DE1772306B2 - MULTI-LAYER COLOR PHOTOGRAPHIC RECORDING MATERIAL - Google Patents

Description

are sensitive. As a rule, the blue-sensitive according to a particularly advantageous embodiment Layered dressing, the green-sensitive layered dressing of the invention has a blue-sensitive, one and the red-sensitive layer combination for producing green-sensitive and a red-sensitive layered yellow, purple and blue-green dye images, respectively. bandaged on.

The dye images are created during color development. 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 usual known color couplers are so-called graphic materials of the invention are used

4-equivalent coupler, i.e. i.e., to form one of the, are advantageously compared to the same

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 added 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. H. 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 a sensitivity,

The disadvantage of the known, color-sensitive ones that are preferably about 0.2 to about 1.0 log exposure

Recording material units containing Schichner volumes are greater than the sensitivities

from the German Auslegeschrift 1 121 470 in the other emulsion layers in the layer assemblies

l:; internal type, all layers of which are called the. Preferably the speed ratio is

Contains 2-equivalent color couplers, but is that the individual layers to each other in such a way that the

Although images with improved sharpness are composed of them, the sensitometric curve (the curve,

let put, but that they are less sensitive. 25 in which the developed image density compared to the loga-

On the other hand, there is the algorithm applied to produce the exposure) of each

ger recording materials used Farbkupp- the two emulsion layers in question

for only 4-equivalent 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 Advantageously, the dye-forming

leaves something to be desired. Layer assemblies of the color photographic material

The object of the invention is to provide a multi-layered layer in such a way that their sensitometric thermal color photographic recording material has such a relationship to one another that a different spectrally sensitive silver halide multi-neutral scale and color scales from the minimum layers which contain color couplers are at least up to to the maximum density can be achieved.
According to an advantageous embodiment of the invention blue-sensitive silver halide emulsion layer, the layer vertically furthest away from the support and possibly further layer assemblies on the other side are blue-sensitive and contain yellow dyes of Herer spectral sensitivity, in which 4-equivalent and 2-equivalent couplers, in which one layer is less sensitive to light, the fact that the 2-equivalent forming a yellow dye is than the other layer and the layers so coupled is a benzoylacetanilide coupler in which the light on imagewise exposure is assigned to one of the Both water at the Λ-carbon atom falls on the more light-sensitive layer, to indicate that hydrogen atoms through a fluorine or chlorine atom or that is extremely sensitive and provides images of high acyloxy, cyclooxy, arylthio, alkylthio, thio sharpness. 45 is substituted by a cyano or sulfo group or a pivot

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

standing named color photographic record- «-Carbon atom seated hydrogen atoms through

tion material the more light-sensitive layer of a fluorine or chlorine atom or an acyloxy, cyclo-

Layer association or the layer association an oxy-, arylthio-, alkylthio-. Thiocyano or sulfo-

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, whose pivalylacetanilide coupler is an A-fluoro-rx-pi-

Absorption maxima in each case for the corresponding valylacetanilide 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 invention thus consists of a yellow dye-forming 4-equivalent coupler base with an open-chain benzoylacetanilide coupler applied thereon and, as arranged, 2-equivalent couplers formed from silver halide emulsion layers forming a yellow dye-sensitive coupler , being an acyloxybenzoylacetanilide coupler.
at least one layer structure of the already described structure. The individual layer assemblies of the invention further under the blue are preferably arranged in such a way that the sensitive layer assembly provides 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 three different- According to a preferred embodiment of the invention

dene layer structures 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 dye an open-chain Benzoylacetanüidkupp-

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

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

d) the magenta dye-forming 2-equivalent coupler a + acyloxy-S-pyrazoion 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 dyed so Photographic material 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 into the * 5 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, preferably between 25:75 and 90:10.

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

The material B described in Example 1 has a yellow dye-forming unit composed of photosensitive Layers which form the outermost or upper unit of the 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 have lower sensitivities consisted of finer grain emulsions. Both emulsions were made by a process as described by Trivelli and Smith in “Phot. Journal ", Vol. 79, p. 330 (1939).

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 blue-sensitive emulsion layer with a yellow one Dye forming couplers;

Layer 3 glass filter layer;

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

Layer 5 less sensitive green sensitive c

Emulsion layer containing a magenta dye forming coupler;

Layer 6 red-sensitive emulsion layer init a cyan dye forming coupler;

Layer 7 less sensitive red sensitive Em 11-

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-Amy] phenoxy) -n-butyrylamino-4-chloro-5-methylphenol, to form a cyan dye image according to U.S. Patent 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 forming a yellow dye, namely the sodium salt of rt-pivalyl-a- ^ sulfophenoxy ^ iN-methyl-N-octadecyIsulfamyl) -acetanilides, ie the 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-chloroacetanilides 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 Süber was ^{applied to a support area of 0.0929 m 2.}

The layer 2 of the photographic material B after imagewise exposure and development of the

contained 75 mg of the yellow dye forming material as described in Example 1

2-equivalent coupler, which in turn is also used to produce the excellent sharp images obtained

Layers 1 and 2 of photographic material A have excellent sensitivity of the used

was used, per 0.0929 m ^{2 support area} and 5 color photographic material.

40 mg silver per 0.0929 m ^{2 support area} . Corresponding favorable results were obtained

The two color photographic materials were used to make up the color photographic material

then in an intensity scale sensitometer under B of Example 1 other blue-sensitive, yellow ones

Using a Wratten No. 47 B filter with blue dye-forming layers that were used

Exposed to light and then color developed. The 4-equivalent couplers which form other yellow dyes

Winding was carried out according to a process that in »Abrid- of the formula I and other yellow dyes

ged Operating Specifications for ECO-2 Process ", containing 2-equivalent couplers of the formula II, where

July 1964, issued by the Eastman Kodak The Ratio of Silver in the More Sensitive Emul-

Company, Motion Picture and Education Marketing sion on silver in the less sensitive emulsion

Division to the Professional Film Processing Labora- 15 could fluctuate between about 1:99 and about 99: 1.

! tories in the Unites States. In the following examples 4 and 5, more

! The photographic material B, which described more SiI-layered color photographic materials

ber contained, as the photographic material A, possessed ben both of the yellow dye forming unit

a relative speed of 182 compared to as well as a magenta dye forming unit

j have a relative sensitivity of 100 of the material A, 20 according to the invention.

with no noticeable loss of sharpness in relation to I 4

occurred same as material A. ^p

The photographic material B had a significant There was a further flour-layered color photo

tend better sharpness than a corresponding material C, graphic material F with the structure of the photo-

in which both yellow dye-forming layers were prepared 25 graphic material B of Example 1,

j th 4-equivalent couplers, in which case, however, instead of layer 5 of the photographic

a higher silver concentration than in the case of material B, a green-sensitive gelatin

! Photographic material B became necessary. Silver bromoiodide emulsion layer was used,

the per 0.0929 m ^a carrier surface 75 mg of the one pure

B is ρ ie 1 2 ₃₀ p _Urred dye-forming 2-equivalent coupler According to the process described in Example 1 l- (2,4,6-trichlorophenyl) -3 - (- 3- [a> - (2,4-di- tert-amyl, a multilayer color photographic maphenoxy) acetamido] benzamido) -4-acetoxy-5-pyrazoterial B was produced, but this time a different ion, ie coupler No. 3 according to the USA patent blue-sensitive, a yellow dye image Educational writing contained 3,311,476. The silver content of the layer unit was formed. In the case of the photographic 35, 40 mg of silver per 0.0929 m ^{2 of support area} corresponded. On material D in layer 2 instead of the position of layer 4 of photographic material B 2-equivalent coupler, which was further used to build up layer 2, a green-sensitive gelatin silver of photographic material B, bromoiodide emulsion layer was used, which per an equimolar amount of the Coupler a-acetoxy - «- {3- 0.0929 m ^{2 support area} 80 mg of the 4-equivalent coupling [ _Ä - (2,4-di-tert-amylphenoxy) butyramido] benzoyl} -40 lers l- ( 2 ', 4', 6'-Trichlorophenyl) -3- [3 "- (2 '", 4'"- di-tert-2-methoxyacetanilide, ie coupler No. 11 of the kanadi- amylphenoxyacetamido) -benzamido] - 5-pyrazolone, seen in Patent Specification 735,836, as a 2-equivalent coupler measured in column 17, lines 56 and 57 of the U.S. patent, further this time contained in layer 1 0346129. The layer was thus used as a 4-equivalent coupler «- {3- |> - (2,4-Di-tert-amyl- applied that on a support surface of 0.0929 m ² phenoxy) butyramido] benzoyl) -2-methoxyacetanilide, 45 80 mg Sil About accounted for. The sensitivity of Layer 4 corresponding to U.S. Patent Coupler No. XIV was 0.7 log exposure greater than that of Emulsion-2,875,057 when used as a 4-equivalent coupler. layer 5.

After imagewise exposure and development, as in After imagewise exposure to blue light, as in

Example 1 described, were again excellent- Example 1 described, and with green light and Entnet Sharp images are obtained which have an excellent 5 ° winding according to the sensitivity described in Example 1 The photographic drive used was in turn awarded images

Material. Get sharpness that has excellent sensitivity of the photographic material. Example 3

Another multi-layer color photo was taken

Graphic material E prepared following the same procedure described in Example 4

Structure like the photographic material B of the example, a further color photographic material G Game 1 owned, but this time in layer 2 as produced, with the construction of layer 5 diesma 2-equivalent color coupler Ä-Fluoro-oc-pivalyl-5-Ij> - (2,4- but forms a purple dye di-tert-amylphenoxyVbutyramidol ^ -chloroacetamlide, 60 2-equivalent coupler 1- (2,4,6-trichlorophenyl) -3- (4-ni according to Coupler No. 5 of U.S. Patent 3,277,155 troanilino) -4-stearoyloxy-5-pyrazolone according to Kupple was used. Also, in Layer 1, No. 2 of U.S. Patent 3,311,476 was used as a 4-equivalent coupler became an equimolar amount. Furthermore, the layer was built up «-Pivalyl-5-Iy '- (2,4-di-tert.-amylphenoxy) -butyramido] - an equimolar amount of the one purple color 2-chloroacetanilide, according to Coupler No. 10 of the USA - 65 substance-forming 4-equivalent coupler 1- (2,4,6-Trichlc Patent 3,265,506, instead of the one used to build up the rophenyl> 3- (3-nitroaniüno) -5-pyrazolone, according to Kupt Layer 1 of Pictographic Material B, US Pat. No. 5, US Pat. No. 3,152,896, to Stell th coupler used. des to build up layer 4 of the photographic

Materials F used 4-equivalent coupler silver bromoiodide emulsion layer containing 80 mg per

turns. 0.0929 m ^{2 support area of} the corresponding 4-equiva-

The photographic material was then as contained in decoupler; H. the coupler whose co-

Example 1 described exposed and developed. The Erlenstoffatom in the 4-position of the phenol ring through

The results obtained corresponded to those in Example 4 with no chlorine atom substituted, these being

held results. Color coupler-containing layer in such a

The following example 6 describes a typical multi-strength that was applied to the silver content of the

layered color photographic material after the layer was 80 g per 0.0929 m ^{2 of support area} . the

Invention, which a yellow dye-forming single sensitivity of layer 6 was 0.7 log load

that is, a magenta dye-forming unit and io exposure greater than that of the emulsion of layer 7.

a cyan dye-forming unit according to the image-wise exposure and development, such as

Invention having. Described in Example 5, images were excellent-

B e 's r> ie 1 6 ^ter sharpness ^nutrition l ^th> the excellent recom-

^p sensitivity of the color photographic material ER-

After the method described in Example 5 15 let know.

Another color photographic material H was used. The same advantageous effects as produced from, but this time with layer 7 of the examples, are then furthermore kept in material F by a red-sensitized gelatine sil- if the berbromoiodide emulsion was replaced in color photographic materials, dieproO, 0929m ² color-forming units of mg in the examples support surface 75 of the cyan dye education "° procedure described different way in the Denden 2-equivalent coupler 2-a- (p-tert-Amylphen- arranges, when the color photographic Mateoxy ) -n-butyryla "iino-4-chloro-5-methylphenol, according to rial only has one color-forming unit of the structure according to the invention, column 15, lines 74 and 75 of the USA patent, i.e. the blue-sensitive 3,046,129 The silver content of layer 7, for example, does not necessarily need to be 40 mg of silver per 0.0929 m ^{2 of} carrier surface The first unit and can, for example, in tere, the layer 6 of the photographic material was interchanged with the red-sensitive unit rials F replaced by a red-sensitized gelatin.

Claims (7)

1 2 claim 2, characterized in that there are claims: blue-sensitive, green-sensitive and red-sensitive layered dressing with yellow, 1. Multilayer color photographic on-purple or blue-green dyes forming Has drawing material with different spectral temperature 5 4-equivalent and 2-equivalent couplers, sensitive silver halide emulsion layers, provided that Color couplers contain at least one Layered structure of two adjacent blue a) the 4-equiva- sensitive silver halide emulsion layers decoupler an open-chain benzoylacetani- and, if necessary, further layer assemblies and - 10 lid couplers, rer spectral sensitivity, in which or b) the yellow dye-forming 2-equiv in which one layer is less light-sensitive valent coupler an a-acyloxybenzoylacetaniiid- is than the other layer and the layers are so coupled, are ordered so that on imagewise exposure c) the purple dye forming Light first onto the more photosensitive layer 15 4-equivalent coupler a 5-pyrazolone coupler, falls, characterized in that d) the purple dye forming the more light-sensitive layer of the layered 2-equivalent coupler is a 4-acyloxy-5-pyrazo- tape or the layer bandages a 4-equilon coupler, valent coupler and the less light-sensitive e) the one which forms a blue-green dye Layer a colorless 2-equivalent couplers corresponds _ao 4-equivalent coupler is a phenolic coupler that form dyes during color development, and their absorption maxima in each case for the ent- f) the blue-green dye forming speaking layer structure in the same spectral 2-equivalent coupler one in 4-position through area lie. a chlorine atom substituted phenolic 2. Multilayer recording material after 25 is coupler. Claim 1, characterized in that there is a
blue-sensitive, one green-sensitive and a red-sensitive layered dressing with yellow, forming purple-red or blue-green dyes
Has color couplers. 30th 3. Multi-layer recording material according to the invention relates to a multi-layer color denier Claims 1 and 2, characterized in that photographic recording material with Verdaß the layer that is furthest away from the layer support, spectrally sensitive silver halide emulband is sensitive to blue and yellow dyes sion layers that contain color couplers, the least 4-equivalent and 2-equivalent coupler 35 contains at least one layer assembly of two adjacent ones, with the proviso that the one yellow dye forms the blue-sensitive silver halide emulsion 2-equivalent coupler a benzoylacetane layers and optionally further layer assemblies Lidkuppler is in which one of the two am \ -Koh- has the other spectral sensitivity, in which hydrogen atoms seated on the hydrogen atom or in which the one layer is less light-sensitive-fluorine- or chlorine atom or an acyloxy-, cyclo- 40 Hch as the other layer and the layers as anoxy-, Arylthio, alkylthio, thiocyano or sulfo are ordered that the light is exposed imagewise group is substituted or a Pivalylacetanilid- falls first on the light-sensitive layer, coupler, in which one of the two at the * -Carbon- The well-known multilayer color photographic substance atom sitting hydrogen atoms through a see recording materials (see. For example Fluorine or chlorine atom or an acyloxy, 45 the USA. Patent 2 252 798) have normal cyclooxy, Arylthio, alkylthio, thioxyano or three selectively sensitized emulsion layers Sulfo group is substituted. on, which is arranged on one side of a support 4. Multilayer recording material according to are. The layer furthest from the substrate is claim 3, characterized in that it is usually blue-sensitive, the middle pivalylacetanilide coupler contains an α-fluoro - * - pivalyl- ₅₀ layer green-sensitive and the layer substrate contains acetanilide coupler. the next layer sensitive to red. In between 5. Multilayer recording material after the blue-sensitive layer and the green-sensitive layer Claim 3, characterized in that it can be a bleachable yellow filter layer as the borrowed layer a yellow dye-forming 4-equivalent coupling arranged to absorb blue radiation ler an open-chain benzoylacetanilide coupler 55 which has passed through the blue-sensitive layer. Ge and, if necessary, an additional intermediate layer can be used as a yellow dye-forming 2-equivalents An x-acyloxybenzoylacetanilidene may be present as a decoupler. includes coupler. There are also (see, for example, the German 6. Multi-layer recording material according to Auslegeschrift 1121 470) color photographic recording Claims 1 and 2, characterized in that 60 drawing materials of the type described be that it knows a blue-sensitive layer structure, in which the individual, differently sensitive and a green-sensitive layer arranged underneath by so-called color-forming Chen layer dressings have been replaced with purple dyes. Layer structures made up of two layers are replaced. Tuesday forming 4-equivalent and 2-equivalent 5-pyra- two layers of each layer structure be zolonkupplern, whereby the rule is that the 65 are usually composed of two light-sensitive 2-equivalent coupler a 4-acyloxy-5-pyrazolone emulsion layers, which are practically opposite to the same coupler is. primary color range, i.e. H. the blue, green 7. Multi-layer recording material according to or red color range of the visible spectrum emr.