of this class favorable properties. Are Bisner from the literature Chrome iil compounds, _w he made famous as acetate, sulfate and the Aiaun to gelatin hardening. For special film materials, Werner-type chromium III compounds for curing are also proposed, as described in DT-PS 1129825. Based on the chromium content, these substances show approximately the same hardening effect. The crucial disadvantage of the compounds, however, is that sealant-containing solutions can only be added in small amounts, since the resulting increases in viscosities of the solutions render casting impossible. The most useful of these is nccn, the chromium acetate, but here, in the case of geiatine solutions in the photographically interesting КопгептгзтіопзЬегэісп between 4 and 6%, only amounts <.% Of chromium, based on the weight of the quelatins, can be used. Increasing the gelatin concentration or using emulsions with hydrophilic color couplers further reduces the usable amount of chromium. However, dosage of this magnitude is not sufficient to obtain satisfactory physico-mechanical properties. Therefore, previously had always used larger amounts of organic hardening in addition to the chromium compounds and thus the disadvantages already described in Kau * be taken _Besides the use of chromium complexes of the _acidic type, chloride ions are also added to the emulsion in large quantities, which can lead to disturbances of the sensitometric values. The purpose of the invention is to improve gelatin-containing materials, in particular photographic silver halide materials, in their physical-mechanical and photographic properties. The invention has for its object to find new chromium-III compounds, which become deaf use in Gelatir.siösungen ига emulsions in high quantity without Vi _s | _<os itätsanstiege occur and without affecting the sensitometrischeri values. In addition, these new chromium compounds also create the possibility of latent curing. Erfindungscemäß the object is achieved in that for hardening gelatmehaltiger layers in Süberhalogenidmateriaüen with chromium ill compounds in water or organic solvents at temperatures of 50 to 70'C ernaltene reaction products of chromium-lll-chloride or acetate and potassium or sodium acetate or Acetic acid can be used. Preferably chromium-Ui-cniond as the chromium-III compound and potassium and / or Nairiumacetat used as acetates. The object is further achieved in that the application of the chromium III hardening agents according to the invention either in iRswrr, ^ ¹ Wi Re & kbws-S &sv; -lд · .jiifaNlsvsw Лгоѵл? ¹ , p . \ R \ r \ ny the first steps are isolated, that the detr? Use triggers again. The curing agents according to the invention are particularly suitable for the curing of photographic gypsum-containing layers. It is also possible to use polymeric binders which, in admixture or as gelatin substitutes, bring about properties such as dimensional stability, flatness, plasticity, elasticity, viscosity, surface properties or specific influencing of the sensitometric data. Seiche polymers are synthetic or natural macromolecular substances, such as. Б. Homopolymers or copolymers of the known vinyl compounds, such as acrylic acid, methacrylic acid, styrene, acrylonitrile, acrylamide, butadiene, propylene, vinyl chloride. Vinylidene chloride, vinylpyrrolidone, maleic acid, acrylic ester. Methacrylic acid esters, etc. wherein the poiymerisi _he te mold is usually used as an emulsion or solution polymer. Polysaccharides, in particular dextran and its derivatives can be used as natural polymers.