DE19916649A1 - Photographic silver halide film or paper had coating containing hardened binder, dye fixative and optionally dye stabilizer for retouching or printing with other information - Google Patents

Abstract

In photographic material with light-sensitive silver halide emulsion layer(s) on the front of a base, the outside layer on at least one side is given a coating containing (a) a binder hardened at least so far that the layer remains unchanged during photographic processing, (b) fixative that makes dye fast to diffusion and wiping, and (c) optionally a dye stabilizer for the dye used in (b).

Description

The invention relates to a photographic material with a support and at least a photosensitive silver halide emulsion layer, which with other, not information to be provided by exposure and development can.

Photographic materials have at least one photosensitive material on a support che silver halide emulsion layer in which by exposure and processing Image is generated. Mistakes in this picture and retouch information on the It is often only possible to apply the back in a quality that is comparable to that of The quality of the photographic image drops.

The object of the invention was therefore to provide a photographic material which overcomes these disadvantages.

It has now been found that this object can be achieved by providing an additional transparent layer as the outermost layer on at least one side of the photographic material

• a) a binder that is at least hardened to the extent that the layer during the photographic processing remains unchanged,
• b) an agent that binds dyes diffusion and smudge-proof, and
• c) optionally a dye stabilizer for those used according to b) Contains dyes.

The photographic material can be a black and white material or a color photograph graphic material that is the usual support for such materials and on it applied photographic layers.

Gelatin is particularly suitable as a binder for the additional layers, which can be hardened with the hardening agents commonly used for gelatine. Preferential wise, the same hardening agent is used as for the gelatin-containing ones Layers of photographic material, taking one in particular to a lesser one Extent hardens so that the additional layers are processing stable on the one hand, d. H. not change in the photographic processing, but on the other hand the do not interfere with photographic processing solution when penetrating the material.

The side of the material on which the at least one photosensitive silver halide emulsion layer is applied as the front, the other as the back designated.

The additional layer applied on the back preferably serves Retouching purposes, in particular the additional layer applied to the front the other to provide additional information, but also the other arrangement is possible. In all cases, the additional information is especially with inkjet Technology applied.

Suitable agents that bind the inkjet dyes diffusion and smudge-proof and Enable transparent layers are z. B. cationic pickling, dyestuff plexing compounds, aluminum hydroxide.

Cationic stains are preferred because azo is usually used as the inkjet dye dyes with acidic groups can be used.

Suitable cationic mordants are e.g. B. Compounds from the classes of poly vinylpyridines, optionally quaternized, of the polyvinylimidazoles, if appropriate quaternized, the poly (-di) allylammonium compounds, the polydialkylaminoalkyl (meth) acrylates, optionally quaternized, the polydialkylammonium alkyl (meth -) - acrylamides, optionally quaternized, the polyvinylbenzyldi or trialkylammo nium compounds, the polyester with quaternary ammonium groups, the polyamides with quaternary ammonium groups, the polyurethane with quaternary ammonium groups, the polymers of N, N, N-trialkyl-N- (meth) acrylamidobenzylammonium links. Preferred stains are copolymers of at least 45% by weight Vinyl pyrrolidone and at least 20% by weight of a quaternary stick monomer substance atom.

The cationic mordants can be water-soluble or water-dispersible. The cationic mordants have a weight average molecular weight of preferably at least 2000, especially at least 20,000.

Compounds containing phosphonium groups (EP 609 930) are used, as well as ground cationic ion exchange resins be finely divided into the pickling layer.

Some examples are shown below.

The dotted bonds in B-5 and B-6 represent a cross-linking of the molecule with other similar chains.

Further suitable binders for the applied layers are in Research Disclosure 37254, Part 2 (1995), p. 286 and Research Disclosure 38957, Part II A (1996), p. 598.

Gelatin is preferred.

The additional layer can also contain so-called spacers.

Suitable spacers are in particular spherical and have a medium one Diameters from 1 to 50 microns, especially from 5 to 20 microns and have a narrow Grain size distribution.

Suitable spacers exist e.g. B. from polymethyl methacrylate, polystyrene, poly vinyl toluene, polyamide, silicon dioxide and insoluble starch.

Preferably contains one arranged above the pickled layers Layer a UV absorber.

Suitable UV absorbers are in Research Disclosure 24239 (1984), 37254, Part 3 (1995), p. 292, 37038, part X (1995), p. 85 and 38957, part VI (1996), p. 607 and EP 306 083 and 711 804.

In a preferred embodiment contains at least one layer, preferably a stain-containing layer has an image stabilizer. Suitable dye stabilizers are from Research Disclosure 37254, Part 8 (1995), pp. 292 and 38957, Part X (1996), pp. 621ff. as well as DE 43 37 862, GB 20 88 777, EP 373 573, EP 685 345 and EP 704 316.

Suitable UV absorbers are, for example, compounds of the formulas (I) and (II):

Examples of suitable dye stabilizers are:

The material is preferably a supervisory material and contains another Embodiment of the invention means that the optical properties of the Improve material, preferably optical brighteners. This means preferably in a layer below that most distant from the support Layer, particularly preferably in a layer below the receiving layer brought in. Suitable compounds are in Research Disclosure 37 254, Part 8 (1995), pp. 292ff and 38 957, part VI. (1996), pp. 607ff.

Suitable curing agents are in Research Disclosure 37 254, Part 9 (1995), p. 294; 37 038 Part XII (1995), pp. 86 and 38 957, Part II B (1996), p. 599ff.

Examples of hardeners are:

It is usually 0.005 to 1 wt .-%, based on the curable binder used, preferably 0.01 to 1 wt .-%.

The additional layers can be made using a cascade or curtain as known from the manufacture of silver halide photographic materials starting from the photographic material and a casting solution for each to be applied additional layer can be produced in one pass.

After watering, the material is dried and is then ready for use.

The inkjet process is known (see for example the chapter Ink Jet Printing by R. W. Kenyon in "Chemistry and Technology of Printing and Imaging Systems", Editor Peter Gregory, Blackie Academic & Professional, Chapman & Hall 1996, pages 113 to 138, and the literature cited therein).

Examples of color photographic materials are color negative films, color reversal films, Color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or silver color bleaching process. An overview can be found in Research Disclosure 37038 (1995) and Research Disclosure 38957 (1996).

The photographic materials consist of a support on which at least one photosensitive silver halide emulsion layer is applied. Own as carrier especially thin films and foils. An overview of carrier material lien and auxiliary layers applied to its front and back are in Research Disclosure 37254, Part 1 (1995), p. 285 and in Research Disclosure 38957, Part XV (1996), p. 627.

The color photographic materials usually contain at least one each in red sensitive, green sensitive and blue sensitive silver halide emulsions layer and, if necessary, intermediate layers and protective layers.

Depending on the type of photographic material, these layers can vary be arranged. This is shown for the most important products:

Color photographic films such as color negative films and color reversal films show in the the following sequence on the carrier 2 or 3 red-sensitive, cyan-coupling silver halide emulsion layers, 2 or 3 green-sensitive, purple-coupling silver halide emulsion layers and 2 or 3 blue-sensitive, yellow-coupling silver halide emulsion layers. The layers are the same spectral sensitivity differ in their photographic sensitivity speed, with the less sensitive sub-layers usually closer to the carrier are arranged than the higher sensitive sub-layers.  

Between the green sensitive and blue sensitive layers is common a yellow filter layer is applied, which prevents blue light from lying in the below layers.

The possibilities of the different layer arrangements and their effects The photographic properties are discussed in J. Inh Rec. Mats., 1994, Vol. 22, pages 183-193 and in Research Disclosure 38957 Part XI (1996), p. 624 described.

Color photographic paper, which is usually much less sensitive to light as a color photographic film, points in the order given below usually a blue-sensitive, yellow-coupling silver halide on the carrier nidemulsion layer, a green-sensitive, purple-coupling silver halide emulsion sion layer and a red-sensitive, cyan-coupling silver halide emul ion layer on; the yellow filter layer can be omitted.

Deviations in the number and arrangement of the photosensitive layers can occur to achieve certain results. For example, you can all highly sensitive layers in one layer package and all low-sensitivity layers layers into another layer package in a photographic film be set to increase sensitivity (DE-25 30 645).

Essential components of the photographic emulsion layers are binders, Silver halide grains and color couplers.

Information on suitable binders can be found in Research Disclosure 37254, part 2 (1995), p. 286 and in Research Disclosure 38957, Part II.A (1996), p. 598.

Information about suitable silver halide emulsions, their preparation, maturation, Stabilization and spectral sensitization including suitable spectral sensi Bilisators can be found in Research Disclosure 37254, Part 3 (1995), p. 286, in Research Disclosure 37038, Part XV (1995), p. 89 and in Research Disclosure 38957, part V.A. (1996), p. 603.

Photographic materials with camera sensitivity usually contain Sil berbromide iodide emulsions, which may also contain small amounts of silver chloride can contain. Photographic copying materials contain either silver chloride bromide emulsions with up to 80 mol% AgBr or silver chloride bromide emulsions with over 95 mol% AgCl.

Information on the color couplers can be found in Research Disclosure 37254, Part 4 (1995), p. 288, in Research Disclosure 37038, Part II (1995), p. 80 and in Research Disclosure 38957, Part XB (1996), p. 616. The maximum absorption of the dyes formed from the couplers and the color developer oxidation product is preferably in the following ranges: yellow coupler 430 to 460 nm, purple couplers 540 to 560 nm, cyan couplers 630 to 700 nm.

In color photographic films, to improve sensitivity, grainy speed, sharpness and color separation are often used in the compounds involved in the reaction with the developer oxidation product release compounds that are photographic are effective, e.g. B. DIR couplers that release a development inhibitor.

Information on such compounds, in particular couplers, can be found in Research Disclosure 37254, Part 5 (1995), p. 290, in Research Disclosure 37038, Part XIV (1995), p. 86 and in Research Disclosure 38957, Part XC (1996), p. 618.

The mostly hydrophobic color coupler, but also other hydrophobic components of the Layers are usually found in high-boiling organic solvents dissolved or dispersed. These solutions or dispersions are then in one emulsified aqueous binder solution (usually gelatin solution) and lie after drying the layers as fine droplets (0.05 to 0.8 µm through knife) in the layers.

Suitable high-boiling organic solvents, methods for incorporation into the Layers of photographic material and other methods, chemical ver Finding bonds in photographic layers can be found in Research Disclosure 37254, Part 6 (1995), p. 292.

The usually indicated between layers of different spectral sensitivity ordered non-photosensitive interlayers can contain agents that an undesirable diffusion of developer oxidation products from a light sensitive to another light-sensitive layer with different spectra Prevent central sensitization.

Suitable connections (white coupler, scavenger or EOP catcher) can be found in Research Disclosure 37254, Part 7 (1995), p. 292, in Research Disclosure 37038, Part III (1995), p. 84 and in Research Disclosure 38957, part XD (1996), p. 621.

The photographic material can also UV-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, anti-oxidants, D _Min dyes, plasticizers (latices), biocides and additives to improve the coupler and dye stability, to reduce the color fog and to reduce yellowing and other included. Suitable compounds are found in Research Disclosure 37254, Part 8 (1995), p. 292, in Research Disclosure 37038, Parts IV, V, VI, VII, X, XI and XIII (1995), p. 84ff and in Research Disclosure 38957, parts VI, VIII, IX and X (1996), pp. 607 and 610ff.

The layers of color photographic materials are typically hardened, i.e. that is Binder used, preferably gelatin, is replaced by suitable chemical Process networked.  

Suitable hardener substances can be found in Research Disclosure 37254, Part 9 (1995), P. 294, in Research Disclosure 37038, Part XII (1995), p. 86 and in Research Disclosure 38957, Part IIB (1996), p. 599.

After photographic exposure, color photographic materials become their character processed according to different processes. Details on ver procedures and the chemicals required for this are in Research Disclosure 37254, Part 10 (1995), p. 294, in Research Disclosure 37038, parts XVI to XXIII (1995), p. 95ff and in Research Disclosure 38957, parts XVIII, XIX and XX (1996), p. 630ff published together with exemplary materials.

example 1

A color photographic recording material was produced by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene. The quantities given relate to 1 m ² . The corresponding amounts of AgNO ₃ are given for the silver halide application.

Layer structure 1 Layer 1

(Substrate layer)
0.10 g gelatin

Layer 2

(blue sensitive layer)
Blue-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.9 µm) from 0.50 g AgNO ₃

, With
1.25 g gelatin
0.42 g gel coupler Y-1
0.18 g yellow coupler Y-2
0.50 g of oil former OF-1
0.10 g dye stabilizer FS-1
0.70 mg blue sensitizer BS-1
0.30 mg stabilizer ST-1

Layer 3

(Intermediate layer)
1.10 g gelatin
0.06 g EOP catcher EF-1
0.06 g EOP catcher EF-2
0.12 g tricresyl phosphate (CPM)

Layer 4

(green sensitive layer)
green-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.47 µm) from 0.28 g AgNO ₃

, With
1.00 g gelatin
0.21 g purple coupler M-1
0.15 g dye stabilizer FS-2
0.21 g of FS-1 dye stabilizer
0.21 g isostearyl alcohol
0.21 g diisodecyl phthalate (DIDP)
0.70 mg green sensitizer GS-1
0.50 mg stabilizer ST-2

Layer 5

(UV protective layer)
0.95 g gelatin
0.30 g UV absorber II-6
0.06 g EOP catcher EF-1
0.06 g EOP catcher EF-2
0.15 g of OF-2 oil generator
0.15 g CPM

Layer 6

(red sensitive layer)
red-sensitive silver halide emulsion (99.5 mol% chloride, 0.5 mol% bromide, average grain diameter 0.5 µm) from 0.30 g AgNO ₃

, With
1.0 g gelatin
0.46 g of cyan coupler C-1
0.46 g CPM
0.03 mg red sensitizer RS-1
0.60 mg stabilizer ST-3
0.30 g 4: 1 mixture of UV absorbers I-1 and I-6

Layer 7

(UV protective layer)
0.30 g gelatin
0.10 g UV absorber II-8
0.10 g of oil former OF-3

Layer 8

(Protective layer)
0.90 g gelatin
0.05 g white toner WT-1
0.07 g polyvinyl pyrrolidone
1.20 mg silicone oil
2.50 mg spacer (polymethyl methacrylate, medium particle size 0.8 µm)
0.30 g of H-1 curing agent

Layer structure 2

A layer structure corresponding to layer structure 1 was produced and, after hardening, poured with a 9th layer, which contains the following components per m ² :

Layer 9

1 g gelatin
1 g phthaloyl gelatin
0.05 g stain B-13
0.01 g of emulsifier E-1
0.015 g of H-1 curing agent
0.25 g dye stabilizer FST-5

Connections used in the example:

The materials of layer structures 1 and 2 are exposed and in the after processed as described below. You get color of equivalent quality photographic images. The material of layer structure 2 can be processed additionally with an inkjet printer, e.g. B. an Epson-850 inkjet printer diffusible and smudge-proof with additional information.

The 9th layer shows no detachment in the processing described above.

processing a) Color developer - 45 s - 35 ° C

Tetraethylene glycol 20.0 g N, N-diethylhydroxylamine 4.0 g N-ethyl-N- (2-methanesulfonamidoethyl) -4-amino-3-methylbenzene sulfate 5.0 g Potassium sulfite 0.2 g Potassium carbonate 30.0 g Polymaleic anhydride 2.5 g Hydroxyethane diphosphonic acid 0.2 g White toner (4,4'-diaminstilbenesulfonic acid derivative) 2.0 g Potassium bromide 0.02 g

make up to 1000 ml with water; pH with KOH or H ₂

SO _4th

to pH 10.2 to adjust.

b) bleach-fix bath - 45 s - 35 ° C

Ammonium thiosulfate 75.0 g Sodium bisulfite 13.5 g Ethylenediaminetetraacetic acid (iron ammonium salt) 45.0 g

make up to 1000 ml with water; pH with ammonia (25% by weight) or Adjust the acetic acid to pH 6.0.

c) Soak - 90 s - 33 ° C d) drying Example 2

A color photographic recording material for color negative color development was prepared by applying the following layers in the order given to a transparent cellulose triacetate support. The quantities given relate to 1 m ² . The corresponding amounts of AgNO ₃ are given for the silver halide application; the silver halides are stabilized with 0.5 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene per mole of AgNO ₃ .

Layer structure 3 1st layer

(Antihalo layer)
0.3 g black colloidal silver
1.2 g gelatin
0.3 g of UV absorber I-7
0.2 g EOP (developer oxidation product) scavenger EF-3
0.02 g tricresyl phosphate (CPM)

2 layer

(low red sensitive layer)
0.7 g AgNO ₃

a spectrally red-sensitized AgBrI emulsion, 4 mol% iodide, average grain diameter 0.42 µm
1 g gelatin
0.35 g of colorless coupler C-2
0.05 g colored RC-1 coupler
0.03 g colored coupler YC-1
0.36 g CPM

3 layer

(medium red sensitive layer)
0.8 g AgNO ₃

a spectrally red-sensitized AgBrI emulsion, 5 mol% iodide, average grain diameter 0.53 µm
0.6 g gelatin
0.15 g of colorless coupler C-3
0.03 g colored coupler RC-1
0.02 g DIR coupler D-1
0.18 g CPM

4th layer

(highly red-sensitive layer)
1 g AgNO ₃

a spectrally red-sensitized AgBrI emulsion, 6 mol% iodide, average grain diameter 0.85 µm
1 g gelatin
0.1 g colorless coupler C-3
0.005 g DIR coupler D-2
0.11 g CPM

5th layer

(Intermediate layer)
0.8 g gelatin
0.07 g EOP catcher EF-2
0.06 g aluminum salt of aurintricarboxylic acid

6th layer

(low green sensitive layer)
0.7 g AgNO ₃

a spectrally green-sensitized AgBrI emulsion, 4 mol% iodide, average grain diameter 0.35 µm
0.8 g gelatin
0.22 g of colorless coupler M-2
0.065 g colored coupler YM-1
0.02 g DIR coupler D-3
0.2 g CPM

7th layer

(medium green sensitive layer)
0.9 g AgNO ₃

a spectrally green-sensitized AgBrI emulsion, 4 mol% iodide, average grain diameter 0.50 µm
1 g gelatin
0.16 g of colorless coupler M-2
0.04 g colored coupler YM-1
0.015 g DIR coupler D-4
0.14 g CPM

8th layer

(highly green-sensitive layer)
0.6 g AgNO ₃

a spectrally green-sensitized AgBrI emulsion, 6 mol% iodide, average grain diameter 0.70 µm
1.1 g gelatin
0.05 g colorless coupler M-3
0.01 g colored coupler YM-2
0.02 g DIR coupler D-5
0.08 g CPM

9th layer

(Yellow filter layer)
0.09 g yellow dye GF-1
1 g gelatin
0.08 g EOP catcher EF-2
0.26 g CPM

10th layer

(low blue sensitive layer)
0.3 g AgNO ₃

a spectrally blue-sensitized AgBrI emulsion, 6 mol% iodide, average grain diameter 0.44 µm
0.5 g AgNO ₃

a spectrally blue-sensitized AgBrI emulsion, 6 mol% iodide, average grain diameter 0.50 µm
1.9 g gelatin
1.1 g of colorless coupler Y-3
0.037 g DIR coupler D-6
0.6 g CPM

11th layer

(highly blue-sensitive layer)
0.6 g AgNO ₃

a spectrally blue-sensitized AgBrI emulsion, 7 mol% iodide, average grain diameter 0.95 µm
1.2 g gelatin
0.1 g colorless coupler Y-3
0.006 g DIR coupler D-7
0.11 g CPM

12th layer

(Mikrat layer)
0.1 g AgNO ₃

a Mikrat-AgBrI emulsion, 0.5 mol% iodide, average grain diameter 0.06 µm
1 g gelatin
0.004 mg K2 [PdCl ₄

]
0.4 g UV absorber UV-1
0.3 g CPM

13th layer

(Protective and hardening layer)
0.25 g gelatin
0.75 g of curing agent H-1

The total layer structure had a swelling factor ≦ 3.5 after curing.

Substances used for the first time in Example 2:

Layer structure 4

A layer structure corresponding to layer structure 3 was produced and on the the layers 1 to 13 opposite side of the support with a another layer that has the same composition as layer 9 of Layer structure 2 had.

After exposure of a gray wedge, the development according to "The British Journal of Photography ", 1974, pages 597 and 598.

Negatives with layer structures 3 and 4 are usually qualitative equivalent deductions made. Of negatives with layer structure 4 can also Prints are produced in which areas of the image that have become too dark (where, for example a fill-in flash would have been necessary). To do this Negatives with layer structure 4 scanned with a film scanner. For a negative The image file is retouched (lightening the print) by forming the difference Original file and processed file formed. After reflection, this will be Difference file printed on the coated back of the negative. This will be Negatively fixed in a guide frame and printed with an Epson 850 printer. After 5 minutes drying, the negative is used with an enlarger the largest possible opening of the enlarger lens on colored paper. A retouched image is obtained in which the corrected areas are lightened.

The additional back layer does not come off in the processing process, but it is Diffusible and smudge-proof printable.

Due to the largest possible opening of the screen, the distance between the printable Back layer and the front photographic layers a slight, ge wanted blurring of the retouching, that of an electronically blurred one Masking corresponds.

Claims (5)

1. Photographic material with a support and at least one photosensitive silver halide emulsion layer applied to the front of the support, characterized in that the outermost layer on at least one side of the photographic material provides a further layer

• a) a binder which is hardened at least to such an extent that the layer remains unchanged during photographic processing,
• b) an agent that binds dyes diffusion and smudge-proof, and
• c) optionally contains a dye stabilizer for the dyes used according to b).

2. Material according to claim 1, characterized in that the carrier trans parent and the additional layer is applied to the back of the carrier. 3. Material according to claim 1, characterized in that the carrier reflector and applied the further layer on the front of the carrier is. 4. Material according to claim 1, characterized in that that mentioned under b) Is a cationic stain. 5. Material according to claim 1, characterized in that the curing agent, that is used to harden the binder mentioned under a) in one Amount of 0.005 to 1% by weight, based on the curable binder, is used.