DE1772306C3 - Multilayer color photographic recording material - Google Patents

Description

a) the 4-equivalent coupler which forms a yellow dye an open chain benzoylacetanilide coupler,

b) the 2-equivalent coupler which forms a yellow dye an acvloxybenzoylacetanilide coupler.

c) the 4-equivalent coupler forming a magenta dye is a 5-pazo-ion coupler.

d) the 2-equivalent coupler which forms a purple-red dye is a 4-acyloxy-5-pvra / olone coupler.

e) the 4-equivalent coupler which forms a light-green dye, a phenolic coupler and

f) the 2-equi \ alentki, which forms a blue-green dye: pp! er in the 4-position is a chlorine atom substituted phenolic coupler.

The invention relates to a multilayer color photography Recording material with different spectral sensitive silver halide emulsion layers. which contain color couplers, the minesiens a layer structure of two blue-sensitive silver halide emulsion layers lying next to one another and optionally has further layer assemblies of different spectral sensitivity, in which or in which one layer is less light-sensitive than the other layer and the layers are so arranged are that in the case of imagewise exposure, the light first falls on the more photosensitive layer.

The known multilayer color photographic recording materials (cf. for example.

U.S. Patent 2,252,798) usually show three selectively sensitized emulsion layers arranged on one side of a support are. The layer furthest away from the substrate is usually blue-sensitive. the middle layer sensitive to green and that of the support the next layer sensitive to red. Between the blue-sensitive layer and the green-sensitive layer Layer may be a bleachable yellow filter layer to absorb blue radiation.

which has passed through the blue-sensitive layer. Possibly intermediate layers can also be present.

There are also (see, for example, German Auslegeschrift 1 121 470) color photographic recording materials of the type described, in which the individual, differently sensitized Layers are replaced by so-called color-forming layer assemblies made up of two layers. the Both layers of each layer structure usually consist of two light-sensitive ones Emulsion layers that are practically against the same primary color range, i.e. H. the blue, green or red color range of the visible spectrum

3 4

There are, as a rule, the blue pin according to a particularly advantageous embodiment Layered dressing, the green-sensitive layered dressing of the invention has a blue-sensitive, one and the natural-sensitive layered bandage for the generation of an original-sensitive and a red-sensitive layered yellow, purple and blue-green dye images connected up.

The dye images are created when the color is developed. 5 The silver halide emulsions that build up

of the emulsion layers containing color couplers. the layers of a layer structure of the color photo

The commonly known color couplers are so-called graphic materials of the invention used.

4-equivalent coupler, i.e. to form one den. are in an advantageous manner compared to the

Molecule dye is the development of 4 moles- primary color range of the spectrum sensitiv-

Cool silver halide required. However, they are io sated if optical sensitization is desired

so-called 2-equivalent couplers are also known or required by adding suitable emulsions

the. d. H. Couplers to be added / 1 to form a dye-optical sensitizing dye

Molecule only develops 2 molecules of silver- The hydrophilic colloid layers that make up the 4-equiva-

require halide. Such 2-equivalent couplers contain decouplers, are more sensitive.

are advantageous because they are sated compared to the 15, i.e. made more sensitive than the emulsion

4-equivalent couplers only coat half of the silver halide that contain the 2-equivalent couplers, see above

require and the photosensitive layers therefore that the more sensitized or more sensitive

can be thinner. Emulsion layers have sensitivity.

The disadvantage of the known, color-sensitive application units, which preferably have about 0.2 to about 1.0 log of Beiich layer dressings, are larger than the sensitivities of the other application layers in the layer dressings from the German Auslegeschrift I 121 470. .know Tvps, all layers of which are called the. Preferably the sensitivity ratio 2-equiialeiU ^r ail> kupplei is included, but is that the individual layers to one another in such a way that the images with improved sharpness are composed of them, although the sensitometric curve (the curve, that they are less sensitive. 25 in which the developed image density compared to the l.oga-

In contrast, the arithmetic used to produce the exposure is applied) of each

ger Aufzeiehnungsmaierialien used Farbkupp- in question two Fmulsioiissehichten one

If only from 4-equivalents of color couplers, too much color-forming layer structure will result in a uniformly

Light is a compound curve dissolving into the necessarily thicker layers.

scatters, so that the sharpness of the images obtained is 30. Advantageous are the dye-forming

leaves something to be desired. Layer associations of the color-pholographic material

It is the object of the invention. a multi-layered design so that their sensoryometric color photographic recording material has such a relationship to one another that a different spectrally sensitive silver halide neutral scale and color scales from the minimumsion layers containing color couplers achieve a minimum density up to the maximum density ,
According to an advantageous embodiment of the silver-blue-sensitive silver halide halide layer, the layer vertically furthest from the layer support and possibly other layer groups and the band is sensitive to lukewarmness and contains yellow dyes in which 4-equivalent couplers and 2-equivalent couplers in which one layer is less sensitive to light, the fact that the 2-equivalent which forms a yellow dye than the other layer and the layers so coupling agent is a benzovlacetanilide coupler. in which it is arranged that with imagewise exposure the light falls on one of the two waters on the v-carbon atom on the more light-sensitive layer, to indicate. hydrogen atoms through a fluorine or chlorine atom or which is extremely sensitive and images of high an acvloxv-. Cyeloox.} -. Arvlthio-. Alkvlthio, Thto prospecting supplies. 45 cvano or sulfo group is substituted or a pivot

This object is achieved in that in the case of the pre-lylacetanilide coupler. at which one of the two on

The farhphotographic recording mentioned in the foregoing carbon atom sit / end through hydrogen atoms

nungsmaterial the more light-sensitive layer of a fluorine or chlorine atom or an acylo \ y-. Cyclo-

Shift association or the Schichtverband an oxv-. Arvlthio-. Alkvlthio-. Thiocvano- or Stilfo-

4-equivalent coupler and the less photosensitive 50 group is substituted.

Layer contains a colorless 2-equivalent coupler. The recording material preferably contains

which form dyes during color development, the pivalvlacetanilide couplers of which have a v-fluoro-v-pi-

Absorption maxima in each case for the corresponding valvlacetanilide coupler.

Layer structure lie in the same spectral range. According to a further advantageous embodiment

The multilayered color photographic recording of the invention contains the recording material as the recording material of the invention, thus consisting of a 4-equivalent coupler layer that forms a yellow dye, with an open-chain benzovlacelanilide coupler applied thereon and, as arranged, 2-equivalent coupler formed from silver halide emulsion layers, a yellow dye-forming coupler color-sensitive dressing bandages. being a v-acyloxvbenzovlacetanilide tipper.
at least one layer structure that has already been described, which advantageously contains the structure. The individual bandages material of the invention further under the blue are preferably arranged in such a way that the sensitive layer structure encompasses a green-sensitive light used for image-appropriate exposure. 5-pyrazolone couplers, build before the light hits a second and 65 where the 2-equivalent coupler falls a 4-acyloxy a third layer structure. In is advantageous 5-pyrazolone coupler.

Way, the recording material has differently. According to a preferred embodiment of the

dene federations of the structure described. discovery, the recording material has a blue

sensitive, one green-sensitive and one red-sensitive layered dressing with yellow, purple and 4-equivalent and 2-equivalent couplers forming cyan dyes, with the proviso that

a) the 4-equivalent coupler which forms a yellow color collision an open chain benzoylacetanilide coupler,

b) the 2-equivalent coupler which forms a yellow dye an acyloxybenzoylacetanilide coupler,

c) the magenta dye forming 4-equivalent coupler a 5-pyrazolone coupler,

d) the 2-equivalent coupler forming a magenta dye is a ^ acyloxy-S-pyrazolone coupler,

e) the 4-equivalent coupler which forms a blue-green dye a phenolic coupler and

f) the 2-equivalent coupler forming a blue-green dye is in the 4-position through a chlorine atom substituted phenolic coupler.

Appropriately for the production of the color photographic Materials according to the invention used couplers on a ballast group so that they are in the silver halide emulsion layers in which they are incorporated cannot diffuse. The matchmakers can according to known processes in the for manufac- turing as Development of the individual emulsion layers used emulsions are incorporated.

Couplers can also be used in the preparation of the color photographic material of the invention that produce diffusible dyes. Such color couplers are used when the dye image formed is to be transferred to an image-receiving layer, for example as described in FIG U.S. Patent 3,227,550. In such a case, the color photographic Materials of the invention advantageously nondiffusible 2-equivalent couplers as well corresponding 4-equivalent couplers, being diffusible Dye images are generated for transfer. The photographic materials of the invention can also be used in color transfer processes where a dye, a A developer compound or a coupler can be transferred to an image receiving layer.

The ratio of more sensitive to less sensitive silver halide in the color-forming Units of the color photographic material of the invention can vary widely. Appropriately lies the ratio of more sensitive to less sensitive silver halide between 1:99 and 99: 1, see above preferably between 25:75 and 90:10.

The total content of 4- and 2-equivalent couplers in a color-forming unit is expediently from about 25 to about 300 mg per 0.0929 m ² , preferably from about 40 to about 150 mg per 0.0929 m ² . Correspondingly, the total silver content of the more sensitive emulsion layer and the less sensitive emulsion layer of a color-forming unit are in the same range.

The material B described in Example 1 has a yellow dye-forming unit of light-sensitive layers, which are the outermost or upper Forms unit of color photographic material (layers 1 and 2).

Those used in making the color photographic materials in Examples 1-6 higher sensitive gelatin-silver halide emulsions consisted of relatively coarse-grained gelatin-silver bromoiodide emulsions, while the gelatin-silver halide emulsions of lower sensitivities consisted of finer grain emulsions. Both emulsions were made by a process as described by Triveüi and Smith in “Phot. Journal ", Vol. 79, p. 330 (1939) is described,

example 1

Two color photographic materials A and B of the following construction were produced:

Layer 1 Blue sensitive emulsion layer with a

top yellow dye forming coupler; layer

Layer 2 Less sensitive more sensitive to blue

Emulsion layer containing a yellow dye forming coupler;

Layer 3 yellow filter layer;

Layer 4 Green sensitive emulsion layer containing a magenta dye forming material Coupler;

Layer 5 less sensitive green sensitive

Emulsion layer containing a magenta dye forming coupler;

Layer a red-sensitive emulsion layer with a cyan dye-forming dye Coupler;

Layer 7 less sensitive red sensitive emulsions

lowermost ionic layer containing a cyan layer dye forming coupler;

Layer 8 support.

Layers 3 to 8 were identical in the two photographic materials A and B.

Layers 4 and 5 contained a 4-equivalent pyrazolone coupler, namely 1- (2 ', 4 \ 6'-trichlorophenyl) -3- [3 "- (2'", 4 '"- di-tert-amylphenoxyacetamido) - benzamido] -5-pyrazolone, for the formation of the magenta dye image, according to US Pat. No. 3,046,129, Column 17, lines 56 and 57.

Layers 6 and 7 contained a 2-equivalent phenolic coupler, namely 2 - \ - (p-tert-amylphenoxy) -n-butyrylamino-4-chloro-5-methylphenol, for the formation of a blue-green dye image according to USA.-Palentschrift 3 046 129, column 15, lines 74 bis 75.

Layers 1 and 2 in material A contained 75 mg per 0.0929 m ² of a 2-equivalent coupler which forms a yellow dye, namely the sodium salt of pivalyl - (4-sulfophenoxy) -4- (N-methyl-N-octadecylsulfamyl) ) -acetanilides, ie coupler no. 25 of French patent specification 1 411 384. Both of these layers were applied in such a thickness that 40 mg of silver were applied to a support area of 0.0929 m ^2.

Layer 1 of photographic material B contained 80 mg of a yellow dye-forming 4-equivalent coupler \ -pivalyl-5 - [/ - (2,4-di-tert-amylphenoxy) -butyramido] -2-chloroacetanilide per 0.0929 m ² , according to US Pat. No. 3,265,506 (Coupler No. 10), this layer being applied in such a thickness that 80 mg of silver were ^{applied to a support area of 0.0929 m 2.}

Layer 2 of the pholographic material B contained 75 mg of the yellow dye-forming 2-equivalent uncoupler. which was also used to produce layers 1 and 2 of photographic material A, per 0.0929 m ^{2 of support area} and 40 mg of silver per 0.0929 m ^{2 of support area} .

The two color photographic materials were then placed in an intensity dial sensitometer Use a Wraiten No. 47-B filter with a blue one Exposed to light and then developed further. The color development was carried out according to a method that is described in »Abridged Operating Specifications for ECO-2 Process, July 1964, published by Eastman Kodak Company, Motion Picture and Education Marketing Division to the Professional Film Processing Laboratories in the Unites States.

Photographic material B, which contained more silver than photographic material A, possessed a relative speed of 182 compared to a relative speed of 100 for material A, there was no noticeable loss of sharpness compared to material A.

The photographic material B had a significantly better sharpness than a corresponding material C, in which both yellow dye-forming layers had 4-equivalent couplers, in which case a higher silver concentration than that required for photographic material B became necessary.

Example 2

Following the procedure described in Example 1, a multilayer color photographic material was obtained B, but this time a different blue sensitive, yellow dye image forming Unit was formed. In the case of photographic material D, layer 2 was used instead of 2 equivalent coupler. the 7um structure of layer 2 of the photographic material B was used, an equimolar amount of the coupler \ -acetoxy-v- {3 - [\ - (2,4-di-tert-amylphenoxy) -butyramido] -benzoyl) -2-methoxyacetanilide. d. H. Coupler No. 11 of Canadian Patent 735,836 as a 2-equivalent coupler used. Furthermore, this time in layer 1 as a 4-equivalent coupler ■ v-! 3-h- (2,4-di-tert-amylphenoxy) -buty ramido] -benzoyl J-2-methoxyacetanilide. corresponding to U.S. Patent No. XIV Coupler 2,875,057, used as a 4-equivalent coupler.

After imagewise exposure and development, as in

Example 1 described, excellently sharp images were again obtained, the excellent sensitivity of the photographic used

Material. Example 3

Another multilayer color photographic material E was produced which had the same structure as the photographic material B of Example 1, but this time in layer 2 as a 2-equivalent color coupler \ -Fluoro-A-pivaiyl-5 - [> - (2, 4-di-tert-amylphenoxyVbutyramidol ^ chloroacetanilid. couplers according to no. 5 of the USA. Patemschrift-3277155 was used. further, in the layer 1 as a 4-equivalent coupler with an equimolar amount of n-Piva! yl-5-l /-(2.4-di-tert.-amylphenoxy)-butyrarnido]-2-chloroacetaniiid, according to Coupler No. 10 of the USA-Paicntvchrift 3 265 506. used in place of the / around the construction of the layer 1 of the photographic material B \ rrwctcn coupler

After imagewise exposure and development of the material as described in Example 1, in turn, excellent sharp images are obtained which have an excellent sensitivity of the used color photographic material.

Similar favorable results have been obtained when constructing the color photographic material B of Example 1, other blue-sensitive, yellow dye-forming layers were used which

ίο 4-equivalent couplers which form other yellow dyes of the formula I and other yellow dyes-forming 2-equivalent couplers of the formula II, where the ratio of silver in the more sensitive emulsion to silver in the less sensitive emulsion could vary between about 1:99 and about 99: 1. In the following examples 4 and 5 multilayer color photographic materials are described the unit forming both a yellow dye and a magenta dye forming unit have according to the invention.

Example 4

A further multilayer color photographic material F was produced with the structure of the photographic material B of Example 1, but instead of the layer 5 of the photographic material B a green-sensitive gelatin silver bromoiodide emulsion layer was used, which per 0.0929 m ^{2 of support area} 75 mg des a pure

purple dye-forming 2-equivalent coupler l- (2,4,6-trichlorophenyl) -3 - (- 3 - [\ - (2,4-di-terl.-amylphenoxy) -acetamido] -benzamido) -4-acetoxy- 5-pyrazolone, ie, Coupler No. 3 in U.S. Patent 3,311,476. The silver content of the layer corresponded to 40 mg of silver per 0.0929 m ^{2 of} carrier area. In place of the layer 4 of the photographic material B, a green-sensitive gelatin-silver bromoiodide emulsion layer was also used which contains 80 mg of the 4-equivalent coupler 1- (2 ', 4', 6'-trichlorophenyl) -3- ^{per 0.0929 m 2 of support area.} [3 "- (2"',4'"- di-tert-amylphenoxyacetamido) -benzamido] -5-pyrazolone, according to column 17, lines 56 and 57 of U.S. Patent 3,046,129. The layer was applied in such a way that 80 mg of silver were ^{applied to a carrier area of 0.0929 m 2.} The sensitivity of layer 4 was greater than that of emulsion layer 5 by 0.7 log exposure.

After imagewise exposure as described in Example 1, with blue light, and green light as well as with decision

Thus, winding according to the method described in Example 1, images were again more excellent Sharpness obtained showing excellent sensitivity of the photographic material.

Example 5

A further color photographic material C was produced according to the procedure described in Example 4, but this was used as a magenta dye to build up the layer S. 2-equivalent coupler 1 - (2,4,6-trichlorophenyl) -3- <4-nitroanilino) -4-stearoyloxy-5-pyra2olone, according to Coupler No. 2 of US Pat. No. 3,311,476. Furthermore, it has to build up the layer <an equimolar amount of a purple Färb material forming 4-ÄquivaIentkupplers l- (2,4.6-Trichlo rophenyl) -3- (3-nitroanilino) -5-pyrazolone, ge;. NäßKupp lcr # 5 U.S. Patent 3,152,896, in place of the construction of layer 4 of the photographic

309649/25

Materials F used 4-equivalent coupler used.

The photographic material was then exposed and developed as described in Example 1. The received Results were the same as those obtained in Example 4.

Example 6 below describes a typical multilayer color photographic material according to the invention, which has a yellow dye-forming unit, a magenta dye-forming unit and a cyan dye-forming unit according to FIG Invention having.

Example 6

A further color photographic material H was prepared according to the process described in Example 5, but this time the layer 7 of the material F was replaced by a red-sensitized gelaline silver bromoiodide emulsion containing 75 mg of the 2-equivalent ^{coupler 2 which forms a cyan dye per 0.0929 m 2 of support area} -, \ - (p-tert-Amylphenoxy) -n-butyrylamino-4-chloro-5-methylphenol, according to column 15, lines 74 and 75 of U.S. Patent 3,046,129. The silver content of layer 7 was 40 mg of silver per 0.0929 m ^{2 of} support surface. Furthermore, the layer 6 of the photographic material F was replaced by a red-sensitized gelatin-silver bromoiodide emulsion layer which contained 80 mg per 0.0929 m ^{2 support area of} the corresponding 4-equivalent coupler, ie the coupler whose carbon atom is in the 4-position of the phenol ring was not substituted by any chlorine atom, the layer containing this color coupler being applied in such a thickness that the silver content of the layer was 80 g per 0.0929 m ^{2 of support area} . The sensitivity of layer 6 was 0.7 log exposure greater than that of the emulsion of layer 7. After imagewise exposure and development as described in Example 5, images of excellent sharpness were obtained, which showed excellent speed of the color photographic material.

The same advantageous effects as they result from the examples are then obtained further, when in color photographic materials the color-forming units are different from that in the examples

ao described way can be arranged differently when the color photographic material has only one color-forming unit of the structure according to the invention, i.e. the blue-sensitive unit Unit, for example, does not necessarily have to be the top unit and can, for example, be in their position can be exchanged for the red-sensitive earnestness.

Claims (7)

Patent claims: ! Multilayer color photographic recording material with different spectrally sensitive silver hulogenide emulsion layers which Contain color couplers, the at least one layer association of two adjacent blue-colored Silver halide absorption layers and, if necessary, further layers were bound by different spectra Has sensitivity in which or in which one layer is less sensitive to light is as the other layer and the layers so arranged are that, in the case of imagewise exposure, the light first hits the more photosensitive layer falls, d u r c h marked that the more light-sensitive layer of the layer assembly or the layer assemblies a 4-equivalents coupler and the less light-sensitive layer contains a colorless 2-equi-decoupler, cue form dyes when developing colors, their absorption maxima in each case for the corresponding seiicimer band in the same range lie. 2. Multi-layered CN recording material according to Claim 1, characterized in that it is a hlauemptindlichen. a green-minded and a red-sensitive shift dog with yellow, forming purple-red or blue-green dyes I work couplers. 3. Multi-layer recording material according to claims 1 and 2, characterized in that the .mn layer support most distant Schichtvcrb.ind is blue-sensitive and 4-equivalent and 2-equivalent couplers which produce yellow dyes with the proviso that the 2-equivalent coupler forming a yellow dye is a benzo} lacetanilide coupler is. at one of the two hydrogen atoms sitting on the v-carbon atom through a Fluorine or chloraloma or an aevloxy, cvclo-OXV-. Arvlthio-. Alkvlthio, thiocyano or sulfo group is substituted or a pivalylacetanilide coupler. called one of the two on the \ carbon atom seated hydrogen atoms by a fluorine or chlorine atom or an aeyloxv-. Cvclooxy-. Arvlthio-. Alkvlthio-. Thioxyano or Sulfo group is substituted. 4. Multi-layer recording material according to claim 3, characterized in that it is as Pivalylacetanilide coupler a \ -Fluor - \ - pival \ lacetanilidkuppter contains. 5. Multi-layer recording material according to claim 3, characterized in that it is as 4-equivalent couplers form a yellow dye an open chain gasoline lacetunilide coupler and as a yellow dye-forming 2-equivalent coupler a v-acvloxvbenzovlacetanilide coupler contains. (■>. Multi-layer recording material according to claims 1 and 2, characterized in that it is a blue-sensitive layer structure and an underlying green layer structure with purple dyes forming 4-equivalent and 2-equivalent 5-pyrazolone couplers with the proviso that the 2-equivalent coupler is a 4-acyloxy-5-pyrazolone coupler is. 7. Multi-layer recording material according to claim 2, characterized in that it is a blue-sensitive, one green-sensitive and one roll-sensitive layer connected with yellow, has purple-red or blue-green dyes forming 4-equivalents and 2-equivalents, where it holds that