EP0251042B1 - Matériau d'enregistrement photographique couleur - Google Patents

Matériau d'enregistrement photographique couleur Download PDF

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Publication number
EP0251042B1
EP0251042B1 EP87108742A EP87108742A EP0251042B1 EP 0251042 B1 EP0251042 B1 EP 0251042B1 EP 87108742 A EP87108742 A EP 87108742A EP 87108742 A EP87108742 A EP 87108742A EP 0251042 B1 EP0251042 B1 EP 0251042B1
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EP
European Patent Office
Prior art keywords
sensitivity
layer
red
sensitive
foreign
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 - Lifetime
Application number
EP87108742A
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German (de)
English (en)
Other versions
EP0251042A3 (en
EP0251042A2 (fr
Inventor
Reinhart Dr. Matejec
Erwin Dr. Ranz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert AG
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Agfa Gevaert AG
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Publication of EP0251042A2 publication Critical patent/EP0251042A2/fr
Publication of EP0251042A3 publication Critical patent/EP0251042A3/de
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Publication of EP0251042B1 publication Critical patent/EP0251042B1/fr
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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
    • G03C7/3041—Materials with specific sensitometric characteristics, e.g. gamma, density

Definitions

  • the invention relates to a color photographic recording material which gives satisfactory density gradations in the case of details of high color saturation.
  • IIE inter-image effect
  • the IIE is measured as a percentage distribution of the color gradation in the case of color separation exposure with light of the corresponding spectral range in relation to that color gradation which is obtained when exposed to white light.
  • the IIE is usually generated by DIR couplers, in the case of color reversal material usually by Ag+ complexing agents such as SCN ⁇ in the reversal first developer.
  • a well-known disadvantage of high IIE is the poor, often completely missing density gradation of details in colors that show high color saturation, especially in the area of red hues. For example, red roses from Color-Material with a large IIE are usually only reproduced as undifferentiated red colored areas in which the detailed drawing is extremely poor.
  • the object of the invention is to modify color material with a large IIE so that density gradations can be better recognized even in the details with high color saturation, without the good color quality achieved by the high IIE being noticeably deteriorated.
  • the color density of the color that is produced when exposed to light of a certain spectral range is to be referred to here as the "main color density” (for red exposure this is blue-green in the color negative system), while the color densities of the other two colors (in purple and yellow in this example) are referred to as "foreign color densities”.
  • the spectral sensitivity for which the halogen silver grains of a particular layer are dominantly sensitive is referred to as the main sensitivity, while the sensitivities of this layer for the other spectral ranges are called spectral foreign sensitivity.
  • the invention thus relates to a color photographic recording material, each with at least one layer, the main sensitivity of which is blue, green or red, which contains the color couplers which complement each other and whose IIE in the blue- and red-sensitive layer is at least 5%, preferably is at least 10% and in the green-sensitive layer is at least 10%, preferably at least 15%, characterized in that a non-red sensitivity is generated in at least one layer whose main sensitivity is green and in at least one layer whose skin sensitivity is blue, the main sensitivity 8 to 25 DIN, preferably 12 to 20 DIN, is greater than the foreign sensitivity.
  • a blue sensitivity is preferably generated in at least one layer whose main sensitivity is green and in at least one layer whose main sensitivity is red, and in at least one layer whose main sensitivity is blue and in at least one layer whose main sensitivity is red , whereby the sensitivity differences indicated above must be observed.
  • the red alien sensitivity in the green-sensitive layer deviate from the red alien sensitivity in the blue-sensitive layer by no more than 3 DIN, preferably 1 DIN, and that the red exposure resulting purple and yellow gradations within an exposure range of at least 5 DIN, preferably at least 10 DIN by no more than 25%, preferably no more than 10% from each other.
  • a possible embodiment of the invention consists in sensitizing a portion of the halosilver grains of one layer, preferably the smaller grains of the low-sensitivity layer of a color, if several sub-layers are assigned to this color, in the above-mentioned manner in a targeted manner to spectral foreign sensitivity.
  • the size of the required foreign sensitivity can best be determined by the amount of the spectral (foreign) sensitizer used in combination with the main spectral sensitivity of the halogen silver grains used for this purpose and other relevant layer parameters (e.g. coupler and DIR coupler content of the layer; positioning of the Layer in the layer structure, stabilizer additive and the like) can be set.
  • the required gradations of the foreign color density curves are expediently set for the given layer parameters by the amount of the spectrally externally sensitized halogen silver grains.
  • the spectrally foreign-sensitive emulsion grains are also accommodated in additional layers in the layer structure.
  • spectrally sensitive AgX grains there are preferably also those in a layer which are spectrally sensitive to foreign and foreign.
  • the layers contain in the usual way the color couplers complementary to the main spectral sensitivity, ie the red-sensitive layer cyan couplers, the green-sensitive layer purple couplers and blue-sensitive layer yellow couplers.
  • the couplers can be incorporated into the goat solution of the silver halide emulsion layers or other colloid layers in a known manner.
  • the oil-soluble or hydrophobic couplers may preferably consist of one Solution in a suitable coupler solvent (oil former), optionally in the presence of a wetting or dispersing agent, can be added to a hydrophilic colloid solution.
  • the hydrophilic casting solution can of course contain other conventional additives in addition to the binder.
  • the solution of the coupler need not be directly dispersed in the casting solution for the silver halide emulsion layer or other water permeable layer; Rather, it can also be advantageously first dispersed in an aqueous, non-photosensitive solution of a hydrophilic colloid, whereupon the mixture obtained, after removal of the low-boiling organic solvents used, may be mixed with the coating solution for the photosensitive silver halide emulsion layer or another water-permeable layer before application. So-called latex couplers are also very suitable.
  • Suitable light-sensitive silver halide emulsions are emulsions of silver chloride, silver bromide or mixtures thereof, possibly with a low silver iodide content of up to 10 mol% in one of the commonly used hydrophilic binders.
  • the silver halide grains can be limited by the usual crystallographic areas (100, 111, 110). They can be homo- or heterodisperse, twinned or non-twisted, bowl-shaped or platelet-like (T-grains), whereby the pure types or mixtures of individual types can be used.
  • Gelatin is preferably used as a binder for the photographic layers. However, this can be replaced in whole or in part by other natural or synthetic binders.
  • the emulsions can be chemically sensitized in the usual way, and the emulsion layers as well as other non-light-sensitive layers can be hardened in the usual way with known hardening agents.
  • Each of the light-sensitive layers mentioned can consist of a single layer or, in a known manner, for example in the case of the so-called double-layer arrangement, also comprise two or more silver halide emulsion partial layers (DE-C-1 121 470).
  • red-sensitive silver halide emulsion layers are arranged closer to the layer support than green-sensitive silver halide emulsion layers and these in turn are closer than blue-sensitive layers, with a non-light-sensitive yellow filter layer generally being located between green-sensitive layers and blue-sensitive layers.
  • a layer which is not sensitive to light is generally arranged between layers of different spectral sensitivity and can contain means for preventing the incorrect diffusion of developer oxidation products.
  • silver halide emulsion layers of the same spectral sensitivity they can be directly adjacent to one another or be arranged such that a light-sensitive layer with a different spectral sensitivity is located between them (DE-A-1 958 709, DE-A-2 530 645, DE-A -2 622 922).
  • the color couplers can be both conventional 4-equivalent couplers and 2-equivalent couplers in which a smaller amount of silver halide is required to produce the color.
  • 2-equivalent couplers are derived from the 4-equivalent couplers in that they contain a substituent in the coupling site, which is split off during the coupling.
  • the 2-equivalent couplers include both those that are practically colorless and those that have an intense intrinsic color that disappears when the color is coupled or is replaced by the color of the image dye produced.
  • the latter couplers can also be present in the light-sensitive silver halide emulsion layers and serve there as mask couplers to compensate for the undesired secondary densities of the image dyes.
  • the known white couplers are also to be counted among the 2-equivalent couplers, but they do not give any dye on reaction with color developer oxidation products.
  • the 2-equivalent couplers are also the known DIR couplers, which are couplers which contain a detachable residue in the coupling point, which is released as a diffusing development inhibitor when reacted with color developer oxidation products.
  • Other photographically active compounds e.g. Development adders or fogging agents can be released from such couplers during development.
  • 2-equivalent couplers of the pyrazolotriazole type preferred for cyan ureidophenol couplers.
  • the color photographic recording material of the present invention may contain further additives, for example antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties.
  • further additives for example antioxidants, dye-stabilizing agents and agents for influencing the mechanical and electrostatic properties.
  • UV-absorbing compounds in one or more of the layers contained in the recording material, preferably in one of the upper layers use. Suitable UV absorbers are described for example in US-A-3 253 921, DE-C-2 036 719 and EP-A-0 057 160.
  • the color photographic recording material according to the invention is developed with a color developer compound.
  • All developer compounds which have the ability in the form of their oxidation product to react with color couplers to form azomethine dyes can be used as the color developer compound.
  • Suitable color developer compounds are aromatic compounds of the p-phenylenediamine type containing at least one primary amino group, for example N, N-dialkyl-p-phenylenediamines, such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methylsulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-ethyl-N-hydroxyethyl-3-methyl-p-phenylenediamine and 1- (N-ethyl-N-methoxyethyl) -3-methyl-p-phenylenediamine.
  • N, N-dialkyl-p-phenylenediamines such as N, N-diethyl-p-phenylenediamine, 1- (N-ethyl-N-methylsulfonamidoethyl) -3 -methyl-p-phenylenediamine, 1- (N-eth
  • Example 2 part of the silver halide grains of layers 6 (pp) and 10 (gb) are also red-sensitized.
  • Example 3 part of the silver halide grains of layers 3 (bg) and 10 (gb) are also green-sensitized, and part of the silver halide grains of layers 6 (pp) and 10 (gb) are also red-sensitized.
  • Example 4 corresponds to Example 3, but contains between layers 2 and 3 an additional control layer with silver halide grains with high blue sensitivity and a bg coupler.
  • 56% by weight of the low-sensitivity emulsion GN (1) present in layer 6 are sensitized with a reduced amount of green sensitizer and with red sensitizer in such a way that the same sensitivity to white light as in Example 1 results and that the green sensitivity of this GN (1) emulsion portion is equal to its red sensitivity.
  • Example 2 is repeated, but 50% by weight of the non-red-sensitized portion of the low-sensitivity emulsion BN (1) from layer 10 is spectrally green sensitized to the same sensitivity with green exposure as with blue exposure; the increase in white sensitivity is reset by adding a stabilizer to the value that existed before this spectral sensitization; 62.5% by weight of the low-sensitivity emulsion RN (1) from layer 3 are sensitized with a reduced amount of red sensitizer and additionally with green sensitizer in such a way that the same sensitivity to white light as in example 1 results, and that the sensitivity to red is the same RN (1) emulsion portion is equal to its green sensitivity.
  • Example 3 is repeated, but the following layer 2a is cast between layer 2 and layer 3:
  • the blue sensitivity is reduced from 28.0 DIN to 26.0 DIN.
  • FIGS. 1 to 6 show the color density curves obtained on the four color negative layer structures of examples 1 to 4 (color densities D yellow (1), purple (2) and blue-green (3) as a function of the exposure log It).
  • Figures 7 to 12 show the color density curves (depending on the exposure log It of the negatives of Examples 1 to 4) which are obtained when the negatives are copied onto color-negative paper for positive copying.
  • 1 and 7 correspond to Example 1 with red exposure 2 and 8 correspond to Example 2 with red exposure 3 and 9 correspond to Example 1 with green exposure 4 and 10 correspond to Example 3 with green exposure 5 and 11 correspond to example 1 with blue exposure 6 and 12 correspond to example 4 in blue exposure.
  • example 3 has the same advantage over example 1 in green exposure, which can be seen from a comparison of FIG. 3 (negative gradation) and FIG. 9 (positive gradation) according to the prior art with FIG. 4 (negative gradation) and FIG. 10 (positive gradation) according to the invention.
  • example 4 corresponds to example 1 with blue exposure, which can be seen from a comparison of FIG. 5 (negative gradation) and FIG. 11 (positive gradation) according to the prior art with FIG. 12 (positive gradation) according to the invention.
  • IIE of Examples 1 to 4 (gradation division of the main color density curves at half the maximum density of percent with color separation exposure in relation to the white exposure): Red exposure from Fig. 1: + 85% Green exposure from Fig. 3: + 50% Blue exposure from Fig. 5: + 45%
  • a color reversal film structure was produced by applying the following layers to a transparent cellulose triacetate support in the order given here.
  • the quantities refer to 1 m2.
  • the corresponding amounts of AgNO3 are given.
  • the silver halide emulsions used are shown in Table 2.
  • Example 6 differs from Example 5 in that all silver halide grains of the low-sensitivity, spectrally blue-sensitized emulsion BN (2) of layer 10 are additionally sensitized spectrally red with so much red sensitizer that the same sensitivity results with red exposure as with blue exposure.
  • the increase in sensitivity to white light caused by this red sensitization is suppressed by as much of a stabilizer as is required to set the same white light sensitivity that was present before the spectral red sensitization.
  • all silver halide grains of the spectrally green-sensitized, low-sensitivity emulsion GN (2) from layer 6 are additionally spectrally red-sensitized.
  • the amount of green sensitizer is reduced, and enough red sensitizer is added to give the same sensitivity to white light as in Example 5 and the red sensitivity is equal to the green sensitivity.
  • FIGS. 13 and 14 show the color density curves obtained on the color reversal layer structures (color densities yellow, purple and blue-green as a function of the exposure (log it)) with red light.
  • the color density curves of the white exposure are shown in dashed lines.
  • Example 5 when Example 5 is red exposed in the log It range of 3.2 ⁇ log it ⁇ 4.2 all three color density curves (gb, pp and bg) run horizontally, ie have no density gradations (in contrast to white exposure, which still provides density gradations in this exposure range).
  • the gradation of the pp curve in Example 5 according to FIG. 13 is on the area 1.7 ⁇ log it ⁇ 3.2 limited, since it is caused by the pp secondary density of the bg image dye and can therefore only occur in the region of the bg gradation.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)

Claims (7)

  1. Matériau d'enregistrement pour photographie en couleurs avec chaque fois au moins une couche dont la sensibilité principale est pour le bleu, le vert ou le rouge, qui contient chaque fois un coupleur chromogène à couplage complémentaire et dont l'effet interimage dans la couche sensible au bleu et dans la couche sensible au rouge est d'au moins 5% et, de préférence, d'au moins 10% et est, dans la couche sensible au vert, d'au moins 10% et de préférence d'au moins 15%, caractérisé en ce que dans au moins une couche dont la sensibilité principale s'adresse au vert et dans au moins une couche dont la sensibilité principale s'adresse au bleu, on crée une sensibilité étrangère s'adressant au rouge, tandis que la sensibilité principale est supérieure de 8 à 25 DIN aux sensibilités étrangères.
  2. Matériau d'enregistrement pour photographie en couleurs selon la revendication 1, caractérisé en ce que la différence de sensibilité entre la sensibilité principale et la sensibilité étrangère est comprise entre 12 et 20 DIN.
  3. Matériau d'enregistrement pour photographie en couleurs selon la revendication 1, caractérisé en ce que les sensibilités étrangères sont réalisées de façon à ce qu'il existe dans une couche, outre les grains de AgX à sensibilité spectrale principale, d'autres qui ont une sensibilité spectrale principale et étrangère.
  4. Matériau d'enregistrement pour photographie en couleurs selon la revendication 1, caractérisé en ce que, en cas de disposition en couche double ou multiple des couches à sensibilité de couleur, la sensibilité étrangère spectrale est réalisée dans la couche d'émulsion d'halogénure d'argent à plus faible sensibilité.
  5. Matériau d'enregistrement pour photographie en couleurs selon la revendication 1, dans lequel on crée en outre, dans au moins une couche dont la sensibilité principale s'adresse au rouge, une sensibilité étrangère s'adressant au bleu et, dans au moins une couche dont la sensibilité principale s'adresse au bleu ainsi que dans au moins une couche dont la sensibilité principale s'adresse au rouge, une sensibilité étrangère s'adressant au vert, tandis que la sensibilité principale est supérieure de 8 à 25 DIN à la sensibilité étrangère.
  6. Matériau pour négatifs en couleurs selon la revendication 1, caractérisé en ce que la sensibilité à la lumière rouge dans la couche sensible à la lumière verte ne diffère de la sensibilité étrangère s'adressant à la lumière rouge dans la couche sensible à la lumière bleue que de 3 DIN au maximum, et que les gradations étrangères de pourpre et de jaune obtenues en cas d'exposition à la lumière rouge ne diffèrent l'une de l'autre que de 25% au maximum dans un domaine d'exposition d'au moins 5 DIN.
  7. Matériau pour négatifs en couleurs selon la revendication 6, caractérisé en ce que la sensibilité pour la lumière rouge dans la couche sensible à la lumière verte ne diffère pas de plus de 1 DIN de la sensibilité à la lumière rouge dans la couche sensible à la lumière bleue et que les gradations étrangères de pourpre et de jaune obtenues en cas d'exposition à la lumière rouge ne diffèrent l'une de l'autre que de 25 % au maximum dans un domaine d'exposition d'au moins 10 DIN.
EP87108742A 1986-06-28 1987-06-19 Matériau d'enregistrement photographique couleur Expired - Lifetime EP0251042B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3621764 1986-06-28
DE19863621764 DE3621764A1 (de) 1986-06-28 1986-06-28 Farbfotografisches aufzeichnungsmaterial

Publications (3)

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EP0251042A2 EP0251042A2 (fr) 1988-01-07
EP0251042A3 EP0251042A3 (en) 1989-07-12
EP0251042B1 true EP0251042B1 (fr) 1991-07-03

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EP87108742A Expired - Lifetime EP0251042B1 (fr) 1986-06-28 1987-06-19 Matériau d'enregistrement photographique couleur

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US (1) US4770980A (fr)
EP (1) EP0251042B1 (fr)
JP (1) JPS6313038A (fr)
DE (2) DE3621764A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4902609A (en) * 1987-08-20 1990-02-20 Eastman Kodak Company Photographic print material with increased exposure latitude
JPH02129628A (ja) * 1988-11-09 1990-05-17 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
JPH02157751A (ja) * 1988-12-09 1990-06-18 Konica Corp ハロゲン化銀写真感光材料の処理方法
JPH02181144A (ja) * 1989-01-05 1990-07-13 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
US5185237A (en) * 1989-06-13 1993-02-09 Fuji Photo Film Co., Ltd. Silver halide color photographic material and process for the formation of color images thereon
JPH0786674B2 (ja) * 1989-06-13 1995-09-20 富士写真フイルム株式会社 ハロゲン化銀カラー写真感光材料及びカラー画像形成方法
JPH03246540A (ja) * 1989-11-07 1991-11-01 Fuji Photo Film Co Ltd 直接ポジカラー写真感光材料
US5180657A (en) * 1989-12-22 1993-01-19 Konica Corporation Color photographic light-sensitive material offering excellent hue reproduction
JPH05504425A (ja) * 1990-12-19 1993-07-08 イーストマン コダック カンパニー 写真材料用アゾアニリンマスキングカプラー類
JPH05323528A (ja) * 1992-05-19 1993-12-07 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
JPH0695284A (ja) * 1992-09-16 1994-04-08 Konica Corp ポジ型カラー感光材料及び画像形成方法

Family Cites Families (11)

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Publication number Priority date Publication date Assignee Title
BE563174A (fr) * 1957-12-02
BE729204A (fr) * 1968-03-21 1969-08-28
BE757399A (fr) * 1969-11-26 1971-03-16 Wolfen Filmfab Veb Materiau en plusieurs couches pour la photographie en couleur
JPS5336780B2 (fr) * 1973-06-19 1978-10-04
JPS593737B2 (ja) * 1973-06-29 1984-01-25 富士写真フイルム株式会社 多層カラ−感光材料
JPS5093147A (fr) * 1973-12-18 1975-07-25
DE2718437A1 (de) * 1977-04-26 1978-11-09 Agfa Gevaert Ag Photographisches aufzeichnungsmaterial mit verstaerktem zwischenbildeffekt
US4387159A (en) * 1980-05-29 1983-06-07 Veb Filmfabrik Wolfen Light sensitive, color photographic silver halide compositions with DIR-couplers
EP0059497B1 (fr) * 1981-03-02 1985-05-15 Agfa-Gevaert N.V. Matériaux photographiques en couleurs aux halogénures d'argent et procédé pour la production d'images en couleurs par diffusion-transfert
EP0111199B1 (fr) * 1982-12-07 1986-07-16 Agfa-Gevaert N.V. Composés libérateurs de colorants ainsi que leur utilisation dans des matériaux photographiques couleurs à base d'halogénure d'argent pour la production d'images en couleurs par un procédé de transfert par diffusion de colorants
JPH0623832B2 (ja) * 1984-08-17 1994-03-30 富士写真フイルム株式会社 ハロゲン化銀カラ−反転反射プリント感光材料

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Publication number Publication date
DE3621764A1 (de) 1988-01-07
DE3771134D1 (de) 1991-08-08
EP0251042A3 (en) 1989-07-12
JPS6313038A (ja) 1988-01-20
US4770980A (en) 1988-09-13
EP0251042A2 (fr) 1988-01-07

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