DE2404189A1 - PHOTO-SENSITIVE SILVER HALOGENIDE EMULSION - Google Patents

Description

concerning lberhalogenidemulsion Photo sensitive Si

The invention relates to highly sensitive silver halide emulsions, in which a disproportionation of silver ions takes place in the latent image.

From J.Am.Cliem.Soc. Pp. 7189-7190 is a ligand-induced _. known

Disproportionation of silver ions Ag 'From this it follows that, in contrast to disproportionation in copper and gold, v / o a relatively high heat of hydration favors the disproportionation of the monovalent metal ions, the relatively low heat of hydration of Ag''does not promote such a reaction, that is, Ag ·· is extremely instabil.Bei application of a relatively large planar macrocyclic ligand, the reaction of Ag * _w ith the ligand relatively high yields of Ag * ^# L and Ag ^0, where L indicates the ligand and Ag ⁰ indicates a silver mirror deposition . The reaction can be carried out in water or methanol in which Ag * is soluble.

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The stability of the complex is possibly the result of the coordination of the Ag "ion by the tetranitrogen inacrocyclic Ligand in an approximately square and plane shape. The stability of the high oxidation state of silver is likely the sequence of the 4 donor nitrogen atoms »which firmly attach Ag * * are bound in a roughly square, even position.

In the case of the emulsion layers according to the invention, the above disproportionation reaction takes place made usable.

The improvement in sensitivity in the silver halide emulsions according to the invention is achieved by disproportionation of the silver ion in the vicinity of the latent image. This disproportionation is achieved by removing the latent image is brought into contact with a substance providing macrocyclic ligands prior to development. Preferably will this substance is already provided within the emulsion before exposure.

According to the invention, the photo-sensitive element receives one macrocyclic ligand showing disproportionation .. in Ag * induced. The presence of such a ligand with the exposed silver halide increases its sensitivity improved. In addition, the formation of fog is significantly reduced.

The ligand is either provided in the silver halide emulsion prior to exposure or on the exposed emulsion applied to the development. In other words, the ligand is reacted with the latent image before development. · ■>

The silver halide crystals consist of positively charged silver ions and negatively charged halogen ions. One from the crystal absorbed photon leads to an electron, which combines with the silver ion and a reduction to the neutral one Causes silver atom Ag. As this process progresses at

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Absorption of a certain amount of photons "forms a small one stable accumulation or a germ of silver (latent image germs). These latent image nuclei serve as catalytic centers for the reduction τοη silver ions to silver in the exposed crystals due to the photographic development. To this In this way the silver image is built up. The sensitivity of a photographic system depends on the number of incident Light quanta on a crystal for the formation of developable latent image nuclei. The fewer light quanta for production of metallic, .Süber is required, the greater is the sensitivity.

It can be assumed that when the silver halide emulsion is touched with the ligands within the meaning of the invention, the size of the latent image nuclei, obtained by exposure of the emulsion, increases, so the sensitivity increases. The monovalent silver ions in the immediate vicinity or on the crystal that are related to the formation of the latent image, are reacted with the ligand and then to metallic Disproportionate silver, which enlarges the latent image silver and leaves behind a divalent silver complex.

2Ag '+ L £ --— ^ Ag' * L + Ag ⁰

The presence of a maki-ocyclic ligand in the emulsion acts so quickly on the formation of metallic silver in the latent image after exposure, making it a substantial one Improvement in sensitivity is coming. The macroeyclic ligands according to the invention can therefore also be used as Sensitizers are called.

The ligand components used according to the invention are spatial seen long and flat and serve to stabilize the divalent silver ions. They have 4 electron donor atoms, preferably those that are able to exert the corresponding stabilizing effect on the silver.

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X,

-N:

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X are the the corresponding nitrogen, phosphorus and sulfur connecting atoms to complete the ring system. Ligands with 4 nitrogen atoms are preferred, in particular saturated and unsaturated macrocyclic amines in the form from ship's view bases.

A.

^H \ l

H ₂ CN

N CH,

N-CH ₂ H

XCH ₃ ) ₂

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/ -ITT ρ C

H ₉ C -N

H N CH,

N-CH ₂

H
CH-.

5% 5,7,12,12,14-hexamethyl-1,4 _} 8,11 -te-traazacyclotetradecane (teta)

^ c

C C

H ₂ CN

N CH,

H ₀ CN

CH

N CH,

(CH-.)

■ 3 ¹ 2

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(CH-)

.C N

CH,

^CH

H H,

(CH ₃ )

H ₂ C

H ₂ C

(CH.)

3'2

-N -N

N-N-

-CH,

-CH ₂ - (CH.)

3 ^y 2

5,5,7,12,14,14-hexamethy1-1,4,8,11-tetraazacyclotetradecane (tet la)

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The preparation of these ligand compounds is known (J.A.C.S. 2644 (1964).

The increase in the sensitivity of the systems according to the invention "is based on a larger amount of reduced silver based on light quantum compared to the usual emulsions.

In additive color photography, the photosensitive silver halide layer is exposed via an optical one Grid or a grid plate, which are selectively permeable to predetermined parts of the incident on the grid or grid plate electromagnetic radiation spectrum. During the development of the exposed silver halide layer, the Deposition of the silver as a puncture of the extent of the exposure behind special segments of the filter elements for the moduli Determination of the amount of light that go through given grid elements while projecting the image thus recorded.

Pur additive color screens can be photosensitive material and Color raster separate and certain elements in a corresponding arrangement on top of each other during exposure and viewing or projection of the image. After the image-wise exposure of the photographic material, the grid is removed for development and building up the silver image and then repositioned for viewing of the final image, but preferred a permanent arrangement of the additive color grid in connection with the photographic material. In such a case it is of course, the grid by z. B. to isolate barrier parts or intermediate layers to prevent it from degradation or To protect the action of the developer composition during the development of the latent image.

In general, such film units comprise a panchromatically sensitized silver halide layer and a multicolor additive screen. A wide variety of photosensitive layers can be used, depending on the prospect development, i.e. whether a negative or a positive is to be produced directly for the reversal technique or a

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Positive with the help of the usual direct working emulsions. The invention can also be used for silver salt diffusion transfer processes or to build up your own positive image in its own layer, which then with the same Grid, as it was applied for the exposure, is brought into congruence.

A preferred film unit includes an image receiving component between photosensitive silver halide and additive multicolor raster. In this case, the emulsion is exposed via the Easter and the image receiving component. The development happens in such a way that a positive silver image in the image receiving component is built in the immediate vicinity of the additive multicolor raster. This film unit is an example of an arrangement where the problems of the exact superposition of the two layers is avoided, since the The exposure grid is also automatically in the correct position for the positive silver image to be viewed. At this Film unit, the halide layer can be removed or else with the remaining parts of the film unit and the positive Silver picture remain connected (US-PSS 2.-861 885; 2 726 154;

2,944,894; 3,536,488; 3,615,427; 3,615,428; 3 615 429 and

3 615 426).

The usefulness of such film units in which the emulsion layer an integral part of the film unit remaining after the positive image is built up is achieved through application an image receiving material in which effective silver precipitation takes place so that the image silver formed is superior Shows opacity to negative silver developed in the silver halide emulsion layer. Edwin H. Land, "One Step Photography "Photographic Journal, Part A, pp. 7 to 15, January 1950.

The above integral film units are particularly suitable as single films for projection (U.S. Patent 3,615,427).

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A wide variety of diffusion transfer systems for producing color images are known. The structure of the color image is based on a different mobility or solubility of the dye image-forming substances depending on the development, so that there is an imagewise distribution of such material which is more diffusible and which is preferred is transferred at least in part by diffusion onto an image material that can be colored over it. The different mobility The ability to dissolve is obtained e.g. through a chemical reaction such as a redox reaction or a coupling reaction.

The dye image forming agents employed in such film units can be characterized as either

1. Initially soluble or diffusible or

2. Initially insoluble or undiffusible in the developer composition, however, they are selectively made undiffusible or diffusible in an image-wise manner Distribution as a puncture of development.

These substances can be complete dyes, dye intermediates or the like, in particular color couplers (US Pat. No. 2,647,049; 2,661,293; 2,698,244;

2,698,798; 2 802 735; 2,774,668 and 2,983,606; 3,443,939;

3,443,940; 3,227,550; 3,227,551; 3,227,552; 3,227,554; 3,243,294; 3 445 228.

In all of these systems, multicolor images are obtained using a film unit made up of at least 2 selectively sensitized silver halide layers, each associated with a corresponding dye image-forming material Spectral properties. Most frequently used are the so-called "tripacks" with blue-green and red-sensitized Silver halide emulsion layers associated with a yellow, purple and cyan dye. Particularly suitable are as dye-building substances in the diffusion transfer process Developer dyes (U.S. Patent 2,983,606).

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In such color diffusion transfer processes, the color images are obtained by exposing a light-sensitive or negative element composed of at least one light-sensitive layer such as gelatin-silver halide emulsion layer a dye image forming material in the same or an adjacent layer. The latent that is formed in it Image is developed with a developing or treatment composition, so that an image-wise distribution of a soluble and diffusible imaging material. This is then at least partially due to diffusion on a Transferred image-receiving or positive element arranged above, by the dye transfer image in the dyeable Layer is built up. The negative and positive elements can be separated and brought together during development, they then remain together or are separated according to the structure of the image. However, it can also be a Act as a film unit, e.g. an integral negative-positive film unit, in which the negative and positive elements are laminated together or in another way at least before the image is built up be held together.

The emulsion layers according to the invention are suitable for all systems which have a colorable image layer in a separate Element or in a film unit. The layer according to the invention is of particular interest for the integral ITegative-positive film units for the production of color transfer images, which can be viewed without separating the elements (US-PSS 3,415,644; 3,415,645; 3,415,646; 3,473,925; 5,573,043; 3,576,625; 3,573,042; ' 3,594,164; 3,594 165.

The special way in which silver halide emulsions are made according to the invention is not critical. So you can wet the emulsions, or develop them for a diffusion transfer process draw in. Direct positive emulsions are also possible. The usual spectral or chemical sensitizers can be used. Optical additives such as coating aids, hardeners,

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thickening agents, stabilizers, preservatives and the like may be included.

The photosensitive material preferably contains crystals of a silver compound, e.g. B. of one or more silver halides, like the chloride, iodide or bromide or of mixed silver halides with different ratios from silver to halide.

The invention is further illustrated by the following examples: Example 1

A film unit was made by resting on a polyester support 0.55 g / m 2 of a purple dye from Poriael

^ v

N-SO ₂ -

—CH ₂ —CH ₂

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applies in about 1.6 g / m of gelatin. This is followed by a blue-sensitized silver iodobromide emulsion layer containing 4 mg Ag / g of compound B at an application weight of O »92 g / m Ag and the same amount of gelatin. A gelatin layer of about 0.325 g / m ^{2 with a content of 85 g / m 2 of} 4-methylphenyl hydroquinone was applied to this emulsion layer.

The negative component obtained in this way was placed over a gray wedge exposed for selectively filtered radiation, then with the developer compound given below with the positive element in place developed in the dark for 10 minutes. The positive element consisted of the following 3 layers. one 0.1 mm thick polyethylene terephthalate carrier

1. Partial butyl ester of polyethylene / maleic anhydride copolymer, produced by refluxing 300 g of highly viscous poly (ethylene / maleic anhydride), 140 g of butanol and 1 cnr 85% phosphoric acid in 14 hours, so that one Layer of a polymeric acid with a thickness of about 19 / µm received.

2. A 10 ^ ige aqueous emulsion of a diacetone acrylamide / acrylamide copolymer, grafted onto a polyvinyl alcohol scaffold, was used as a spacer layer in a thickness of about 7.6 / µm applied.

3 · Image layer in the form of a 2: 1 mixture of polyvinyl alcohol and poly-4-vinylpyridine in an application rate of 6.5 g / m 2 or an approximately 10 μm thick image layer.

• z.

The treatment liquid contained 7 * 5 g of KOH, 4.7 g of CsOH, 50 g of TiO ₂ , 3.5 g of sodium _{carboxymethyl cellulose per 100 cubic meters of water;} 1 g benzotriazole, 0.1 g 5-bromo-6-methyl-4-azabenzimidazole, 0.35 g 2-methylimidazole and 1.75 g N-phenethyl-d, -picolinium bromide.

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Filiiiemensitlichkeit according to the invention to otherwise identical pilmin material with the exception of the macrocyclic Ligand showed an improvement in sensitivity of about 1 level / a.

The emulsions according to the invention are suitable for both Color photography as well as black and white photography. This is especially true for black and white silver transfer processes.

Diffusion transfer techniques are well known. Included is exposed silver halide and silver-precipitating nuclei of an aqueous alkaline liquid containing at least a developer and a solvent for the silver halide. The soluble silver complex formed becomes the silver-precipitating germs are transported and used to build up the visible silver image.

Example 2

A film unit was made by placing on a polyester support 0.53 g / m 2 of a yellow developer dye of the formula

NO,

C ₃ H ₇ O

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about O, β g / m '~ gelatin was applied. This was followed by a blue-sensitized silver iodobromide emulsion containing 4 mg Ag / g compound B with an application weight of 0.92 g / m Ag and the same amount of gelatin. This was followed by a gelatin layer of about 0.325 g / m ² containing 80 mg / m ^{2 of} 4'-methylphenylhydroquinone. This negative was developed in the sense of Example 1 with the image receiving element and applied as a treatment ^{solution to 100 cm 5 of} water, 10.6 g of KOH, 0.45 g of IiOH.H ₂ O, 95.8 g of TiO ₂ , 1.84 g of sodium carboxymethyl cellulose, 1.27 g benzotriazole, 0.064 g 5-bromo-6-methyl-4-azabenzimidazole, 1.65 g N-phenethylsL-picolinium bromide, 0.67 g 6-methyluracil, 0.22 g LiN03, 1> 9 g Hydroxymethyldiamine tetraacetic acid, 0.05 bis-hydroxyethylaminosulfide, 1.23 g Carbowax, 1.67 g silica, 2.86 g U-benzyl-cL-picoliniuinbroinid and 0.62 g 6-benzylaminopurine were used. The developer solution still contained 2.4 g

COOH

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Example 3

A film unit was made by placing on a polyester support 0.53 g / m of cyan dye developer

CH

was applied in about 0.8 g / m gelatin. This was followed by a blue-sensitized silver iodobromide emulsion layer containing 4 mg - ^ g / g of compound B in an application amount of 1.6 g / m 2 Ag and approximately the same amount of gelatin. This was then followed by a

ink layer in an amount of about 32.5yum / m. The development took place in the sense of Example 1 with an image receiving layer there. The developer solution contained 10.5 g of KOH per 100 cm ^ of water, 0.45 g of _{LiOH.H 2 O, 95.8 g of TiO 2} , 2.31 g of sodium carboxymethyl cellulose, 1.27 g of benzotriazole, and 5-bromo-6-methyl -4-azabenzimidazole 0.064 g, IT-phenethyl- ^ j -picolinium bromide 1.65 g, 6-methyluracil 0.67 g, lithium nitrate 0.22 g, hydroxyethyldiamine acetic acid 1.9 g, bis-hydroxyethylaminosulfide 0.05 g, Carbowax 1 , 23 g, silica 1.67 g, N-benzyl ck / picolinium bromide 2.86, 6-benzylaminopurine 0.62 g

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1.37 g

H COOH

OH

-COOH

COOH

6 _f 18 g

0

OH

-12-

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Example 4

0.53 g / m 2 of hydroquinone in the same amount of G-elatin was applied to a polyester film support, and a blue-sensitized silver iodobromide emulsion containing 4 mg of Ag / g of compound B in an amount of about 1.6 g / m of Ag in the same amount of G-elatin was applied thereon. ^{This was followed by a gelatin soft top at 32.5 mg / m 2} and followed by a layer of succinic anhydride at about 0.125 g / m 2. It was exposed via a gray wedge and treated for 6 minutes under a polyester distribution film in the dark with the following developer composition: 7.5 g of KOH, 4.7 g of CsOH, 50 g of TiO ₃ , 3.5 g of carboxymethyl cellulose, 1 g on 100 cm ^ of water Benzotriazole, 0.1 g of 5-bromo- (3-methyl-4-azabenzimidazole, 0.35 g of 2-methylimidazole and 1.75 g of N-phenethyl- O ^ -picolinium bromide. Development was then stopped by washing the negative with Acetic acid. If these images obtained according to the invention are compared with those from comparison film units, it is found that the film speed was about 1 step better.

Example 5

The measures of Example 1 were repeated, only in this case no ligand-containing emulsion was used. The exposed In this case, the emulsion was treated with a methanolic solution of the ligand-donating substance before exposure. The sensitivity increase was about 1 level. The minimum Identity was lower than in the comparison image.

Claims

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Claims (1)

IJH. ING. 1 \ WlJKSTlIOFK DH. IC. v.I'ECHMAS.V VH. IN". I). «KIIHHXS I) IPI ,. TNG. H. f Ji) IiTZ I'ATEKIANWAl.TE / 9 240418S 8 MU X CII EN »O SCH VV .EH) KIISTHASSi: a τκι, κρο» (osii) Gcaoni TElKI 5 24 TKl. KCIHAMMK: ΡηϋΤΕΟΤΓΑΤΚΝΤ MtiNCIIKN "1A-43 claims 1. Containing light-sensitive silver halide emulsion a macrocyclic ligand with 4 electron donor atoms. A silver halide emulsion according to Claim 1, characterized in that it is e indicates that the ligand is a compound of the formula -Ps ep -X- X or X ^S ~ N: Vx / S: X \ is where X is those necessary to complete the ring system Represent atoms. 3 · silver halide emulsion according to claim 2, characterized in that the ligand is a tetramine. 4. Use of the silver halide emulsion according to claim 1 to 3 for the silver diffusion transfer process. 8143 409831/1015