CA1109716A - Colour photographic recording material - Google Patents
Colour photographic recording materialInfo
- Publication number
- CA1109716A CA1109716A CA278,751A CA278751A CA1109716A CA 1109716 A CA1109716 A CA 1109716A CA 278751 A CA278751 A CA 278751A CA 1109716 A CA1109716 A CA 1109716A
- Authority
- CA
- Canada
- Prior art keywords
- sensitive
- silver halide
- emulsion layer
- halide emulsion
- layers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
- G03C2001/03517—Chloride content
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/3029—Materials characterised by a specific arrangement of layers, e.g. unit layers, or layers having a specific function
- G03C2007/3034—Unit layer
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
Abstract
COLOUR PHOTOGRAPHIC RECORDING MATERIAL
Abstract of the disclosure In a colour photographic material comprising a plurality plurality of light-sensitive and non light-sensitive layers including at least two red sensitive coupler-containing silver halide emulsion layers of different speed, at least two green sensitive coupler-containing silver halide emulsion layers of different speed and a blue sensitive coupler-containing silver halide emulsion layer as well as a yellow filter layer located closer to the support than the blue sensitive silver halide emulsion layer but further removed from the support than any of the red-sensitive or green sensitive layers, the sensitivity of the magenta and particularly of the cyan partial image is significantly improved if the more sensitive red sensitive together with the more sensitive green sensitive silver halide emulsion layer forms a comparatively more sensitive emulsion layer unit which is located further removed from the support than a corresponding comparatively less sensitive emulsion layer unit formed by the less sensitive green sensitive and the less sensitive red sensitive silver halide emulsion layer and an additional comparatively insensitive silver halide emulsion layer which contains silver chloride and has an average grain diameter of less than 0.1 µm is arranged within the comparatively more sensitive emulsion layer unit or closely adjacent thereto.
Abstract of the disclosure In a colour photographic material comprising a plurality plurality of light-sensitive and non light-sensitive layers including at least two red sensitive coupler-containing silver halide emulsion layers of different speed, at least two green sensitive coupler-containing silver halide emulsion layers of different speed and a blue sensitive coupler-containing silver halide emulsion layer as well as a yellow filter layer located closer to the support than the blue sensitive silver halide emulsion layer but further removed from the support than any of the red-sensitive or green sensitive layers, the sensitivity of the magenta and particularly of the cyan partial image is significantly improved if the more sensitive red sensitive together with the more sensitive green sensitive silver halide emulsion layer forms a comparatively more sensitive emulsion layer unit which is located further removed from the support than a corresponding comparatively less sensitive emulsion layer unit formed by the less sensitive green sensitive and the less sensitive red sensitive silver halide emulsion layer and an additional comparatively insensitive silver halide emulsion layer which contains silver chloride and has an average grain diameter of less than 0.1 µm is arranged within the comparatively more sensitive emulsion layer unit or closely adjacent thereto.
Description
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This invention relates to a colour photographic recording material comprising several silver halide emulsion layers, at least two of which contribute to the formation of the cyan partial colour image and at least two others to the formation of the magenta partial colour image and in which improved sensitivity, particularly in the cyan partial colour image, is achieved by a special arrangement of the layers.
I.t is known to produce coloured photographic images by means of recording materials comprising a substrate carrying a red-sensitive, a green-sensitive and a blue-sensitive silver halide emulsion layer, each of said silver halide emulsion layers l~aving associated with it non~diffusible colour c~ lers for production of the cyan, magenta and yellow partial colour images respectively ; 15 the colour of the partial colour image produced being in each case complementary to the spectral sensitivity of the associated silver halide emulsion layer. The usual colour photographic materials contain other layers in addition, for example a yellow filter layer between the blue-sensitive silver halide emulsion layer whlch lies on top and the green-sensitive silver halide emulsion layer underneath it, as well as an antihalation layer ~etween the sub~trate and the lowermost silver halide emulsion layer.
Additional intermediate layers of gelatine and a covering layer may also be provided.
It is also known to produce colour photographic images by means of photographic materials in which at least two silver halide emulsion layers are provided for producing each of one or more of the three partial colour images. Thus according to British Patent Specification No.818,687, the ; ~0 lowermost light-sensitive colour producing layer unit of a colour photographic multilayered material consists of two partial layers containing silver halide and colour coupler and . ~
.,,; , both sensitized to light of the same spectral region, the upper of these two partial la~ers havin~ the ~reater sensi-tivity. Gen~ Patent Specification No. 1,121,470 discloses the use of such double layers of differing sensitivity to light of the same spectral region in whi~- the more sensi~ive layer yields the lcwer colour density on colour development. This makes it possible to increase the sensitivity without at the same time deleteriously affecting the graininess Colour photogr~hic recording materials having double layers for the various spectral regions have also been dis-closed in US Patent Specifications No.3,663,228 and 3,849,138.
Here ~gain, the upper of the two partial layers which are sensitive to the same spectral region has the higher sensitivity, However, the layer combinations described in these Patent Specifications are principally intended to increase the ex-posure latitude and there is no mention of an increase in the sensitivity, Figure lc of these two US Patent Specifications shows a material containing two laminates which are separated from each other by a neutral grey filter and each of which consists of a red-sensitive, a green-sensitive and a blue-; sensitive silver halide emulsion layer This Jneans that the two partial layers of differingsensitivity (s~) wl~ich are both sensitive to light of the same spectral region are in this case not situated adjacent to each other but in separate laminates which differ from each other in their general sensitivity (sp~), each lam~te oontaining several silver halide emulsion layers of differing spectral sensi-tivity but c~rable general sensitivity (speed). Partial layers having the same spectral sensitivity are in each case separated frcm each other by at least one layer having different spectral sensitivities and by the grey filter. A similar arrangement of layers which also achieves an increased exposure latitude :
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but contains coloured filters has been disclosed in US
Defensive Publication No. T 8~0 00~.
Futhermore, arrangements of layers in which red-sensitive and/or green sensitive partial layers are situated ~Dve the blue-sensitive silver halide emulsion layer in order to improve the sharpness of the image have been disclosed in - German Offenlegungsschriften No.2,453,654 and No.2,453,664.
These arrangements, however, are inferior in their colour reproduction and the materials are therefore only suitable when used with certain sources of light, e.g. tungsten light.
Lastly, an arrangement of layers designed to improve the sensitivity has been disclosed in German Offenlegungsschrift No.2,530,645, according to which 1. the more sensitive of the two green-sensitive silver halide emulsion layers and the more sensitive of the two red-sensitive silver halide emulsion layers are situated adjacent to each other in an emulsion layer unit which is comparatively more sensitive;
This invention relates to a colour photographic recording material comprising several silver halide emulsion layers, at least two of which contribute to the formation of the cyan partial colour image and at least two others to the formation of the magenta partial colour image and in which improved sensitivity, particularly in the cyan partial colour image, is achieved by a special arrangement of the layers.
I.t is known to produce coloured photographic images by means of recording materials comprising a substrate carrying a red-sensitive, a green-sensitive and a blue-sensitive silver halide emulsion layer, each of said silver halide emulsion layers l~aving associated with it non~diffusible colour c~ lers for production of the cyan, magenta and yellow partial colour images respectively ; 15 the colour of the partial colour image produced being in each case complementary to the spectral sensitivity of the associated silver halide emulsion layer. The usual colour photographic materials contain other layers in addition, for example a yellow filter layer between the blue-sensitive silver halide emulsion layer whlch lies on top and the green-sensitive silver halide emulsion layer underneath it, as well as an antihalation layer ~etween the sub~trate and the lowermost silver halide emulsion layer.
Additional intermediate layers of gelatine and a covering layer may also be provided.
It is also known to produce colour photographic images by means of photographic materials in which at least two silver halide emulsion layers are provided for producing each of one or more of the three partial colour images. Thus according to British Patent Specification No.818,687, the ; ~0 lowermost light-sensitive colour producing layer unit of a colour photographic multilayered material consists of two partial layers containing silver halide and colour coupler and . ~
.,,; , both sensitized to light of the same spectral region, the upper of these two partial la~ers havin~ the ~reater sensi-tivity. Gen~ Patent Specification No. 1,121,470 discloses the use of such double layers of differing sensitivity to light of the same spectral region in whi~- the more sensi~ive layer yields the lcwer colour density on colour development. This makes it possible to increase the sensitivity without at the same time deleteriously affecting the graininess Colour photogr~hic recording materials having double layers for the various spectral regions have also been dis-closed in US Patent Specifications No.3,663,228 and 3,849,138.
Here ~gain, the upper of the two partial layers which are sensitive to the same spectral region has the higher sensitivity, However, the layer combinations described in these Patent Specifications are principally intended to increase the ex-posure latitude and there is no mention of an increase in the sensitivity, Figure lc of these two US Patent Specifications shows a material containing two laminates which are separated from each other by a neutral grey filter and each of which consists of a red-sensitive, a green-sensitive and a blue-; sensitive silver halide emulsion layer This Jneans that the two partial layers of differingsensitivity (s~) wl~ich are both sensitive to light of the same spectral region are in this case not situated adjacent to each other but in separate laminates which differ from each other in their general sensitivity (sp~), each lam~te oontaining several silver halide emulsion layers of differing spectral sensi-tivity but c~rable general sensitivity (speed). Partial layers having the same spectral sensitivity are in each case separated frcm each other by at least one layer having different spectral sensitivities and by the grey filter. A similar arrangement of layers which also achieves an increased exposure latitude :
'` ` ' `' .` ' ' '' :
but contains coloured filters has been disclosed in US
Defensive Publication No. T 8~0 00~.
Futhermore, arrangements of layers in which red-sensitive and/or green sensitive partial layers are situated ~Dve the blue-sensitive silver halide emulsion layer in order to improve the sharpness of the image have been disclosed in - German Offenlegungsschriften No.2,453,654 and No.2,453,664.
These arrangements, however, are inferior in their colour reproduction and the materials are therefore only suitable when used with certain sources of light, e.g. tungsten light.
Lastly, an arrangement of layers designed to improve the sensitivity has been disclosed in German Offenlegungsschrift No.2,530,645, according to which 1. the more sensitive of the two green-sensitive silver halide emulsion layers and the more sensitive of the two red-sensitive silver halide emulsion layers are situated adjacent to each other in an emulsion layer unit which is comparatively more sensitive;
2. the less sensitive of the two green-sensitive silver halide emulsion layers and the less sensitive of the two red-sensitive silver halide emulsion layers are ; arranged adjacent to each other in a comparatively less sensitive emulsion layer unit;
3, the less sensitive emulsion layer unit is situated closer to the substrate than the more sensitive emulsion layer unit;
4. in each of the two emulsion layer units, the red-sensitive emulsion layer is closer to the substrate than the green-sensitive emulsion layer and
5. the less sensitive green-sensitive silver halide emulsion layer is adjacent to the more sensitive red-sensitive silver halide emulsion layer.
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According to German Offenlegungsschrift No.2,530,645, the light used for exposure passes through the blue-sensitive layer or layers before reaching the red-sensitive and green-sensitive layers. This means that the blue-sensitive layers are situated above the layers which are sensitive to red and green light and above the yellow filter layer.
lt is an object of the present invention to provide a colour photographic recording material comprising several silver halide emulsion layers of differing sepctral sensi-tivities, which material shows an even greater improvement insensitlvity compared with known colour photographic materials, particularly in the cyan and magenta partial colour images.
The invention relates to a colour photographic recording material consisting of (a) a substrate, (b) applied to this substrate, differently sensitized silver halide emulsion layers containing non-diffusible colour couplers, at least two of which emulsion layers are sensitive to red light and differ from each other in their sensitivity (s~) and at least two others of which are sensitive to green light and differ from each other in their sensitivity ~speed), the more sensitive of the .. ..
two red-sensitive and the more sensitive of the two green-sensitive silver halide emulsion layers being in each case further removed from the substrate than the corresponding less sensitiv¢ silver halide emulsion layer, at least one of the silver halide emulsion layers being sensitive to blue light and further removed from the substrate than any of the red sensitive or green sensitive silver halide emulsion layers, and (c) at least one yellow filter layer which is further removed from the substrate than any of the red-sensitive or green-sensitive silver halide emulsion layers, and (d) ....
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optionally additional layers which are not light-sensitive, characterised in that the silver halide emulsion layers are arranged on the substrate in such a manner that l, the more sensitive of the two green-sensitive silver halide emulsion layers and the more sensitive of the two red-sensitive silver halide emulsion layers are combined to ~orm a comparatively more sensitive emulsion layer unit which is arranged further away from the substrate than both the less sensitive green-sensitive and the less sensitive red-sensitive silver halide emulsion layer; and that 2, at least one additional comparatively insensitive chloride-oontaining silver halide emulsion layer is arranged within the comparatively more sensitive emulsion layer unit or immediately adjacent thereto, The additional, comparatively insensitive silver halide emulsion layer which contains chloride is preferably a non-sensitized silver halide emulsion containing at least 20 mol :' % of sllver chloride. This additional layer is said to ; 20 be comparatively insensitive to indicate that its .~
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sensitivity to light is very low and even lower than that of the silver halide of the comparatively less sensitive emulsion layer unit. As this layer acts mainly as a source of silver halide for development in other layers there is no need for any light sensitivity in this layer. ~he silver halide in this additional layer thus preferably consists of pure silver chloride or a silver chlorobromide containing up to 80 mol /0 of silver bromide, i.e. the proportion of silver chloride in the total quantity of silver halide is between 20 and lO0 mol /0.
Sensitization, in particular spectral sensitization, is unnecessary. The silver halide emulsions used for the additional, chloride-containing silver halide emulsion layers are preferably of the kind in which the silver halide grains have an average grain diameter of less than 0.5 ~m. Emulsions of this kind include the silver halide emulsions known a~
Mikrat emulsion or Lippman emulsions which have an average grain diameter of less than O.l ~m. These emulsionsare . .
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relatively insensitive to light. The sensitivity of the additional, chloride-containing silver halide emulsions to blue light is preferably less by 10 to 50 log I.t units than that of the image recording blue sensitive layer.
The additional, comparatively insensitive silver halide emulsion layer may be arranged in any position within ; the comparatively more sensitive emulsion layer unit, i.e., - between the more sensitive red-sensitive silver halide emulsion layer and the more sensitive green-sensitive silver halide emulsion layer or above or below these layers. At the same time, two or three additional, relatively insensitive chloride-containing emulsion layers can be incorporated in the com-paratively more sensitive emulsion layer unit, for example immediately above and below the comparatively more sensitive emulsion layer unit as well as within the comparatively more sensitive emulsion layer unit between the red-sensitive and the green-sensitive silver halide emulsion layer. In this way, the more sensitive partial layers of the arrangement are more or less embedded in intermediate layers containing silver chloride.
In one arrangement which is particularly preferred, a chloride Mikrat emulsion layer is arranged instead of the usual gelatine intermediate layer between the more sensitive red-sensitive and the more sensitive green-sensitive silver halide emulsion layer. In another preferred arrangement, a chloride-containing silver halide emulsion layer having an average grain diameter of preferably between 0.1 and 0.5JLm is arranged between the comparatively more sensitive emulsion layer unit and the yellow filter layer in addition to the above mentioned chloride Mikrat emulsion layer which is arranged between the red-sensitive and the green-sensitive silver halide emulsion layer.
.:' ~1~97i~i It is not intended that an i~age should be recorded in the comparatively insensitive chloride-containing silver halide emulsion layer used according to the invention. Such - a layer, however, has an advantageous effect on the sensitivity of the adjacent, image recording layers, particularly on the more sensitive of the red-sensitive and/or the more sensitive o~ the green-sensitive silver halide emulsion layers. This effect o~ enhancing the sensitivity is evidently the greater the smaller the grain size of the silver halide grains in the additional silver halide emulsion layer and hence the greater their solubility and their capacity to contribute to the physical development of the adjacent, more sensitive silver halide emulsion layers.
The use of relatively insensitive silver halide emulsion layers in colour photographic multilayered materials is not new. Layers of this kind have previously been used mainly to prevent unwanted diffusion of sensitizing dyes into adjacent layers of diffe~ing spectral sensitivity (sensitizer barrier s, layer), to prevent unwanted diffusion of development inhibitor into other - 20 layers or into the processing solution (inhibitor barrler layer) or to pro-. duce a mas]cing image in a process following colour developnEnt.
In the colour photographic materials according to the .. invention, the additional, comparatively light-insensitive, : chloride-containing silver halide emulsion layers function as silver halide donors in the development of the adjacent ; silver halide layers which contain highly sensitive, and hence relatively coarse grained, silver halide. A marked increase in sensitivity is observed in the presence of such additional layers. This effect is particularly marked in the layer arrangement according to the invention in which, in contrast to the conventional double layer arrangement, the highly sensitive red-sensitive or green-sensitive silver ;' . -~1~97~
halide emulsion layers are not situated adjacent to the : corresponding less sensitive layers of the same spectral sensitivity, which would otherwise also function as silver halide donors The optimum quantity of silver halide to be used in the additional, less sensitive silver halide emulsion layer can easily be determined by the man of the art with the aid of a few comparison tests. It preferably corresponds to a silver nitrate quantity of from ~.05 to 1.2 g/m .
The additional, chloride-containing silver halide emulsion layers used according to the invention are able to exert yet another advantageous effect, that is to say they are able to suppress the diffusion of bromide or iodide ions released by development in other layers into layers of diffe~
rent spectral sensitivity. Such an effect i9 particularly important between the blue sensitive layer and the comparatively more sensitive emulsion layer unit. Such an additional layer is therefore provided between the blue sensitive silver halide emulsion layer and the comparatively more sensitive emulsion layer unit in order to suppress the diffusion of bromide or iodide ions and it is particularly advantageous to provide such a layer between the last mentioned, comparatively more sensitive emulsion layer unit and the yellow filter layer.
These silver halide emulsion layers preferably have an average grain diameter of between O.l to 0.5,um.
The red-sensitive and greenffensitive silver halide ` emulsion layers may be arranged in any sequence in the comparatively more sensitive emulsion layer unit. The red-sensitive silver halide emulsion layer may be arranged either above or below the green-sensitive layer but is preferably arranged below it.
In the comparatively less sensitive emulsion layer unit, the two light-sensitive layers of differing spectral sensitivi-~1~9~
ties may again be arranged as desired but again the green-sensitive silver halide emulsion layer is preferably arranged above the red-sensitive layer. The comparatively less sensitive emulsion layer unit may also contain two or more red-sensitive and two or more green-sensitive silver halide emulsion layers instead of the single red-sensitive and single green-sensitive silver halide emulsion layer, i~ which case the two or more layers having the same spectral sensitivity preferably differ from each other in their general sensitivity (speed) and are arranged so that the higher the sensi-tivity of a layer having a given spectral sensitivity, the further is such a layer removed from the substrate. Such a plurality of layers may be subdivided into sub-units of sub-stantially comparable general sensitivltyor sub-units of the same spectral sensitivity.
In the colour photographic recording material according to the invention, two or more blue sensitive silver halide emulsion layers may be provided in known manner instead of a single blue-sensitive silver halide emulsion layer for producing the yellow partial colour image.
In addition to the layers already mentioned above, the colour photographic recording material according to the invention may contain other, light-insensitive auxiliary layers, e.g. adhesive layers, antihalation layers or covering layers and in particular intermediate layers between the light-sensitive layers to ensure effective prevention of diffusion of developer oxidation products from one layer into another. For this purpose, such inter-mediate layers may also contain certain compounds which are ~0 capable of reacting with developer oxidation products.
Layers of this kind are preferably arranged between adjacent light-sensitive layers which differ from each other in their : `
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spectral sensitivity.
As already mentioned above, the colour photographic recording material accordin~ to the invention contains at . .
least two light-sensitive partial layers of differing speed for producing each partial colour image, at least for producing the cyan and the magenta partial colour image.
The relevant sensitivity in these partial layers is not the absolute sensitivity but the effective sensitivity, taking into account the particular position of the partial layer within the multilayere~ colour photographic material. The absolute sensitivity is the sensitivity of an individual layer if determined separately, that is in absence of other layers. The effective sensitivity of a light sensitive layer within a multilayer colour photographic element ., may be somewhat lower than the absolute sensitivity partly due to the absorption of certain amounts of .: exposure light in upper layers and partly due to the fact that development in lower layers proceeds more slowly than in upper layers. Absolute sensitivity and effective sensitivity refer to the "general sensitivity"
which in contrast to the spectral sensitivity may also be called "speed".
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The difference in effective sensitivity is suitable between 0.2 and l.0 relative log I.t units. In any individual case, the sensitivity difference is chosen so that colour photo-graphic processing results in a balanced gradation curve without perceptible distortion. The composition of the more sensitive layer is then suitable calculated to produce a lower colour density on colour development than that obtained in the less se~itive layer. This can be achieved by using a lower application of silver and/or a different coupler/silver ratio.
Associated with each of the above mentioned light-sensitive silver halide emulsion layers (with the exclusion of the additional, chloride-containing comparatively light insensitive silver halide emulsion layers) is a colour coupler ; 15 wh~ch is capable of reacting with colour developer oxidation products to form a non-diffusible dye. However, the additional, chloride-containing silver halide emulsion layer may also contain colour couplers. The colour couplers are preferably also non-diffusible and situated in the light-sensitive layer itself or in a layer closely adjacent thereto. The colour couplers associated with the two partial layers which ., .
have the same spectral sensitivity need not necessarily be ' `''''`
., ~1~97~6 ' the same, provided that they give rise to substantially the same oolour on colour development, normally a colour which is complementary to the colour of the light to which the light-sensitive silver halide emulsion layers are sensitive. The red-sensitive silver halide emulsion layers therefore have associated with them at least one non-diffusible colour coupler each for the production of the cyan partial colour image, generally a coupler based on phenol or a-naphthol.
The green-sensitive silver halide emulsion layers each contain at least one non-diffusible colour coupler for producing the magenta partial colour image, usually a colour coupler based on 5-pyrazolone or indazolone. The blue-sensitive silver halide emulsion layers each contain at least one non-diffusible colour coupler for producing the yellow partial colour image, generally a colour coupler having an open chain keto methylene group. Large numbers of colour couplers of these kinds are known and have been d0scribed in numerous Patent Specifications. References may be found, for example9 in "Farbkuppler" published by W.Pel~
in "Mitteilungen aus den Forschungslaboratorien der Agfa, Leverkusen/M~nchen", Volume III, 111, (1961), and in the publication by K.Venkataraman in "The Chemistry of Synthetic dyes", Vol.4, 341 to 387, Academic Press (1971).
The colour couplers may either be the usual 4-equivalent couplers or they may be 2-equivalent couplers which require a smaller quantity of silver halide for colour production.
2-equivalent couplers are derived, as is known, from 4-equivalent couplers in that they contain, in the coupling position, a substituent which is released in the coupling reaction. 2-equivalent couplers which may be used according to the invention include both couplers which are practically colourless and couplers which have an intense colour of their ,~ .
own which disappears during the colour coupling reaction or is replaced by the colour of the image dye produced. Accord-ing to the invention, the last mentioned couplers may in addition be present in the light-sensitive silver halide emulsion layers, where they serve as masking couplers to compensate for unwanted side densities of the image dyes.
Suitable 2-equivalent couplers also include the known white couplers, but these do not give rise to a dye in their ~' reaction with colour developer oxidation products and there-fore do not directly contribute to the formation of the colour image. The 2-equivalent couplers also include the known DI~ couplers, which are couplers containing, in the coupling position, a group which is released as a diffusible development inhibitor by the reaction with colour developer oxidation products.
Colour coupler mixtures may be used as required to . ., obtain a desired colour shade or reactivity, Water-soluble couplers, for example, may be used in combination with . .
hydrophobic, water-insoluble couplers.
Whereas the water-soluble couplers are in most cases added to the emulsion in the form of aqueous alkaline solutions, the hydrophobic colours are suitably incorporated by means of - one of the known emulsification processes in which, for example, the coupler is dissolved in an organic solvent, optionally in the presence of a high boiling coupler solvent, and is then dispersed in a gelatine solution. Dibutyl phthalate and tricresyl phosphate are examples of high boiling . .
coupler solvents. Other coupler solvents have been described, for example, in US Patent Specifications No.2,322,027;
3,689,271; 3,764,336 and 3,765,897.
It is also possible to prepare aqueous dispersion of the hydrophobic couplers and add them to the casting solutions.
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For this purpose, aqueous suspensions of the couplers are finely milled in absence of substantial amounts of organic solvents, for example by vigorous stirring with the addition of sharp sand and/or by means of ultrasound. Reference may be had in this connection to German Patent Application P 26 09 741.6.
Preferably at least one silver hal de emulsion layer in the comparatively less sensitive emulsion layer unit contains a non-diffusible compound which is capable of reacting with colour developer oxidation products to release a diffusible development inhibitor. The silver halide emulsion layers of the comparatively more sensitive emulsion layer Ullit may also contain such a non-diffusible compound capable of releasing a diffusible development inhibitor in its reaction with developer oxidation products. Compounds which release development inhibitors include, for example, the known DIR coupleTs which are colour couplers containing, in the coupling position, a releasable substituent which is released from the coupler molecule as a diffusible development inhibitor by the colour coupling reaction while the coupler molecule itself becomes a dye.
DIR couplers of this kind have been described, for example, in United States Patent Specification No. 3,227,554.
It is particularly preferred, however, to use development inhibitor releasing compounds of the kind which release a development inhibitor in their reaction with colour developer oxidation products without at the same time forming a dye. Compounds of this kind, which may be referred to as DIR compounds in contrast to DIR couplers, have been described, for example, in United States Patent Specification No. 3,632,345, and German Offenlegungsschriften No. 2,363,752; 2,359,295; 2,405,442;
2,448,063 and 2,529,350.
The intermediate layers which are arranged between the .~, , .
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light-sensitive silver hali~e emulsion layers and in which the binder is preferably gelatine may contain compounds which are capable of reacting with colour developer oxidation products and hence to prevent unwanted diffusion of the colour developer oxidation products. Examples of such com-pounds include non-diffusible reducing agents such as hydroquinone derivatives or couplers which react with colour ~e~t~loper oxidation products without producing a dye which remains in the layers. Particularly suitable for this purpose are the white couplers already mentioned above or also colour couplers giving rise to a soluble dye which is washed out of the layers during colour photographic processing. Other suitable compounds for suppressing un-wanted diffusion of colour developer oxidation products have been described, for example, in the monograph entitled "Stabilization of Photographic Silver Halide Emulsions" by E.J.Birr, The Focal Press, 1st Edition, 1974, pages 116 to 122.
Information on other suitable additives for the colour photographic recording materials according to the invention or for one of the layers thereof may be found in the article printed in the Journal "Product Licensing Index", Volume 92, December 1971, pages 107 to 110.
The usual colour developers are suitable for the colour photographic processing of the material according to the invention, in particular colour developers based on p-phenylene-diamine, e.g. 4-amino-N,N-dimethylaniline; 4-amino-N,N,-diethyl-aniline; 4-amino-3-methyl-N,N-diethylaniline; 4-amino-3-methyl-N-methyl-N-(~-methylsulphonamidoethyl)-aniline; 4-amino-N-ethyl-, .
N~ hydroxyethyl)-aniline; 4-amino-3-methyl-N-ethyl-N-(~-hydroxyethyl)-aniline; 4-amino-3-methyl-N-ethyl-N-(~-methoxy-ethyl)-aniline; 4-amino-3-methyl-N-ethyl-N-(~-methyl-sulphon-:`~
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amidoethyl)-aniline; 4-amino-N-butyl-N-( ~ -sulphobutyl)-aniline and 4-amino-3-methyl-N-isopropyl-N-(~ - sulphobutyl)-aniline.
Other suitable colour developers have been described, for example, in J.Amer.Chem.Soc., 73, 3100-3125 (1951).
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.-: ' - . ' -11~97~
Example 1 Two layer arrangements were prepared for comparison purposes by the~methods indicated below. In these arrange-ments, the layers mentioned were applied to a transparent substrate in the sequence given. The quantities indicated refer to l m2. The quantity of silver applied is given in terms of the corresponding quantities of silver nitrate.
Arran~ement 1 (according to 5erman Offenlegungsschrift ~ No.2,530,6~5) l. A less sensitive red-sensitive layer containing a red-sensitized silver iodobromide emulsion (5 mol /0 silver iodide) of 3.0 g of silver nitrate containing 790 mg of a cyan coupler of the formula CO_NH_(cH2)4 ~ -C4Hg(t-) :
25 m~ of a DIR coupler of the formula ~ 20 ~ CO-NH
.: ~C C14H29 : I 1~
~ and l.6 g of gelatine.
; 25 2. An intermediate layer of 0,7 g of gelatine.
3. A less sensitive green-sensitive layer containing a green s~nsitized mixture of a relatively sensitive silver iodobrcmide emulsion (5 mol % silver iodide) of 1.5 9 of silver nltrate and a relatively insensitive silver iodbbromide emLlsion (5 mol %
3o of silver iodide) of 1.9 g of silver nitrate containing 600 mg of a magenta coupler of the formula ~L~ 7~
0 1 ~ ~ ,2 ~ CS~ t) C5Hll(t) 60 mg of a DI~ coupler of the formula ~ 4~iN - ~
'Y
NH
CO-C~2~
: Ct 4H29 80 mg of a masking coupler of the formula C16~33 5 2~N~ -N~ -C~2-C~2 ~ 0 ~CF2-Cl~clP
and 2.0 g of gelatine.
4. An intermediate layer containing 0.7 g of gelatine.
5. A highly sensitive red-sensitive layer of red-sensitized silver iodobromide emulsion (5 mol /0 silver iodide) o: of 2.0 g of silver nitrate containing 250 mg of the : cyan coupler from layer 1 and 1.0 g of gelatine.
97~
, . .
According to German Offenlegungsschrift No.2,530,645, the light used for exposure passes through the blue-sensitive layer or layers before reaching the red-sensitive and green-sensitive layers. This means that the blue-sensitive layers are situated above the layers which are sensitive to red and green light and above the yellow filter layer.
lt is an object of the present invention to provide a colour photographic recording material comprising several silver halide emulsion layers of differing sepctral sensi-tivities, which material shows an even greater improvement insensitlvity compared with known colour photographic materials, particularly in the cyan and magenta partial colour images.
The invention relates to a colour photographic recording material consisting of (a) a substrate, (b) applied to this substrate, differently sensitized silver halide emulsion layers containing non-diffusible colour couplers, at least two of which emulsion layers are sensitive to red light and differ from each other in their sensitivity (s~) and at least two others of which are sensitive to green light and differ from each other in their sensitivity ~speed), the more sensitive of the .. ..
two red-sensitive and the more sensitive of the two green-sensitive silver halide emulsion layers being in each case further removed from the substrate than the corresponding less sensitiv¢ silver halide emulsion layer, at least one of the silver halide emulsion layers being sensitive to blue light and further removed from the substrate than any of the red sensitive or green sensitive silver halide emulsion layers, and (c) at least one yellow filter layer which is further removed from the substrate than any of the red-sensitive or green-sensitive silver halide emulsion layers, and (d) ....
, ~
~ AG 1437 . .
. ~, ~1~9~
;
optionally additional layers which are not light-sensitive, characterised in that the silver halide emulsion layers are arranged on the substrate in such a manner that l, the more sensitive of the two green-sensitive silver halide emulsion layers and the more sensitive of the two red-sensitive silver halide emulsion layers are combined to ~orm a comparatively more sensitive emulsion layer unit which is arranged further away from the substrate than both the less sensitive green-sensitive and the less sensitive red-sensitive silver halide emulsion layer; and that 2, at least one additional comparatively insensitive chloride-oontaining silver halide emulsion layer is arranged within the comparatively more sensitive emulsion layer unit or immediately adjacent thereto, The additional, comparatively insensitive silver halide emulsion layer which contains chloride is preferably a non-sensitized silver halide emulsion containing at least 20 mol :' % of sllver chloride. This additional layer is said to ; 20 be comparatively insensitive to indicate that its .~
:
sensitivity to light is very low and even lower than that of the silver halide of the comparatively less sensitive emulsion layer unit. As this layer acts mainly as a source of silver halide for development in other layers there is no need for any light sensitivity in this layer. ~he silver halide in this additional layer thus preferably consists of pure silver chloride or a silver chlorobromide containing up to 80 mol /0 of silver bromide, i.e. the proportion of silver chloride in the total quantity of silver halide is between 20 and lO0 mol /0.
Sensitization, in particular spectral sensitization, is unnecessary. The silver halide emulsions used for the additional, chloride-containing silver halide emulsion layers are preferably of the kind in which the silver halide grains have an average grain diameter of less than 0.5 ~m. Emulsions of this kind include the silver halide emulsions known a~
Mikrat emulsion or Lippman emulsions which have an average grain diameter of less than O.l ~m. These emulsionsare . .
j 20 ;~ ,.
~ 25 '"' .; .
.
, 97~ ~
relatively insensitive to light. The sensitivity of the additional, chloride-containing silver halide emulsions to blue light is preferably less by 10 to 50 log I.t units than that of the image recording blue sensitive layer.
The additional, comparatively insensitive silver halide emulsion layer may be arranged in any position within ; the comparatively more sensitive emulsion layer unit, i.e., - between the more sensitive red-sensitive silver halide emulsion layer and the more sensitive green-sensitive silver halide emulsion layer or above or below these layers. At the same time, two or three additional, relatively insensitive chloride-containing emulsion layers can be incorporated in the com-paratively more sensitive emulsion layer unit, for example immediately above and below the comparatively more sensitive emulsion layer unit as well as within the comparatively more sensitive emulsion layer unit between the red-sensitive and the green-sensitive silver halide emulsion layer. In this way, the more sensitive partial layers of the arrangement are more or less embedded in intermediate layers containing silver chloride.
In one arrangement which is particularly preferred, a chloride Mikrat emulsion layer is arranged instead of the usual gelatine intermediate layer between the more sensitive red-sensitive and the more sensitive green-sensitive silver halide emulsion layer. In another preferred arrangement, a chloride-containing silver halide emulsion layer having an average grain diameter of preferably between 0.1 and 0.5JLm is arranged between the comparatively more sensitive emulsion layer unit and the yellow filter layer in addition to the above mentioned chloride Mikrat emulsion layer which is arranged between the red-sensitive and the green-sensitive silver halide emulsion layer.
.:' ~1~97i~i It is not intended that an i~age should be recorded in the comparatively insensitive chloride-containing silver halide emulsion layer used according to the invention. Such - a layer, however, has an advantageous effect on the sensitivity of the adjacent, image recording layers, particularly on the more sensitive of the red-sensitive and/or the more sensitive o~ the green-sensitive silver halide emulsion layers. This effect o~ enhancing the sensitivity is evidently the greater the smaller the grain size of the silver halide grains in the additional silver halide emulsion layer and hence the greater their solubility and their capacity to contribute to the physical development of the adjacent, more sensitive silver halide emulsion layers.
The use of relatively insensitive silver halide emulsion layers in colour photographic multilayered materials is not new. Layers of this kind have previously been used mainly to prevent unwanted diffusion of sensitizing dyes into adjacent layers of diffe~ing spectral sensitivity (sensitizer barrier s, layer), to prevent unwanted diffusion of development inhibitor into other - 20 layers or into the processing solution (inhibitor barrler layer) or to pro-. duce a mas]cing image in a process following colour developnEnt.
In the colour photographic materials according to the .. invention, the additional, comparatively light-insensitive, : chloride-containing silver halide emulsion layers function as silver halide donors in the development of the adjacent ; silver halide layers which contain highly sensitive, and hence relatively coarse grained, silver halide. A marked increase in sensitivity is observed in the presence of such additional layers. This effect is particularly marked in the layer arrangement according to the invention in which, in contrast to the conventional double layer arrangement, the highly sensitive red-sensitive or green-sensitive silver ;' . -~1~97~
halide emulsion layers are not situated adjacent to the : corresponding less sensitive layers of the same spectral sensitivity, which would otherwise also function as silver halide donors The optimum quantity of silver halide to be used in the additional, less sensitive silver halide emulsion layer can easily be determined by the man of the art with the aid of a few comparison tests. It preferably corresponds to a silver nitrate quantity of from ~.05 to 1.2 g/m .
The additional, chloride-containing silver halide emulsion layers used according to the invention are able to exert yet another advantageous effect, that is to say they are able to suppress the diffusion of bromide or iodide ions released by development in other layers into layers of diffe~
rent spectral sensitivity. Such an effect i9 particularly important between the blue sensitive layer and the comparatively more sensitive emulsion layer unit. Such an additional layer is therefore provided between the blue sensitive silver halide emulsion layer and the comparatively more sensitive emulsion layer unit in order to suppress the diffusion of bromide or iodide ions and it is particularly advantageous to provide such a layer between the last mentioned, comparatively more sensitive emulsion layer unit and the yellow filter layer.
These silver halide emulsion layers preferably have an average grain diameter of between O.l to 0.5,um.
The red-sensitive and greenffensitive silver halide ` emulsion layers may be arranged in any sequence in the comparatively more sensitive emulsion layer unit. The red-sensitive silver halide emulsion layer may be arranged either above or below the green-sensitive layer but is preferably arranged below it.
In the comparatively less sensitive emulsion layer unit, the two light-sensitive layers of differing spectral sensitivi-~1~9~
ties may again be arranged as desired but again the green-sensitive silver halide emulsion layer is preferably arranged above the red-sensitive layer. The comparatively less sensitive emulsion layer unit may also contain two or more red-sensitive and two or more green-sensitive silver halide emulsion layers instead of the single red-sensitive and single green-sensitive silver halide emulsion layer, i~ which case the two or more layers having the same spectral sensitivity preferably differ from each other in their general sensitivity (speed) and are arranged so that the higher the sensi-tivity of a layer having a given spectral sensitivity, the further is such a layer removed from the substrate. Such a plurality of layers may be subdivided into sub-units of sub-stantially comparable general sensitivltyor sub-units of the same spectral sensitivity.
In the colour photographic recording material according to the invention, two or more blue sensitive silver halide emulsion layers may be provided in known manner instead of a single blue-sensitive silver halide emulsion layer for producing the yellow partial colour image.
In addition to the layers already mentioned above, the colour photographic recording material according to the invention may contain other, light-insensitive auxiliary layers, e.g. adhesive layers, antihalation layers or covering layers and in particular intermediate layers between the light-sensitive layers to ensure effective prevention of diffusion of developer oxidation products from one layer into another. For this purpose, such inter-mediate layers may also contain certain compounds which are ~0 capable of reacting with developer oxidation products.
Layers of this kind are preferably arranged between adjacent light-sensitive layers which differ from each other in their : `
-. ^^` 11'~97~.~
spectral sensitivity.
As already mentioned above, the colour photographic recording material accordin~ to the invention contains at . .
least two light-sensitive partial layers of differing speed for producing each partial colour image, at least for producing the cyan and the magenta partial colour image.
The relevant sensitivity in these partial layers is not the absolute sensitivity but the effective sensitivity, taking into account the particular position of the partial layer within the multilayere~ colour photographic material. The absolute sensitivity is the sensitivity of an individual layer if determined separately, that is in absence of other layers. The effective sensitivity of a light sensitive layer within a multilayer colour photographic element ., may be somewhat lower than the absolute sensitivity partly due to the absorption of certain amounts of .: exposure light in upper layers and partly due to the fact that development in lower layers proceeds more slowly than in upper layers. Absolute sensitivity and effective sensitivity refer to the "general sensitivity"
which in contrast to the spectral sensitivity may also be called "speed".
..
9~
The difference in effective sensitivity is suitable between 0.2 and l.0 relative log I.t units. In any individual case, the sensitivity difference is chosen so that colour photo-graphic processing results in a balanced gradation curve without perceptible distortion. The composition of the more sensitive layer is then suitable calculated to produce a lower colour density on colour development than that obtained in the less se~itive layer. This can be achieved by using a lower application of silver and/or a different coupler/silver ratio.
Associated with each of the above mentioned light-sensitive silver halide emulsion layers (with the exclusion of the additional, chloride-containing comparatively light insensitive silver halide emulsion layers) is a colour coupler ; 15 wh~ch is capable of reacting with colour developer oxidation products to form a non-diffusible dye. However, the additional, chloride-containing silver halide emulsion layer may also contain colour couplers. The colour couplers are preferably also non-diffusible and situated in the light-sensitive layer itself or in a layer closely adjacent thereto. The colour couplers associated with the two partial layers which ., .
have the same spectral sensitivity need not necessarily be ' `''''`
., ~1~97~6 ' the same, provided that they give rise to substantially the same oolour on colour development, normally a colour which is complementary to the colour of the light to which the light-sensitive silver halide emulsion layers are sensitive. The red-sensitive silver halide emulsion layers therefore have associated with them at least one non-diffusible colour coupler each for the production of the cyan partial colour image, generally a coupler based on phenol or a-naphthol.
The green-sensitive silver halide emulsion layers each contain at least one non-diffusible colour coupler for producing the magenta partial colour image, usually a colour coupler based on 5-pyrazolone or indazolone. The blue-sensitive silver halide emulsion layers each contain at least one non-diffusible colour coupler for producing the yellow partial colour image, generally a colour coupler having an open chain keto methylene group. Large numbers of colour couplers of these kinds are known and have been d0scribed in numerous Patent Specifications. References may be found, for example9 in "Farbkuppler" published by W.Pel~
in "Mitteilungen aus den Forschungslaboratorien der Agfa, Leverkusen/M~nchen", Volume III, 111, (1961), and in the publication by K.Venkataraman in "The Chemistry of Synthetic dyes", Vol.4, 341 to 387, Academic Press (1971).
The colour couplers may either be the usual 4-equivalent couplers or they may be 2-equivalent couplers which require a smaller quantity of silver halide for colour production.
2-equivalent couplers are derived, as is known, from 4-equivalent couplers in that they contain, in the coupling position, a substituent which is released in the coupling reaction. 2-equivalent couplers which may be used according to the invention include both couplers which are practically colourless and couplers which have an intense colour of their ,~ .
own which disappears during the colour coupling reaction or is replaced by the colour of the image dye produced. Accord-ing to the invention, the last mentioned couplers may in addition be present in the light-sensitive silver halide emulsion layers, where they serve as masking couplers to compensate for unwanted side densities of the image dyes.
Suitable 2-equivalent couplers also include the known white couplers, but these do not give rise to a dye in their ~' reaction with colour developer oxidation products and there-fore do not directly contribute to the formation of the colour image. The 2-equivalent couplers also include the known DI~ couplers, which are couplers containing, in the coupling position, a group which is released as a diffusible development inhibitor by the reaction with colour developer oxidation products.
Colour coupler mixtures may be used as required to . ., obtain a desired colour shade or reactivity, Water-soluble couplers, for example, may be used in combination with . .
hydrophobic, water-insoluble couplers.
Whereas the water-soluble couplers are in most cases added to the emulsion in the form of aqueous alkaline solutions, the hydrophobic colours are suitably incorporated by means of - one of the known emulsification processes in which, for example, the coupler is dissolved in an organic solvent, optionally in the presence of a high boiling coupler solvent, and is then dispersed in a gelatine solution. Dibutyl phthalate and tricresyl phosphate are examples of high boiling . .
coupler solvents. Other coupler solvents have been described, for example, in US Patent Specifications No.2,322,027;
3,689,271; 3,764,336 and 3,765,897.
It is also possible to prepare aqueous dispersion of the hydrophobic couplers and add them to the casting solutions.
9~
For this purpose, aqueous suspensions of the couplers are finely milled in absence of substantial amounts of organic solvents, for example by vigorous stirring with the addition of sharp sand and/or by means of ultrasound. Reference may be had in this connection to German Patent Application P 26 09 741.6.
Preferably at least one silver hal de emulsion layer in the comparatively less sensitive emulsion layer unit contains a non-diffusible compound which is capable of reacting with colour developer oxidation products to release a diffusible development inhibitor. The silver halide emulsion layers of the comparatively more sensitive emulsion layer Ullit may also contain such a non-diffusible compound capable of releasing a diffusible development inhibitor in its reaction with developer oxidation products. Compounds which release development inhibitors include, for example, the known DIR coupleTs which are colour couplers containing, in the coupling position, a releasable substituent which is released from the coupler molecule as a diffusible development inhibitor by the colour coupling reaction while the coupler molecule itself becomes a dye.
DIR couplers of this kind have been described, for example, in United States Patent Specification No. 3,227,554.
It is particularly preferred, however, to use development inhibitor releasing compounds of the kind which release a development inhibitor in their reaction with colour developer oxidation products without at the same time forming a dye. Compounds of this kind, which may be referred to as DIR compounds in contrast to DIR couplers, have been described, for example, in United States Patent Specification No. 3,632,345, and German Offenlegungsschriften No. 2,363,752; 2,359,295; 2,405,442;
2,448,063 and 2,529,350.
The intermediate layers which are arranged between the .~, , .
9~
:
/:
light-sensitive silver hali~e emulsion layers and in which the binder is preferably gelatine may contain compounds which are capable of reacting with colour developer oxidation products and hence to prevent unwanted diffusion of the colour developer oxidation products. Examples of such com-pounds include non-diffusible reducing agents such as hydroquinone derivatives or couplers which react with colour ~e~t~loper oxidation products without producing a dye which remains in the layers. Particularly suitable for this purpose are the white couplers already mentioned above or also colour couplers giving rise to a soluble dye which is washed out of the layers during colour photographic processing. Other suitable compounds for suppressing un-wanted diffusion of colour developer oxidation products have been described, for example, in the monograph entitled "Stabilization of Photographic Silver Halide Emulsions" by E.J.Birr, The Focal Press, 1st Edition, 1974, pages 116 to 122.
Information on other suitable additives for the colour photographic recording materials according to the invention or for one of the layers thereof may be found in the article printed in the Journal "Product Licensing Index", Volume 92, December 1971, pages 107 to 110.
The usual colour developers are suitable for the colour photographic processing of the material according to the invention, in particular colour developers based on p-phenylene-diamine, e.g. 4-amino-N,N-dimethylaniline; 4-amino-N,N,-diethyl-aniline; 4-amino-3-methyl-N,N-diethylaniline; 4-amino-3-methyl-N-methyl-N-(~-methylsulphonamidoethyl)-aniline; 4-amino-N-ethyl-, .
N~ hydroxyethyl)-aniline; 4-amino-3-methyl-N-ethyl-N-(~-hydroxyethyl)-aniline; 4-amino-3-methyl-N-ethyl-N-(~-methoxy-ethyl)-aniline; 4-amino-3-methyl-N-ethyl-N-(~-methyl-sulphon-:`~
g7~
amidoethyl)-aniline; 4-amino-N-butyl-N-( ~ -sulphobutyl)-aniline and 4-amino-3-methyl-N-isopropyl-N-(~ - sulphobutyl)-aniline.
Other suitable colour developers have been described, for example, in J.Amer.Chem.Soc., 73, 3100-3125 (1951).
, .
' . .
: . .
, . .
`:,' ',' :
.-: ' - . ' -11~97~
Example 1 Two layer arrangements were prepared for comparison purposes by the~methods indicated below. In these arrange-ments, the layers mentioned were applied to a transparent substrate in the sequence given. The quantities indicated refer to l m2. The quantity of silver applied is given in terms of the corresponding quantities of silver nitrate.
Arran~ement 1 (according to 5erman Offenlegungsschrift ~ No.2,530,6~5) l. A less sensitive red-sensitive layer containing a red-sensitized silver iodobromide emulsion (5 mol /0 silver iodide) of 3.0 g of silver nitrate containing 790 mg of a cyan coupler of the formula CO_NH_(cH2)4 ~ -C4Hg(t-) :
25 m~ of a DIR coupler of the formula ~ 20 ~ CO-NH
.: ~C C14H29 : I 1~
~ and l.6 g of gelatine.
; 25 2. An intermediate layer of 0,7 g of gelatine.
3. A less sensitive green-sensitive layer containing a green s~nsitized mixture of a relatively sensitive silver iodobrcmide emulsion (5 mol % silver iodide) of 1.5 9 of silver nltrate and a relatively insensitive silver iodbbromide emLlsion (5 mol %
3o of silver iodide) of 1.9 g of silver nitrate containing 600 mg of a magenta coupler of the formula ~L~ 7~
0 1 ~ ~ ,2 ~ CS~ t) C5Hll(t) 60 mg of a DI~ coupler of the formula ~ 4~iN - ~
'Y
NH
CO-C~2~
: Ct 4H29 80 mg of a masking coupler of the formula C16~33 5 2~N~ -N~ -C~2-C~2 ~ 0 ~CF2-Cl~clP
and 2.0 g of gelatine.
4. An intermediate layer containing 0.7 g of gelatine.
5. A highly sensitive red-sensitive layer of red-sensitized silver iodobromide emulsion (5 mol /0 silver iodide) o: of 2.0 g of silver nitrate containing 250 mg of the : cyan coupler from layer 1 and 1.0 g of gelatine.
6. An intermediate layer containing 0.7 g of gelatine.
7. A highly sensitive green-sensitive emulsion contain-ing a green-sensitized silver iodobromide emulsion (7 mol /0 of silver iodide) of 2.8 g of silver nitrate and 170 mg of a magenta coupler of the formula :
C13~27 Cl ~N
C ~ Cl 37 mg of a magenta coupler of the formula cl7~3$-C-NH~82 ~ S0 and 2.1 g of gelatine.
C13~27 Cl ~N
C ~ Cl 37 mg of a magenta coupler of the formula cl7~3$-C-NH~82 ~ S0 and 2.1 g of gelatine.
8. An intermediate layer containing 0.7 g of gelatine.
9. A yellow filter layer containing colloidal silver to produce a yellow density of 0.8.
: 10. A blue-sensitive layer containing a mixture of a sensitive silver iodobromide emulsion (9 mol /0 silver iodide) of 1.0 g of silver nitrate and an insensitive silver iodobromide emulsion (3 mol /0 silver iodide) of o.6 g of silver nitrate containing 1.0 g of a yellow coupler of the formula C~3 ~ -C0-C~2-C0-NH ~ 2 . 3 and 2.0 g of gelatine.
3 11. A covering layer of 0.7 g of gelatine.
11~97~6 rran~emellt 2 (according to the invention) The same layers having the same compositions were applied as in Arrangement 1 but with the following modifications in layer 6:
6. An insensitive layer containing a mixture of a silver chlorobromide emulsion of medium sensitivity (64 mol silver chloride) of 0.2g of silver nitrate and an in-sensitive silver chloride emulsion offinest grain from ; 0.2 g of silver nitrate containing 70 mg of the yellow coupler used in layer 10 of Arrangement 1 and 0.7 g of gelatine.
After colour photographic processing carried out as described in the ~ritish Journal of Photography, July 1974, pages 597 and 598, the sensitivities measured in relative log I.t units at density 0.2 above fog shown in Table 1 below were obtained.
Table 1 , Sensitivity rel.log. I.t~
i ` 20 Yellow Magenta Cyan Arrangement 1 4.30 3.91 3.82 Arrangement 2 4. 32 4, o6 3 . 92 :' A distinct increase in sensitivity in the magenta and cyan were obtained with the arrangement of layers according to the invention, in addition to an increase in the yellow ^gradation at high densities.
Example 2 Two arrangements of layers were again prepared, Arrangement 1 being similar to Arrangement 1 of Example 1.
iLl~9 ,'`',:
.:
rrangement 2 The sa~e layers having the sa~e compositions as in Arrangement 1 of Example 1 were applied except that the following alterations were made to layers 6 and 8:
6. An insensitive, finest grained silver chloride emulsion layer (chloride Mikrat) of 0.4 g of silver nitrate containing 0.7 g of gelatine.
8. A layer containing a silver chlorobromide emulsion of ~edium sensitivity (64 mol % silver chloride) of 0.4 g of silver nitrate containing 0.8 g of gelatine.
The results obtained after processing as in Example 1 are shown in Table 2 below.
Table 2 ,. _ Sensitivity [rel. log I,t]
:...................................... Yellow Magenta Cyan . Arrangement 1 4.28 3.94 3.78 Arrangement 2 4.30 4.OB 3.91 .`" .
: 10. A blue-sensitive layer containing a mixture of a sensitive silver iodobromide emulsion (9 mol /0 silver iodide) of 1.0 g of silver nitrate and an insensitive silver iodobromide emulsion (3 mol /0 silver iodide) of o.6 g of silver nitrate containing 1.0 g of a yellow coupler of the formula C~3 ~ -C0-C~2-C0-NH ~ 2 . 3 and 2.0 g of gelatine.
3 11. A covering layer of 0.7 g of gelatine.
11~97~6 rran~emellt 2 (according to the invention) The same layers having the same compositions were applied as in Arrangement 1 but with the following modifications in layer 6:
6. An insensitive layer containing a mixture of a silver chlorobromide emulsion of medium sensitivity (64 mol silver chloride) of 0.2g of silver nitrate and an in-sensitive silver chloride emulsion offinest grain from ; 0.2 g of silver nitrate containing 70 mg of the yellow coupler used in layer 10 of Arrangement 1 and 0.7 g of gelatine.
After colour photographic processing carried out as described in the ~ritish Journal of Photography, July 1974, pages 597 and 598, the sensitivities measured in relative log I.t units at density 0.2 above fog shown in Table 1 below were obtained.
Table 1 , Sensitivity rel.log. I.t~
i ` 20 Yellow Magenta Cyan Arrangement 1 4.30 3.91 3.82 Arrangement 2 4. 32 4, o6 3 . 92 :' A distinct increase in sensitivity in the magenta and cyan were obtained with the arrangement of layers according to the invention, in addition to an increase in the yellow ^gradation at high densities.
Example 2 Two arrangements of layers were again prepared, Arrangement 1 being similar to Arrangement 1 of Example 1.
iLl~9 ,'`',:
.:
rrangement 2 The sa~e layers having the sa~e compositions as in Arrangement 1 of Example 1 were applied except that the following alterations were made to layers 6 and 8:
6. An insensitive, finest grained silver chloride emulsion layer (chloride Mikrat) of 0.4 g of silver nitrate containing 0.7 g of gelatine.
8. A layer containing a silver chlorobromide emulsion of ~edium sensitivity (64 mol % silver chloride) of 0.4 g of silver nitrate containing 0.8 g of gelatine.
The results obtained after processing as in Example 1 are shown in Table 2 below.
Table 2 ,. _ Sensitivity [rel. log I,t]
:...................................... Yellow Magenta Cyan . Arrangement 1 4.28 3.94 3.78 Arrangement 2 4.30 4.OB 3.91 .`" .
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A colour photographic recording material comprising arranged on a substrate, a comparatively less sensitive emulsion layer unit comprising a relatively less sensitive red-sensitive silver halide emulsion layer and a relatively less sensitive green-sensitive silver halide emulsion layer; a comparatively more sensitive emulsion layer unit arranged further from the substrate than the comparatively less sensitive emulsion layer unit, and comprising a relatively more sensitive red-sensitive silver halide emulsion layer and a relatively more sensitive green-sensitive silver halide emulsion layer; a yellow filter layer arranged further from the substrate than any of the red-or green-sensitive emulsion layers and at least one blue-sensi-tive silver halide emulsion layer arranged further from the substrate than the yellow filter layer, each of said light sensi-tive silver halide emulsion layers having associated with it a non-diffusing colour coupler; and the comparatively more sensi-tive emulsion layer unit having associated with it an additional comparatively insensitive silver halide emulsion layer which contains silver chloride.
2. A material as claimed in claim 1 in which the addi-tional silver halide emulsion layer contains at least 20 mol of silver chloride.
3. A material as claimed in claim 1 or claim 2 in which the additional silver halide emulsion layer contains a silver chlorobromide emulsion.
4. A material as claimed in claim 1 in which the addition-al silver halide emulsion layer is one in which the silver halide grains have an average grain diameter of less than 0.5 µm.
5. A material as claimed in claim 4 in which the addition-al silver halide emulsion layer is one in which the silver halide grains have an average grain diameter of less than 0.1 µm.
6. A material as claimed in claim 1 in which the addition-al emulsion layer is a chloride Mikrat layer arranged between the more sensitive red-sensitive and the more sensitive green-sensi-tive silver halide emulsion layers.
7. A material as claimed in claim 6 in which the further chloride-containing, comparatively insensitive, silver halide emulsion layer is arranged between the more sensitive emulsion layer unit and the yellow filter layer.
8. A material as claimed in claim 7 in which the emulsion layer arranged between the more sensitive emulsion layer unit and the yellow filter layer has an average grain diameter of from 0.1 to 0.5 µm.
9. A material as claimed in claim 1 or 7 in which the silver halide content of the additional halide emulsion layer corresponds to a silver nitrate quantity of from 0.1 to 1.2 g/m2.
10. A material as claimed in claim 1 or 7 in which the sensitivity of the additional chloride-containing silver halide emulsion layer is lower by from 10 to 50 log.I.t units than that of the image recording blue-sensitive layer.
11. A material as claimed in claim 1 or 7 in which at least one silver halide emulsion layer in the comparatively less sensitive emulsion layer unit contains a non-diffusible compound which is capable of releasing a diffusible development inhibitor as a result of its reaction with colour developer oxidation pro-ducts.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19762622924 DE2622924A1 (en) | 1976-05-21 | 1976-05-21 | COLOR PHOTOGRAPHIC RECORDING MATERIAL |
| DEP2622924.3 | 1976-05-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1109716A true CA1109716A (en) | 1981-09-29 |
Family
ID=5978724
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA278,751A Expired CA1109716A (en) | 1976-05-21 | 1977-05-19 | Colour photographic recording material |
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| Country | Link |
|---|---|
| JP (1) | JPS52143016A (en) |
| BE (1) | BE854532A (en) |
| CA (1) | CA1109716A (en) |
| DE (1) | DE2622924A1 (en) |
| FR (1) | FR2352324A1 (en) |
| GB (1) | GB1560965A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1500497A (en) * | 1974-07-09 | 1978-02-08 | Kodak Ltd | Photographic silver halide multilayer colour materials |
| DE2704797C2 (en) * | 1977-02-05 | 1982-05-27 | Agfa-Gevaert Ag, 5090 Leverkusen | Color photographic recording material |
| JPS5910947A (en) * | 1982-07-10 | 1984-01-20 | Konishiroku Photo Ind Co Ltd | Silver halide color photographic sensitive material |
| JPS5969754A (en) | 1982-10-14 | 1984-04-20 | Fuji Photo Film Co Ltd | Color photosensitive silver halide material |
| JPS59160135A (en) * | 1983-03-02 | 1984-09-10 | Fuji Photo Film Co Ltd | Silver halide photosensitive material |
| JPS6066250A (en) * | 1983-09-21 | 1985-04-16 | Konishiroku Photo Ind Co Ltd | Silver halide photosensitive material |
| JPS60194450A (en) * | 1984-03-16 | 1985-10-02 | Konishiroku Photo Ind Co Ltd | Silver halide color photosensitive material |
| DE3420173A1 (en) * | 1984-05-30 | 1985-12-05 | Agfa-Gevaert Ag, 5090 Leverkusen | COLOR PHOTOGRAPHIC RECORDING MATERIAL |
| EP0369486B1 (en) * | 1988-11-18 | 1997-03-12 | Fuji Photo Film Co., Ltd. | Negative type silver halide color photographic lightsensitive material |
| FR2688604A1 (en) * | 1992-03-16 | 1993-09-17 | Kodak Pathe | Method of photographic processing and photographic products comprising an overlayer with fine grains |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR959735A (en) * | 1943-05-27 | 1950-04-04 | ||
| DE1959239A1 (en) * | 1960-05-07 | 1971-06-03 | Agfa Gevaert Ag | Addition to yellow dye filter |
| JPS5336779B2 (en) * | 1973-05-04 | 1978-10-04 | ||
| JPS5055332A (en) * | 1973-09-13 | 1975-05-15 |
-
1976
- 1976-05-21 DE DE19762622924 patent/DE2622924A1/en active Pending
-
1977
- 1977-05-12 BE BE1008126A patent/BE854532A/en unknown
- 1977-05-18 GB GB2086477A patent/GB1560965A/en not_active Expired
- 1977-05-19 CA CA278,751A patent/CA1109716A/en not_active Expired
- 1977-05-20 JP JP5777177A patent/JPS52143016A/en active Pending
- 1977-05-20 FR FR7715541A patent/FR2352324A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52143016A (en) | 1977-11-29 |
| FR2352324B1 (en) | 1982-06-18 |
| FR2352324A1 (en) | 1977-12-16 |
| DE2622924A1 (en) | 1977-12-01 |
| GB1560965A (en) | 1980-02-13 |
| BE854532A (en) | 1977-11-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |