DE1547797B1 - Photographic light-sensitive material - Google Patents

Description

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The invention relates to a photosensitive photocomposer-containing layer after it has been produced graphic recording material, consisting of the visible image with an acidic or basic one a layer support, a silver solution applied thereon is brought into contact, the dye halide copying or direct copying occurs and forms into a light absorbing filter dye another, above the silver halide layer, is transferred.

ordered, containing a colloidal binder, Furthermore, the production of the filter color

silver halide free layer. Substance thus take place in that one as a dye

It is known e.g. B. from the German patent bildner used a color coupler. In this case 1 004 046, images produced by photographic means become the recording material after development to protect against exposure caused by prolonged exposure of the visible image to an oxidized developer Protect destruction by keeping compounds containing developer solution in Konman Filter layers were applied to the images with a damaging tact, whereby the color coupler contained in the Applying radiation absorbing dye. A filter dye is produced in the layer. However, applying such layers is time consuming, sensitizing dyes are used to

as there is an additional coating and drying factor to the sensitivity range of the emulsion layer took orders. It is also well known, e.g. B. or layers according to longer wavelength ranges from German Patent 1 036 639, to move in photo, the absorption of the graphic recording materials for the her- dye former in wavelength ranges of over Position of colored images can be shifted by developing a 300 millimicron, with anyway reducible silver salt by means of an aromatic ao exposure and photodevelopment of the emulsion amino developing agent are determined, color layers are possible. The filter dye itself is supposed to Coupler in a light-sensitive silver layer, but as little or no light as possible from a wave halide emulsion layer adjacent, light imperfections over the 460 to 500 millimicron range sensitive layer. With these photographi- absorb, otherwise the image will be in the emulsion layer see recording materials that would mask the color domes or layers, ler however the task of generating image dyes. Typical dye formers, which are practically none

The object of the invention is to absorb a highly sensitive light of wavelengths above 300 ταμ , to provide photographic recording material, which, however, can easily be converted into compounds or salts, in contrast to the known methods, which have favorable light absorbing recording materials already at 30 tion properties Besides color couplers, its production is modified in such a way that the leuco dyes and the well-known acid-base application of a filter dye to the developed indicator dyes.

Picture unnecessary. Typical suitable leuco dyes are substituted

The object of the invention is based on a light phenols, triarylmethane dyes and triarylmethane-sensitive photographic recording material 35 dyes with one or more heteroatoms as rial, consisting of a layer support and a bridge atom on top.

applied silver halide copying or -direct- Particularly advantageous dye formers are p-nitro-

copier layer and another, over the silver halophenol and 4-nitro-2ichlorop, 6-dhenol. Another vorgenidschicht arranged, a colloidal binder partial dye formers, which consists of a substituted, containing, silver halide-free layer of and 40 phenol is, for example, the 2-nitro-4-n-octylist is characterized in that the silver halide phenol. Another advantageous dye former is the free layer of a p-diazodiethylaniline which is permeable to actinic light in a mixture with acetoacetanilide. Dye former, which by treatment with a - Typical suitable color couplers are open-chain aqueous treatment solution in up to 460 ταμ methylene coupler compounds , such as absorbent filter dye, contains. 45 from US Pat.

the exposure of the silver halide layer or layer. Some particularly advantageous color couplers are

did not. yellow dye-producing, open-chain methylene

Suitable as dye formers are weakly colored couplers, such as, for example, 4-benzoylacetamido-3-me- or colorless compounds, which are 50 thoxy- (2 ', 4'-di-t.-amylphenoxy) acetanilide, i.e. coloration, z. B. with an activator solution, such as couplers, as z. B. from the German patent a solution containing an acid or a base, 1036 639 are known and for the production of image or an oxidized developing agent can be used in strong dyes.

colored compounds or salts can be transferred. Particularly suitable acid-base indicator dyes

Dye formers in filter layers for copy or 55 are those that come into contact with an acid or base On-the-fly emulsions should preferably not form an orange or yellow dye. As special radiation of over 300 millimicrons, which advantageous dye formers of this type have so that enough light can pass through the layer, eosin compounds have been shown, an image-appropriate exposure and, in the case of this includes, for example, eosin yellow (CI 768),

Direct copy materials, a photo development of the 60's color changes at a pH of 2 to 3.5 To enable latent image, as it is well known that there is light, acridine orange (CI 788), its color change occurs in the wavelength range of 300 to 460 millimicrons at a pH value of 3 to 4.0, erythrosine, for exposure and photo development of most of its color change at pH 4.0 to usual copier or direct copier emulsions 6.0 takes place, resorufin, whose color changes with a is used because the silver halide starts in this 65 pH value from 8.0 to 10.0 and bis- (l-butyl range is sensitive to light. 2,5-dimethyl-3-pyrrole) methine cyanine perchlorate.

The production of the filter dye can thus be The dye formers can be the silver halide

simply take place in that the color-free layer alone or together with a color

fabric mordants to prevent migration of the Dye are incorporated.

If a combination of compounds is necessary to form the desired dye, one will not migrating mordant is used to prevent migration of at least one of the dye formers. The dye mordants commonly used in the photographic field are used to prevent the Migration of dyes and couplers used mordants in question, as for example from the British Patent 850 281 are known.

The binder of the silver halide-free layer can be any conventionally known binder, which has sufficient porosity to allow the dye former to contact the treatment solution to let come. Suitable binders are those customarily used for the production of photographic layers used hydrophilic colloids, such as gelatin, colloidal albumin, polysaccharides, cellulose derivatives, synthetic resins such as polyvinyl compounds including polyvinyl alcohol derivatives and acrylamide polymers. Optionally, in addition to the hydrophilic colloids can be used to form the layer also has hydrophobic colloids, such as dispersed polymerized vinyl compounds, be used. Suitable compounds of this type are water-insoluble polymers of acrylic acid alkyl esters or methacrylic acid alkyl esters, polymers of acrylic acid from acrylic acid sulfoalkyl esters or methacrylic acid sulfoalkyl esters.

The photosensitive layer or layers of the recording material can be made of any conventional silver halide emulsion layers, including conventional gelatin silver halide emulsion layers. However, the light-sensitive layers can also consist of silver halide layers vapor-deposited in vacuo on a layer support exist.

Particularly advantageous results are obtained when the invention is used to protect on-the-fly images is applied in the emulsion layers z. See U.S. Patents 3,271,157; 3,287,136 and 3 033 682, or for protecting copy-out images in emulsion layers, e.g. B. in U.S. Patent 2,592,250 and in the journal "Photographic Chemistry", Vol. 1, pp. 31/32, Fountain Press, London.

In the case of direct copy papers, it is known that a latent can be produced by brief exposure to high-intensity light Generate image, which by a so-called photo development by exposure to room light or fluorescent light can be developed into a visible image. To manufacture more advantageous On-the-fly emulsions use an emulsion which mainly contains silver halide crystals has internal sensitivity and contains a halogen acceptor. Such emulsions are for example, in U.S. Patents 3,271,157 and 3,287,136.

The layer containing the dye former, which is converted into a filter layer, forms in the Usually the outermost layer of the photographic material. If necessary, however, can also additional layers can be arranged over the filter layer, as long as only those containing the dye former Layer is further from the support than the silver halide layer or layers because the filter layer only in this case constitutes an effective protection of the silver halide emulsion layer or layers.

Preferably all silver

halide layers between the dye-former-containing layer and the support, therewith as much light as possible is absorbed before it reaches the silver halide.

By means of the photographic recording material according to the invention with the one containing a dye Layer becomes the previously known, more complex method of applying a filter layer avoided on the exposed and developed photographic recording material. Bringing in contact the layer containing the dye former with the aqueous treatment solution to form the Dye is pretty straightforward. The processing solutions to be used in the recording material of the invention are in contrast to the complex ones usually used for the application of filter layers Dye solutions, which are usually unstable, completely stable.

example 1

A direct copy recording paper having a photo-developable silver chlorobromide emulsion layer was on the emulsion side with various aqueous dispersions of dye formers coated. The dispersions each contained 9 percent by weight gelatin. The pH of the Dispersions were adjusted to 3.5 using dilute nitric acid.

Samples of the uncoated and coated direct copy papers were exposed for 2 microseconds using a xenon discharge tube (the tube output was approximately 50 joules at a distance of 76.2 cm). The various samples were then photo-developed by exposure to fluorescent room light for 45 minutes. The samples were then bathed in an aqueous alkaline solution (10 percent by weight borax or sodium hydroxide solution) for 5 seconds and dried. The reflection densities of the background and image areas were then measured under yellow light. The respective differences between the image densities (Dmax) and the background densities (D _n H _n ) were calculated. They are given in the table below. The individual samples were then exposed again for 92 hours to fluorescent light with an intensity of about 6.5 lumens / dm ^2. D H _{n n} calculated - from the measured reflection densities of the image and background areas turn OiSetenz ^ D _m ax was. The values obtained in this way are also given in the table below.

55 Dye formers Dmax - - D min before the after 92 hours 92 hours 1. without exposure exposure 60 2. p-Nitrophenol (2 g / l) ... 0.38 0.06 3. p-Nitrophenol (8 g / l) ... 0.40 0.17 4. 4-nitro-2,6-dichloro 0.40 0.17 phenol (lg / 1) 5. p-Diazo-diethylaniline 0.38 0.14 65 (2.8 g / l) and aceto acetanilide (3.6 g / l) 6. 2-nitro-4-n-octyl- 0.34 0.13 phenol (4 g / l) 0.41 0.10

Example 2

Samples of a direct copy paper were on the emulsion side with a 7 ° / ₀ gelatin solution containing per liter 50 ml of a 10% sodium hydroxide solution and 1 g of bis (l-butyl-2,5-dimethyl-3-pyrrole) -methincyaninperchlorat contained, coated. The bis (1-butyl-2,5-dimethyl-3-pyrrole) methine cyanine perchlorate was dissolved in 50 ml of ethanol (per gram of dye) before it was added to the gelatin solution.

The samples were exposed and photo-developed in the manner indicated in Example 1. One of the samples was then bathed for 5 seconds in a 10 ° / ₀ citric acid solution and then dried. After measuring the reflection densities and calculating the Dmax-Dmin values , the samples were exposed for 65 hours to fluorescent light with an intensity of about 35 lumens / dm ² . After the reflection densities were measured again, the values D _max - D _m in were calculated again. The results are given in the following table:

Control sample uncoated

Control sample coated,
However not
acid treated

Coated with the
Acid solution treated
paper

before the
exposure

Dmax Dmin

after a 65 hour exposure

0.36
0.38
0.36

25th

0.04 0.05

0.09

Example 3

35

40

A piece of a direct copy paper as described in Example 1 was coated on the emulsion side in such a manner with a 5 ° / ₀ gelatin solution containing 4 g per liter of p-nitrophenol contained and having a pH value of 1.9, coated in that about 0.65 ml of the gelatin solution were used per dm ^{2 of support surface.} After the coating, the paper was dried. Two samples of the paper were exposed and photo-developed using the procedure described in Example 1. One of the two samples was then bathed long 5 seconds in a 4 ° / ₀ aqueous solution of borax, and then dried. The image stability of both samples was determined by calculating the values D _max -Dmin before and after 43 hours of exposure to fluorescent light with an intensity of about 35 lumens / dm ² from the measurement of the reflection densities. The results obtained are given in the following table:

60

Example 4

By melting together 90.5 g of pig skin gelatin and 760 of a 12 ° / ₀ solution ml of a polymeric mordant, which was obtained by reacting polymerized methyl vinyl ketone with aminoguanidine and subsequent reduction of the reaction product obtained at 50 ° C and solidifying the aufgeschmolzenenMischung was a coating composition manufactured. The resulting gel was crushed, washed with tap water for 6 hours and allowed to dry overnight. The washed gel was melted at 60 ° C., whereupon the pH value was adjusted to 4.5 with 6.0 n-glycolic acid. The volume was then brought to 3500 ml.

4 g / l of p-nitrophenol, dissolved in a little ethanol, admitted. The pH of the mordant mass was adjusted to 3.5. With the mordant mass a Pieces of paper coated and then dried. After exposure according to the example 1 procedures described were excellently sharp Received pictures.

In a first test series an image-bearing sample of the photographic material was 10 seconds bathed in a 10 ° / ₀ aqueous solution of borax, wherein a colored protective layer. After drying, both the sample treated as described and a control sample were exposed ^{to fluorescent light with an intensity of about 6.5 lumen / dm 2 for 92 hours.}

In a second test series images were having samples of the photographic material of different length in a 4 ° / ₀ aqueous solution of borax bathed and then dried. Together with a control sample, the samples were exposed to fluorescent light with an intensity of about 35 lumens / dm ^{2 for 68 hours.} The Dmax-Dmin values of the individual samples before and after exposure were used to assess the image stability. They are given in the following table:

D max ' - D _m in before the after exposure exposure Control sample not Alkali treated 0.44 0.03 With the borax solution treated paper 0.44 0.08

Dmax - - Dmin before the after exposure exposure Investigation 1 Control sample 0.38 0.06 Photographic mate rial according to the invention alkali treated 0.39 0.17 Investigation 2 Control sample 0.39 0.03 Photographic mate rial after the inventor Alkali-treated dung: 5 seconds 0.39 0.12 20 seconds 0.39 0.14 80 seconds 0.39 0.16

Corresponding results were obtained when the acid indicators eosin yellow, erythrosine and resorufin were used and the borax solution was replaced with citric acid.

Example 5

Following the procedure described in Example 4, a photographic material according to the invention was obtained manufactured.

The concentration of p-nitrophenol in the gelatin solution was 8 g / l, and the pH of the coating material was adjusted to 1.9 before it was used. The image stability of a ungebadeten control sample and of a 5 seconds in a 4 ° / ₀ aqueous solution of borax gebädeten sample was determined by calculating the values of Dmax - DfM _n from the before and after a 43stündigen exposure with an intensity of about 35.0 lumens / dm ² measured reflection densities determined. The values obtained are given in the following table:

In the manner described in Example 1, the samples were exposed for 92 hours. The samples with the color couplers showed similarly favorable results as the samples with the dyes in Example 1, ie, at least a 15 ° / _o percent improvement values

Unbathed sample
Bathed sample.

D _max - D _n

before the
exposure

after
exposure

0.41
0.40

0.03
0.12

25th

Example 6

This example illustrates the use of a color coupler to create a filter layer.

A solution of 1 g of the yellow dye forming coupler 4-benzoylacetamide-3-methoxy- (2 ', 4'-di-t-amylphenoxy) acetanilide in 0.5 g of di-n-butyl phthalate coupler solvent was added in 5 ml a 5 ° / _o aqueous solution of photographic gelatin in which is 0.1 ml saponin was dispersed. The dispersion obtained in this way was ground three times in a colloid mill and then added to 50 ml of a 10% strength aqueous solution of photographic gelatin which contained 0.4 ml of saponin and 0.1 ml of a 10% strength formaldehyde solution. After adding 20 ml of distilled water, the coating material was applied to direct copy paper in such a way that about 12.5 mg of coupler, about 6.25 mg of coupler solvent and about 65.66 mg of gelatin were used ^{per dm 2 of support surface.} The paper was exposed and photo-developed in the manner described in Example 1. The paper was then bathed for 5 seconds in an aqueous solution with 5 g of the color developer 2-amino-5-diethylaminotoluene · HCl and in an aqueous solution with 10 g of potassium ferricyanide.

In a parallel experiment, the photo-developed material with a single bath, which both the color developer 2-Amino-5-diethylaminotoluene and the oxidizing agent potassium ferricyanide contained in contact brought. Correspondingly favorable results were obtained in this fading test.

Claims (5)

Patent claims: 1. Photosensitive photographic recording material, consisting of a support, a copy-out or direct copy layer of silver halide applied thereon and one further, arranged over the silver halide layer, containing a colloidal binder, silver halide-free layer, characterized in that the silver halide-free Layer a for actinic light permeable dye former, which by treatment with a aqueous treatment solution in an up to 460 m /! absorbent filter dye is transferable contains. 2. Photosensitive photographic recording material according to claim 1, characterized in that that the layer containing the dye former is p-nitrophenol as the dye former contains. 3. Photosensitive photographic recording material according to claim 1, characterized in that that the layer containing the dye former is 4-nitro-2,6-dichlorophenol as the dye former contains. 4. Photosensitive photographic recording material according to claim 1, characterized in that that the layer containing the dye former is a dye former contains yellow dye-forming open chain couplers. 5. Photosensitive photographic recording material according to claim 1, characterized in that that the layer containing the dye-forming agent is an eosin compound as the dye-forming agent contains. 009 546/298