JPS58156931A - Negative type silver pigment bleaching photographic material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a new silver dye bleached photographic material of negative type.

It is known that silver dye-bleachable photographic materials contain image dyes which are bleached in accordance with the image by strongly acidic solutions containing silver complexing agents in the presence of silver. This reductive bleaching can be accelerated by engineering bleach catalysts.

The reducing action of silver on image dyes can be utilized to convert photographically produced silver images into dye images. By the way, silver images made by subjecting photographic materials to non-lighting are usually negative. That is, it is the opposite of the original. Dye bleaching, which follows development, yields a positive dye image from the negative silver image, ie, a color image corresponding to the original. Photographic materials that behave in this way are called positive-type silver dye bleached photographic materials.

Therefore, such a positive type silver dye bleached photographic material is
(Positive) Color slide to positive dye image (Color/
It is mainly used for making prints. Color·
If a color negative were used instead of a slide, a corresponding negative dye image would be obtained.

In order to be able to obtain a positive color image even from a color negative using a silver dye bleaching method photographic material, it is necessary to use a negative type photographic material in which a positive silver image is produced by development after exposure. is necessary. In this case, the positive silver image formed is then processed to
The result is a positive color image, which is the opposite of a color negative. Therefore, when using this negative type silver dye bleached photographic material, a negative dye image is given when a positive color slide is used as the original.

Suitable methods for forming positive silver images are known, for example, those based on silver complex diffusion, or those based on bromide ion diffusion. The former method is described, for example, in German Patent Publication No. 1572206 or British Patent Publication No. 6.
56131, the latter method being disclosed, for example, in German Patent Publication No. 859711. If the silver complex diffusion method is selected, a developer solution containing a silver complexing agent is used for developing the negative silver image. Undeveloped non-light 7. The tough part. Current f□j
A silver complex is formed which diffuses into the receiving layer containing development nuclei in accordance with the image. Then, by physical development at the development nucleus, silver is precipitated from the developer solution containing the silver complex, and a positive image is produced. In the case of the bromide ion diffusion method, one photographic material must contain development nuclei, a large amount of a silver chloride emulsion with low photosensitivity, and a small amount of a highly sensitive silver bromide emulsion in the same layer. . After exposure, bromide ions are liberated corresponding to the image during silver bromide development,
This on the other hand suppresses the development of silver chloride. At this time, therefore, at the same time one pale negative image arises from the silver bromide emulsion and one dark, and therefore in the final result predominately positive, image from the chloride emulsion.

These methods of obtaining silver reversal images with silver dye-bleaching materials are already known from US Pat. No. 2,673,800.

The material disclosed therein contains development nuclei within the dye-containing layer. The unexposed non-reducing salts of the photosensitive silver halide emulsion layered above that layer diffuse into the layer containing the development nuclei as silver complexes and form a positive silver image therein. This positive silver image is converted to a negative dye image during dye bleaching. However, in this method, it is difficult to control the reactions that occur during development. That is, the development of the exposed areas, the dissolution of the non-original silver halide crystals, the diffusion of the resulting silver complex into the underlying layer and the physical development of the diffusive complex within the dye layer, with good whiteness and sufficient maximum It is difficult to control so that a color image with density is produced. According to DE 2053751-2053751, the bromide ion diffusion method is used to create the positive silver image required for dye bleaching. That is, according to this, an intermediate layer containing particulate silver chloride is arranged to separate the respective layers assigned to each color from each other.

By trapping bromide ions that diffuse in undesired directions, incorrect color combinations in a multicolor photographic material can be avoided. However, this method #i
The use of bromide or other additives commonly used as antifoggants, such as benztriazole, in developer solutions is prohibited. In practice, it is extremely difficult to satisfy this condition.

Furthermore, the company, which obtains positive silver images with silver dye-bleached photographic materials,
For example, it is disclosed in European Patent Publication No. 44812.

In this method, a masked core-shell emulsion (core-5hell-
emulsion) is used. Development is carried out chemically.

That is, the developer solution does not contain a silver complexing agent. The composition of this developer is therefore distinct from developer solutions such as those used for self-masking, positive-type silver dye-bleached photographic materials. The latter differs from the former in that it contains, for example, a silver complex forming agent. This is one major drawback, contrary to the desire to make positive-type silver dye-bleached photographic materials and negative-type silver dye-bleached photographic materials as similar as possible in terms of processing.

It is therefore an object of the present invention to provide a negative-type silver dye-bleached photographic material which can be processed in a developer solution containing a silver complexing agent.

According to the invention, this objective is achieved by using a photographic material that makes use of iodide ion diffusion while allowing development in a solution containing a silver complexing agent and that yields a high-quality image inverse to the original. This is achieved by

That is, the present invention provides on a support at least one layer comprising: (a) a bleachable image dye, a low-speed silver halide emulsion, and colloidal nuclei that aid in silver precipitation; and (b) a high-speed iodide. A negative-type silver dye-bleached photographic material is provided containing at least one layer containing a silver halide emulsion and gold containing.

The use of the material according to the invention for the production of photographic images is also a subject of the invention.

+I! Also included within the subject of the invention are methods for making images, images made with the material according to the invention, as well as compositions for the development of this material.

A suitable support for the photographic material according to the invention can be, for example, transparent or pigmented cellulose triacetate or polyester. If paper felt is used as support material, it may be coated on both sides with a layer of varnish or polyethylene.

The image dye must be bleachable under the conditions of conventional processing baths for silver dye whitening techniques. Suitable dyes are described, for example, in U.S. Pat. No. 3,454,402, Ken 3443.
No. 953, No. 3804630, No. 3331142,
No. 4051123.

For the photographic materials according to the invention, conventional photographic silver halide emulsions can be used.

Suitable silver halides include silver chloride, iron bromide, silver iodide and mixtures of these halides. The proportions between the different halides in the mixture can vary within wide limits.

Low speed silver halide emulsions should be essentially free or contain less than 1 mole percent iodide, preferably 0.9 mole percent or less.

Higher contents of iodide are generally not suitable. This is because, at higher contents, the control of development necessary for the process according to the invention may be impaired by the migrating iodide ions. Therefore, suitable silver halides for low-speed halogen 1G silver emulsions are silver chloride,
Silver bromide or silver chlorobromide. The sensitive silver halide emulsions used according to the invention contain, in addition to silver chloride and/or silver bromide, more than 1 mole percent of silver iodide. Preferably 1 to 10 mole percent silver iodide is used.

Gelatin is preferably used as a protective colloid for silver halide. However, other water-soluble protective colloids such as polyvinyl alcohol or polyvinylpyrrolidone are also suitable. Furthermore, a portion of gelatin may be replaced by a dispersion of a water-insoluble polymer compound. For example, dispersion polymers obtained from α,β-unsaturated compounds such as acrylic esters, vinyl esters, vinyl ethers, vinyl chloride, vinylidene chloride and other mixtures and copolymers can be used.

The nuclei present in the low-speed silver halide emulsion layer and serving for the precipitation of metallic silver are colloidal hydrosils or sulfides of heavy or noble metals. For example, silver sulphide, nickel sulphide or gold, silver and palladium hydrosils come into consideration. The amount of the core incorporated into the layer is, for example, 0, 1 to 10
The amount is extremely small, on the order of 0 da/m' film material.

A development retardant may be included in the low-speed layer for kinetic control of development. In principle, all known development retarders can be used as long as they satisfy the conditions. Preferred, however, are compounds that can be stored in the form of a diffuse resistor within the photographic layer. Such compounds are primarily essentially water-insoluble or slightly water-soluble compounds containing ballast groups.

By way of example, the 1-position is by a 7-aryl group, preferably by a polynuclear aryl such as naphthyl or diphenyl, and optionally preferably by a long-chain alkyl group (C1s-e
5-mercaptotetrable which is substituted by an aryl group, in particular a phenyl group, and also by an aralkyl or preferably by an alkyl having at least 3, especially 3 to 18 carbon atoms.

Particularly suitable development retarders are 5-mercaptotetrables substituted in the l-position by one of the following groups: n-propyl, l-propyl, n-butyl, i-butyl, t- Butyl, i-7 mil, i-octyl, t-octyl, nonyl, decyl, lauryl, myristyl, palmityl, stearyl, di-t-butylphenyl, octylphenyl, dodecylphenyl, naphthyl, α- or β-
Naphthyl or diphenyl.

Diffuse non-monomeric mercaptotetracils without true ballast groups can also be used.

However, care must be taken in this case to ensure that the development retardant does not diffuse into adjacent layers in undesired directions and retards the development of the emulsion, which supplies, for example, iodide ions. This is achieved, for example, by interposing an intermediate layer. Given this condition, it is also possible to use 5-mercaptotetrables substituted in the 1-position by, for example, groups such as: phenyl, hydroxyl, halogen (chlorine, bromine) or lower alkyl (C2-C3 ) directly converted phenyl,
Benzoic acid-methyl ester or monoethyl ester, methyl or ethyl. , but generally the use of diffusion-resistant development retarders is advantageous. This is because it substantially simplifies the layer construction, especially for photographic materials having multiple dye and silver halide emulsion layers. The development retarder is 0.2 per mole of silver in the emulsion.
It can be used in amounts of from 1039 mol to 1039 mol, preferably from 0.5 to 2 mmol.

The low speed layer is preferably placed directly adjacent to the high speed layer. These two layers constitute a layer pair. in this case,
Usually, the high-sensitivity layer is placed above the low-sensitivity layer when viewed from the direction of incident light. This arrangement gives the photographic material a high sensitivity. This makes it possible, for example, to create highly light-sensitive black-and-white negative materials by placing a bleachable black dye in the slow-speed layer. In this case 1, the silver used as silver halide can be virtually completely recovered from the processing solution. Two more layers? They can also be separated from each other by an intermediate layer. In this case,
Preferably, a bleach inhibitor is included in the intermediate layer in the form of a diffusion resistor. Bleach inhibitors of this type are described, for example, in DE 15 47 725.

The color sensitivity of the image dye and iodide-containing silver halide emulsion of a set of layer pairs is typically adjusted as follows. That is, the emulsion is adjusted to reach its maximum sensitivity exactly in the region of the spectrum where the corresponding image dye has its absorption maximum. For example, a yellow dye is associated with a blue-sensitive emulsion.

The photographic material according to the invention may contain multiple pairs of such layers. Preferably, a material with three layer pairs is used. In this case, the first set of layer pairs on the support contain a cyan dye;
A second set of layer pairs contains a magenta dye and a third set of layer pairs contains a yellow dye. This results in the photographic material covering the entire visible spectral range. By selecting different combinations of the sensitivity maxima of the silver halide emulsions (of high speed) and the absorption maxima of the image dyes, so-called false color negative materials can be obtained for special effects.

Barrier layers can also be arranged between each pair of layers. The barrier layer contains a diffusion-resistant material that absorbs iodide ions and prevents undesirable interactions between the layer pair.

Furthermore, the photographic material according to the invention has an additional intermediate layer containing, besides gelatin, further additives such as bleach inhibitors, light stabilizers, fluorescent brighteners, filter dyes or plasticizers. I can do it.

The exposed and developed silver dye-bleached photographic material can be processed according to conventional methods, including the steps of silver development, dye bleaching, silver bleaching, fixing, and washing. Washing with water is performed not only after putting on the feet, but also between steps in some cases. It is possible to combine color pigmentation whitening, silver coloring whitening, and possibly fixation into a single processing step.

Processing baths of conventional composition can be used for silver development. For example, baths which additionally contain hydroquinone or even 1-phenyl-3-pyrazolidone as developing substance can be used for silver development.

The developer solution must also contain the necessary silver complexing agent to induce spontaneous development in the slow layer. Suitable ones include, for example, the sodium salt of thiosulfate,
Alkali metal salts such as potassium salts or ammonium salts of thiosulfuric acid, and also salts of thiocyanic acid. However, sodium thiosulfate is preferred. For example, 1t
The developer bath contains 0.3 to 60 mmol of sodium thiosulfate. However, the optimum lid can vary within a -9 range depending on the properties of the material, the temperature of the developer bath, the desired working time, etc. It is also possible to contain a developer-containing metal material or a developer-like substance in the emulsion layer. In this case, appropriate buffering is necessary so that these substances remain active during storage in a dry layer.

In such cases, all that is needed to initiate development is a high pH activation bath, which does not need to contain any developer compounds.

When dye bleaching is carried out as a separate processing step,
As the dye bleaching bath, it is preferable to use a bath containing, in addition to a strong acid, a water-soluble iodide, an antioxidant for the iodide, and a dye bleaching contact wire. In addition to the Ift component described above, the combined dye bleaching and silver bleaching bath also in principle also contains a water-soluble oxidizing agent t. Suitable dye bleaching catalysts are, in particular, diazine compounds, such as pyrazines, quinoxalines or phenazines, such as those disclosed in the examples of German Patent Publication No. 2010280.

The strong acids used in the above-mentioned baths are to be understood as those acids which give the dye bleaching bath or the dye bleaching-silver source white combination bath a pH value of at most 2. Thus, for example, hydrochloric acid, phosphoric acid and especially sulfuric acid, p-toluenesulfonic acid or sulfamic acid can be used.

As water-soluble iodides, use may be made of alkali metal iodides such as, for example, potassium iodide or sodium iodide; suitable oxidizing agents include nitroso compounds such as p-nitrosodimethylaniline, nitrides such as aromatic Nitro compounds and preferably aromatic mono- or di-nitrobenzenesulfonic acids such as m-nitrobenzenesulfonic acid.

As antioxidants used are reduktones or water-soluble mercapto compounds as well as water-soluble tertiary phosphines. The latter are also effective as bleach catalysts, as described in German Patent Publication No. 2,651,969. Suitable reductones include reductinic acid 3-carbonyl-ene-1
, acy-reductone having a 2-diol group, triose-reductone or preferably ascorbic acid.

As a mercapto compound, a compound represented by 2, 2H8A (B)m is used. where A is an aliphatic, cycloaliphatic, araliphatic, aromatic or heterotactic bridging member, B is a water-solubilizing group, and m is an integer of at most 4 (German Patent Publication No. No. 2258076 and No. 24
23819).

The thiolactones disclosed in German Patent Publication No. 3,045,059 are also suitable antioxidants.

The fixing bath can be prepared according to known and commonly used methods. Suitable fixing agents are, for example, sodium thiosulfate or preferably ammonium thiosulfate, and optionally additives such as sodium bisulfite, sodium metabisulfite or ammonium bisulfite, and optionally ethylenediamine tetra. A chelating agent such as acetic acid is added and used.

All processing baths may contain other conventional additives such as hardeners, wetting agents, phosphor brighteners or UV stabilizers.

Exposure of the photographic material according to the invention produces a latent image only in its sensitive iodide-containing silver halide emulsion layer. This latent image is converted into a negative silver image through a subsequent development process.

In the first layer, which contains an iodide-free, low-speed silver halide emulsion and development nuclei, the cooperative action of the silver halide complex-forming agent under the reducing conditions prevailing in the developer solution is Spontaneous physical development is induced at the development nucleus. However, at the same time, when the silver iodide-containing emulsion is developed into a negative silver image in the upper second layer, iodide ions are released corresponding to the image, and these released iodide ions are It diffuses into the first layer and inhibits silver precipitation onto development nuclei within this layer. Controlled by the diffusing iodide ions, a positive silver image is produced within the dye-containing layer. That is, in the non-exposed areas where iodide ions were not liberated in the second layer, the first layer
Physical development proceeds to complete blackness within the layer, whereas physical development is inhibited by liberated iodide ions at the most intensely exposed locations, resulting in a positive silver image. In order to delay physical development in the nucleated layer until sufficient iodide ions have diffused from the adjacent layer, the silver chloride and silver bromide crystal sizes of the slow emulsion in the first layer and 3 All you have to do is change the percentage. Furthermore, the development rate can be controlled by the addition of retarding additives such as phenylmercaptote trouble. By using this method, excellent whiteness can be achieved during color accumulation,
Pigments with the desired contrast and high maximum degree +! I
It is possible to make the development rate of the two layers t'=* such that a positive silver image is produced giving the Ii image.

In the next processing step, the silver image is converted into a reverse dye image in the dye-containing layer by known methods. Both the negative silver image in the silver iodide-containing second layer and the positive silver image in the dye-containing first layer disappear during this process, leaving only the dye image produced by dye bleaching.

Examples of the present invention are shown below. Example 1 The following layers were sequentially coated on a white opaque polyethylene coated paper support.

(1) Gelatin layer (coating amount: 2117 m1): This layer contains a magenta dye of the following formula 200 WIg/, colloidal silver (10 m!/lI?), and a low-sensitivity monodisperse silver bromide emulsion (2
5CIF silver/W? : crystal edge length 0.2 μm), and phenylmercaptotetracil as a development retardant (
0.2#/m").

(2) Iodosilver bromide gelatin emulsion green-sensitized with symmetrical oxacarbocyanine (95 mole percent silver bromide, 5 mole percent silver iodide; 0.21/silver/W?)
. and (3) gelatin protective layer (1,5 g/m').

This material is exposed to green light passed through a stepped optical wedge,
Then, the following treatment was performed at a temperature of 30°C.

1. Silver developing bath 1 minute 30 seconds Ethylenediaminetetraacetic acid tetrasodium salt 29/ Potassium carbonate 30 l Potassium metabisulfite 10 1 Anhydrous sodium sulfite 30 #l-Phenyl-3-pyrazolidone 0.41 Hydroquinone 61 Benztriazole o, 6g 1t Odor Potassium chloride 2, Ol anhydrous sodium thiosulfate 1 〃2, Washing with water 30 seconds 3, Bleach bath 2 minutes Sulfuric acid 409I
1m-Nitrobenzenesulfonic acid sodium salt 8I Bis-(β-cyanoethyl)-sulfoethylphosphine sodium salt 31 Potassium iodide
612.3.6-1'
Limethylquinoxaline 1.3 #4, washed with water
30 seconds 5° fixing bath 2 minutes ammonium thiosulfate 200g/
l Potassium metabisulfite 25
〃Potassium hydroxide (85%) 10
6. Washing with water for 2 minutes The obtained Mazienta image was a color image opposite to that of the Orisina JL stepwise optical wedge.

Example 2 The following layers were coated on a white opaque polyethylene coated paper support.

(1) Dye layer This contains m”a and the following components: Gelatin I
N, a dye of the following formula (1): 0.311% silver in the form of a low-sensitivity silver bromide emulsion with a crystal edge length of about 0.2 μm, and 0.2 to 0.2% red colloidal gold.

(2) Gelatin layer This consists of - per gelatin II and finely dispersed 2,5-bis-(5-n-hexyloxycarbonyl-2-methylbent-2-yl)-1, as a bleach inhibitor. Contains 0.59 of 4-benzoquinone.

(3) High-sensitivity bromosilver iodide layer containing 2,5 I gelatin, 0.5 g silver and 5 moles iodide per layer.

(4) Gelatin protective layer This contains per d gelatin II and 1-amino-3-hydroxy-5-methylmorpholinium-triazine-tetrafluoride boron salt 8511I9 as a hardening agent.

The above material was exposed and processed as in Example 1 in a photosensitive needle. The resulting image is the opposite of the original step optical wedge, i.e. a negative black dye image, with a maximum density of 2, 0%, a minimum density of 0.15, and a contrast of 1.5 (highest density). (measured between 20 and 804).

Example 3 Coat the following layers onto a transparent polyester support.

(1) Dye layer This is made of silver in the form of a low-sensitivity stereo-monodisperse silver bromide emulsion with 2.5 ji of gelatin per gelatin and the following formula (ship yellow dye 0.139 crystal edge length 0.2 Am). 2001v and red colloidal gold 0.14M9.

(2) Gelatin interlayer, which contains 1,9 gelatin and finely dispersed 2,5-bis-(5-n-hexyloxycarbonyl-2-methylbent-2-) as a whitening inhibitor. )-1,4-
Contains 0.51% of benzoquinone.

(3) Bromosilver iodide layer containing 15 moles of iodide per zl of gelatin, 0.25.9 g of silver (iodide content 1 as 5 moles of silver halide) and bleach inhibitors as described above. Contains lI.

(4) Gelatin protective layer according to Example 2 The above materials,
It was exposed and processed in the same manner as in Example 1 in a photosensitive needle. This resulted in a negative yellow dye image. O1 at its highest concentration
8. The lowest density was 0.1 and the contrast was 0.5 (measured between the highest density of 20 and 804).

Example 4 The following layers were coated onto a transparent polyester support.

(1) Dye layer This is gelatin 1.8, 9. 0.135 g of blue-green pigment of the following formula V), 0.3 g of silver as a low-sensitivity sterically monodisperse silver bromide emulsion with a crystal edge length of 0.2 μm, and colloidal silver sulfide 11169
Contains.

(phantom bromosilver iodide layer) This corresponds to layer (3) of Example 3, in which iodide ions are uniformly dispersed in the form of crystals.

(3 gelatin protective layer This corresponds to layer (4) of Example 20.

The above material was exposed and processed in the same manner as in Example 1 in a photosensitive needle. This results in a maximum density of 0.5 and a minimum density of 0.0.
2. A negative yellow dye image with a contrast of 0.5 was obtained.

Example 5 In the material according to Example 4, a bromosilver iodide emulsion containing iodide ions in the crystals was used. This resulted in a contrast of 2.0.

Claims (1)

[Claims] 1. On a support: (a) at least one layer comprising a bleachable image dye, a low-speed silver halide emulsion and a colloidal nucleus on which precipitation of silver occurs; and (b) 1. A negative-type silver dye-bleached photographic material characterized in that it has at least one layer comprising a highly sensitive iodide-containing silver halide emulsion. 2. The photographic material according to claim 1, wherein the low-sensitivity silver halide emulsion is a silver chloride emulsion, a silver bromide emulsion, or a silver chlorobromide emulsion. 3. The colloidal core is a heavy metal or a sulfide of a heavy metal.
Photographic material according to claim 1, characterized in that it is a cIri colloidal hydrosil. 4. The photographic emulsion according to claim 1, wherein the silver halide emulsion is a silver halide gelatin emulsion. 5. The low-sensitivity layer (a) and the high-sensitivity layer (a) form a pair of layers, and the layer (b) is placed on & (a) when viewed from the direction of incident light. The reaggregated material according to claim 1, characterized in that: 6. The photographic material according to claim 5, wherein the layer (a) contains a development retardant. 7. Photographic material according to claim 5, characterized in that layer (a) contains a bleachable black image dye. 8. Claim 1, characterized in that it contains a plurality of layer pairs consisting of the layers (a) and (b), and a barrier layer is interposed between each layer pair. photographic materials. 9. A first layer pair containing a cyan dye, a second layer pair containing a magenta dye, and a third layer pair containing a yellow dye are contained on the support, and a barrier layer is interposed between each layer pair. 9. A photographic material according to any one of claims 1 to 8, characterized in that: 10. The photographic material according to claim 8 or 9, wherein the barrier layer contains a diffusion resisting agent that absorbs iodide ions. 11. The photograph according to claim 1, characterized in that it contains an intermediate layer containing a bleaching inhibitor, a filter dye, a base stabilizer, a base brightener, a plasticizer or a wetting agent. material. 12. State laws for the use of photographic materials as claimed in claim 1 for the production of photographic images. 13. A photographic image created using the photographic material according to claim 1. 14. A method of making photographic images using NECA type silver dye-whitening materials comprises: (a) a m-whiteable image dye, a low-speed silver halide emulsion, and a silver halide emulsion on a support; (b) at least one layer comprising a sensitive iodide-containing silver halide emulsion, in a developer solution containing a silver halide complexing agent; A method characterized in that the method comprises: developing the product, performing dye bleaching and silver bleaching, and then fixing. 15. Claim 14, characterized in that the silver halide complex forming agent is an alkali metal salt or ammonium salt of thiosulfuric acid, or a salt of thiocyanic acid.
The method described in section. 16. Claim 14, characterized in that said silver bleaching, dye bleaching and fixing are each carried out in separate processing baths or in a single combined processing bath. The method described in. 17. The method according to claim 16, characterized in that the silver bleaching and dye bleaching are carried out in a single processing bath. 18. The exposed and developed material is washed with water not only at the end of processing but also optionally between the processing steps of development, dye bleaching, silver bleaching and fixing. The method described in Section 14. A composition for developing a photographic material according to claim 1, characterized in that it contains from 0.3 to 60 mmol of silver complexing agent per ic+, iz't-.