EP0011051B1 - Matériel d'enregistrement photographique en couleurs, procédé pour sa stabilisation et préparation d'images photographiques en couleurs - Google Patents

Matériel d'enregistrement photographique en couleurs, procédé pour sa stabilisation et préparation d'images photographiques en couleurs Download PDF

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Publication number
EP0011051B1
EP0011051B1 EP79810141A EP79810141A EP0011051B1 EP 0011051 B1 EP0011051 B1 EP 0011051B1 EP 79810141 A EP79810141 A EP 79810141A EP 79810141 A EP79810141 A EP 79810141A EP 0011051 B1 EP0011051 B1 EP 0011051B1
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Prior art keywords
carbon atoms
alkyl
recording material
light
hydrogen
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Expired
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EP79810141A
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German (de)
English (en)
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EP0011051A2 (fr
EP0011051A3 (en
Inventor
David G. Dr. Leppard
Michael Dr. Rasberger
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Novartis AG
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Ciba Geigy AG
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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
    • G03C7/392—Additives
    • G03C7/39208—Organic compounds
    • G03C7/3924—Heterocyclic
    • G03C7/39244—Heterocyclic the nucleus containing only nitrogen as hetero atoms
    • G03C7/39248—Heterocyclic the nucleus containing only nitrogen as hetero atoms one nitrogen atom

Definitions

  • the present invention relates to a color photographic recording material which contains at least one light stabilizer in at least one light-sensitive silver halide emulsion layer and / or in at least one of the customary auxiliary layers.
  • Phenols or lX- naphthols are usually used as cyan couplers, pyrazolones as purple couplers and acylacetylamides as yellow couplers.
  • the dyes formed after development are accordingly indophenols, indamines or azomethines.
  • the ultraviolet absorbers In order to achieve adequate light protection, however, relatively large amounts of the ultraviolet absorbers must be used, which generally has the consequence that the thickness of the photographic layers into which the ultraviolet absorbers are incorporated must be increased. Such a measure is highly undesirable for the photographic properties of the material.
  • the ultraviolet absorbers also do not provide effective protection against fading of color images by visible light.
  • Another disadvantage of using relatively large amounts of ultraviolet absorbers is that large amounts of solvent are required in order to achieve the desired fine distribution of these compounds in the aqueous binder emulsions. If concentrated solutions of the ultraviolet absorbers are used, there is a risk that they will become uncontrolled during incorporation into the binder emulsions. H. do not deposit in the desired fine distribution and so uniform protection against ultraviolet radiation cannot be achieved.
  • the present invention therefore provides a color photographic recording material comprising at least p nt sexual a piperidine compound as light stabilizer in at least one photosensitive silver halide emulsion layer, an intermediate layer and / or a protective layer, characterized in that the piperidine compound of formula corresponds, in which R 1 is hydrogen or alkyl having 1 to 4 carbon atoms, R 2 is alkyl or hydroxyalkyl each having 1 to 12 carbon atoms, alkenyl or alkynyl having 3 or 4 carbon atoms, benzyl or R 6 C0-, in which R 6 is hydrogen, alkyl phenyl or phenylethyl substituted by 1 to 12 carbon atoms, alkenyl having 2 or 3 carbon atoms, chloromethyl, cyclohexyl, benzyl or optionally substituted by two alkyl groups each having 1 to 4 carbon atoms and a hydroxyl group, R 3 is hydrogen or methyl, R 4 and R 5 each are alkyl having 1 to
  • the light stabilizers can also be used in combination with conventional ultraviolet absorbers.
  • the present invention furthermore relates to a process for stabilizing color photographic recording materials by incorporating at least one light stabilizer of the formula (1), if appropriate in combination with an ultraviolet absorber, into at least one light-sensitive and / or auxiliary layer of the material, a process for the preparation of the harmful action light-stabilized color photographic images by imagewise exposure and color development of said recording materials and the color photographic images thus obtained.
  • R 1 is alkyl with 1 to 4 carbon atoms, such as. As methyl, ethyl, n-propyl or n-butyl. Ethyl and especially methyl are preferred.
  • R 2 is alkyl having 1 to 12 carbon atoms
  • primary alkyl groups such as those mentioned above generally come, furthermore, for. B. n-amyl, n-hexyl, n-octyl, n-nonyl, n-decyl or n-dodecyl in question.
  • the analogous radicals apply to the meaning of hydroxyalkyl.
  • R 2 in the meaning alkenyl or alkynyl with 3 or 4 carbons can, for. As allyl, methallyl or propargyl.
  • R 2 are alkyl or hydroxyalkyl each having 1 to 4 carbon atoms, alkenyl or alkynyl having 3 or 4 carbon atoms, benzyl and also acyl, where formyl, acetyl, propionyl, acrylyl, methacrylyl, crotonyl, benzoyl or benzylcarbonyl can be mentioned.
  • the substituent Y as an optionally present substituent on the central carbon atom in the compounds of the formula (1) can be hydrogen, straight-chain or branched alkyl having 1 to 12 carbon atoms, such as, for. B. methyl, ethyl, propyl, iso-propyl, butyl, n-amyl, n-hexyl, n- and iso-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl or dodecyl and the corresponding Isomers.
  • R 7 may be hydrogen, methyl, ethyl or a radical of the formula (1a).
  • R 8 is methyl or ethyl, furthermore phenyl or benzyl; Y is also cyan, benzyl or a radical of the formula (1b).
  • the substituents in the radicals of the formulas (1a) and (1b) have the meanings given.
  • the substituent Rg in the formula (1 b) has the meaning hydrogen, methyl or ethyl.
  • Color photographic recording materials which have at least one compound of the formula as light stabilizers are preferred contain, wherein R 10 is methyl, ethyl, benzyl, acetyl, acrylyl, methacrylyl, crotonyl, allyl or propargyl.
  • the compounds of the formulas (1) to (31) are known compounds which, for. B. are described in DE-OS 2 456 364, 2 647 452, 2 654 058 and 2 656 769.
  • the compounds can be prepared by various methods, generally requiring several reaction steps.
  • Starting materials for the first reaction stage are e.g. B. the malonic acid, or one of its reactive derivatives, such as the dialkyl esters, and 4-hydroxy- or 4-aminopiperidines, where the substituents (R 2 ) on the nitrogen atom of the piperidine ring may already be present in the molecule or in a later N.
  • -Alkyl ists- or N-acylation step can be introduced into the molecule by conventional methods.
  • Suitable alkylating or acylating agents are, for example, alkyl halides, alkenyl halides, propargyl chloride, benzyl chloride or carboxylic acid chlorides, which are preferably reacted with the piperidine derivative in the presence of molar amounts of a base.
  • Hydroxyalkyl residues are introduced into the molecule by reaction with epoxides, for example ethylene oxide or propylene oxide.
  • the hydroxybenzyl group can be introduced by reaction with an alkyl-substituted hydroxybenzyldithiocarbamate of the formula HO-benzyl-S-CS-N (R ") 2 , where R" denotes an alkyl group with 1 to 5 carbon atoms or both groups R "together with the nitrogen one Such morpholine, pyrrolidine or piperidine ring .
  • Such dithiocarbamates can be obtained by reacting a phenol with formaldehyde, carbon disulfide and a secondary amine.
  • substituent Y is present in the compounds of the formulas (1) and (2), it can be introduced into the molecule by the known methods of C-alkylation of activated methylene compounds.
  • the compounds of the formulas (1) and (2) are hardly soluble in water, and they are therefore in a low-boiling organic solvent, such as methaloacetate, ethyl acetate, carbon tetrachloride, chloroform, methanol, ethanol, n-butanol, dioxane, acetone or benzene, a high-boiling organic solvent, such as tricresyl phosphate, dimethylformamide, dimethyl sulfoxide, di-n-butyl phthalate or ethyl-N-diphenylcarbamate, or a solvent mixture of the above-mentioned low-boiling and high-boiling organic solvents, the resulting solution becomes a protective colloid solution, such as, in particular, an aqueous gelatin solution , given and dispersed by means of a colloid mill, a homogenizer or by using ultrasound.
  • a protective colloid solution such as, in particular, an
  • the dispersions thus obtained are then used to produce the layers of color photographic recording materials (for example film, paper or silver color bleaching materials).
  • These layers can e.g. B. Intermediate or protective layers, but especially photosensitive (blue and red sensitive) silver halide emulsion layers, in which the cyan (cyan), magenta (magenta) and yellow dyes are formed during the development of the exposed recording material from the corresponding color couplers .
  • ultraviolet absorbers are also used, they are located in the same layers, but preferably in the intermediate or protective layers.
  • Any cyan, magenta and yellow couplers that are used to form the dyes mentioned and thus the color images can be used.
  • the silver halide emulsions preferably contain gelatin as a binder, optionally in a mixture with other high-molecular natural or synthetic compounds.
  • the silver halide emulsions can, for example, be silver bromide, silver chloride or silver iodide emulsions or also those emulsions which contain a mixture of silver halides, such as, for. B. silver bromide-iodide or silver chloride bromide emulsions.
  • the emulsions can be chemically sensitized, they can also be conventional organic stabilizers and antifoggants and also conventional plasticizers, such as. B. glycerin.
  • the emulsions can also be hardened with the hardeners customary for gelatin.
  • the emulsions may also contain conventional pouring aids.
  • the emulsions can be applied to conventional supports for photographic recording material.
  • the customary developer baths can be used to develop the color photographic recording material. These usually contain a developer substance of the p-phenylenediamine type, a development retardant such as potassium bromide, an antioxidant such as sodium sulfite, and a base, e.g. B. an alkali hydroxide or alkali carbonate.
  • the developing baths may also contain a conventional antifoggant and complexing agent.
  • the ultraviolet absorber can be present together with the light stabilizer in one layer or in an adjacent layer.
  • the weight ratio between a conventional ultraviolet absorber and the light stabilizer of the formula (1) is approximately (5-10): 1, the molar ratio approximately (10-20): 1.
  • Examples of ultraviolet absorbers are e.g. B. Compounds of the benzophenone, acrylonitrile, thiazolidine, benzotriazole, oxazole, thiazole and imidazole type.
  • the color images obtained with the recording material according to the invention by exposure and development show a clearly improved light fastness to visible and ultraviolet light.
  • the compounds of formula (1) are practically colorless, so that there is no discoloration of the images; in addition, they are well compatible with the usual photographic additives present in the individual layers; Because of their good effectiveness, their use amount can be reduced and their precipitation or crystallization can be avoided if they are incorporated as an organic solution in the aqueous binder emulsions used for the production of photographic layers.
  • the individual processing steps necessary for the production of the color images after the exposure of the photographic recording material are not adversely affected by the light stabilizers. Furthermore, the so-called pressure fog formation that frequently occurs with blue-sensitive emulsions can be largely suppressed.
  • 0.4 ml of 1.5% aqueous gelatin solution and 4.0 ml of water are mixed together, adjusted to a pH of 6.5 and poured at 40 ° C. onto a 13 x 18 cm format glass plate. After the layer has solidified at 10 ° C., the plate is dried in a drying cabinet with ambient air at room temperature.
  • a strip of the coated glass plate cut to a format of 4.0 cm x 6.5 cm is exposed to 500 lux for 6 seconds under a step wedge and then processed at 32.8 ° C ( ⁇ 0.3 ° C) as follows:
  • the developer bath has the following composition:
  • a conventional bath is used as a bleach-fixing bath, e.g. B. has the following composition.
  • the step wedge obtained in this way is irradiated in an Atlas device (lamp 2500 W) with 10,000 Langley units each with and without an ultraviolet filter (Kodak filter 2C).
  • a step wedge produced in an analog manner, which contains no additive, and further step wedges which were produced using the compounds of the formulas (104) and (107) to (110) are used for comparison.
  • the data show the good protection of the photographic material against the harmful influence of light, which can be achieved when using the light stabilizers used according to the invention.
  • the effects are significantly improved compared to those that can be achieved with known light stabilizers already used in photographic materials.
  • Good results are also obtained with the compounds of the formulas (4), (6), (8) to (22) and (24) to (31).
  • a strip of the coated glass plate cut to a format of 4.0 cm ⁇ 6.5 cm is exposed under a step wedge at 500 lux for 6 seconds and then at 32.8 ° C. ( ⁇ 0.3 ° C) processed as described in Example 1.
  • a clear, sharp, blue-green colored step wedge is obtained with an absorption maximum at 653 nm and a maximum density of 1.10.
  • step wedge and step wedges produced analogously, which were produced using the compounds (105) to (110), are exposed and measured as described in Example 1. Table 2 contains the results.
  • 3,510- 3 mol of the yellow coupler of the formula (DE-OS 2716204) are dissolved in 10 ml of ethyl acetate and mixed with 1.5 g of tricresyl phosphate.
  • This solution is emulsified in 100 ml of 4% gelatin solution, which contains 0.3 g of an alkyl aryl sulfonate emulsifier, using an ultrasound device.
  • the ethyl acetate is then distilled off.
  • a light-sensitive silver chloride bromide dispersion average particle size of the silver halide crystals about 1 ⁇ m which was chemically sensitized in the usual way is then mixed in at about 40 ° C.
  • ⁇ D min so-called pressure veil.
  • the increase in the minimum density compared to the blank is a measure of the bending stress.
  • Gelatin solutions are prepared as in Example 1, but the light stabilizers of the formulas (23) (according to the invention) and (105) and (106) (comparison) and the yellow coupler of the formula are used or the formula (DE-OS 2 757 380).
  • the light stabilizers and the yellow couplers are used in a molar ratio of 1: 1.
  • Example 1 The production of the coated glass plates, the exposure and photographic processing and the light fastness test are carried out as in Example 1.
  • the light fastness test is carried out with an irradiation of 15,000 Langley units.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Hydrogenated Pyridines (AREA)

Claims (8)

1. Matière d'enregistrement de photographies en couleurs contenant au moins un dérivé de la pipéridine comme agent de protection contre la lumière dans au moins une couche d'émulsion d'halogénure d'argent sensible à la lumière, une couche intermédiaire, et/ou une couche de protection; caractérisé par le fait que le dérivé de la piperidine a la formule
Figure imgb0064
dans laquelle R1 est l'hydrogène ou un radical alcoyle ayant 1 à 4 atomes de carbone; R2 est un radical alcoyle ou hydroxyalcoyle ayant chacun 1 à 12 atomes de carbone, àlcényle ou alcinyle ayant 3 ou 4 atomes de carbone, benzyle ou R6CO―, dans lequel R6 est l'hydrogène, alcoyle ayant 1 à 12 atomes de carbone, alcényle ayant 2 ou 3 atomes de carbone, cyclohexyle, benzyle, ou un radical phényle éventuellement substitué par deux groupes alcoyle ayant chacun 1 à 4 atomes de carbone et un groupe hydroxyle, ou le radical phényléthyle; R3 est l'hydrogène ou le radica! méthyle; R4 et R5 sont chacun un radical alcoyle ayant 1 à 5 atomes de carbone ou cycloalcoyle ayant 5 à 8 atomes de carbone; Y est l'hydrogène un radical alcoyle ayant 1 à 12 atomes de carbone, ―CnH2nCOOR7 dans lequel n est 0 ou un nombre entier de 1 à 10 et R7 est l'hydrogène, un radical alcoyle ayant 1 à 18 atomes de carbone, de préférence méthyle ou éthyle ou le radical de formule
Figure imgb0065
ou bien Y est un radical CH2CH2CHn ―NHCOR8 dans lequel R8 est un radical méthyle, éthyle, phényle ou benzyle, Y est encore un radical cyanogène, benzyle ou le radical de formule
Figure imgb0066
dans laquelle R1 et R2 ont les significations indiquées, R9 est l'hydrogène ou un radical alcoyle ayant 1 à 4 atomes de carbone; m est 1 ou 2 et p est 1 ou 0.
2. Matière d'enregistrement de photographies en couleurs selon la revendication 1, caractérisée par le fait que le dérivé de la pipéridine a la formule:
Figure imgb0067
dans laquelle Rio est un radical méthyle, éthyle, benzyle, acétyle, acrylyle, méthacrylyle, crotonyle, allyle ou propargyle.
3. Matière d'enregistrement de photographies en couleurs selon une des revendications 1 ou 2, caractérisée par le fait qu'elle contient l'agent de protection contre la lumière en combinaison avec des absorbants de l'ultra-violet.
4. Matière d'enregistrement de photographies en couleurs selon la revendication 3, caractérisée par le fait que les absorbants de l'ultra-violet sont des composés du type benzophénone, acrylonitrile, thiazolidone, benzotriazole, oxazole, thiazole ou imidazole.
5. Matière d'enregistrement de photographies en couleurs selon une des revendications 1 à 4, caractérisée par le fait qu'elle contient 1 à 500 mg de l'agent de protection contre la lumière et éventuellement de l'absorbant de l'ultra-violet par m2 de la couche dans laquelle ils sont incorporés.
6. Procédé de stabilisation des matières d'enregistrement de photographies en couleurs contenant au moins une couche d'émulsion d'halogénure d'argent sensible à la lumière, contre l'action nuisible de la lumière; caractérisé par le fait qu'on incorpore dans au moins une couche d'émulsion d'halogénure d'argent, une couche intermédiaire, et/ou une couche de protection, 1 à 500 mg par m2 de couche d'au moins un agent de protection contre la lumière selon la revendication 1, éventuellement en combinaison avec des absorbants de l'ultra-violet.
7. Procédé de fabrication d'images photographiques en couleurs par exposition à la lumière image par image et développement des couleurs d'une matière d'enregistrement de photographies en couleurs selon une des revendications 1 à 5.
8. Les images photographiques en couleurs obtenues selon le procédé de la revendication 7.
EP79810141A 1978-11-06 1979-10-31 Matériel d'enregistrement photographique en couleurs, procédé pour sa stabilisation et préparation d'images photographiques en couleurs Expired EP0011051B1 (fr)

Applications Claiming Priority (2)

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CH11396/78 1978-11-06
CH1139678 1978-11-06

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EP0011051A2 EP0011051A2 (fr) 1980-05-14
EP0011051A3 EP0011051A3 (en) 1980-05-28
EP0011051B1 true EP0011051B1 (fr) 1982-09-15

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US (1) US4268593A (fr)
EP (1) EP0011051B1 (fr)
JP (1) JPS5565954A (fr)
CA (1) CA1145605A (fr)
DE (1) DE2963689D1 (fr)

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JPS58102231A (ja) * 1981-12-14 1983-06-17 Fuji Photo Film Co Ltd カラ−写真感光材料
DE3275592D1 (en) * 1981-12-17 1987-04-09 Ciba Geigy Ag Colour-photographic recording material
EP0103540A1 (fr) * 1982-08-18 1984-03-21 Ciba-Geigy Ag Matériel d'enregistrement photographique en couleurs
EP0104146B1 (fr) * 1982-09-21 1986-07-30 Ciba-Geigy Ag Matériau d'enregistrement photographique couleur
DE3375431D1 (en) * 1982-11-18 1988-02-25 Ciba Geigy Ag Colour-photographic recording material
DE3375432D1 (en) * 1982-11-26 1988-02-25 Ciba Geigy Ag Colour-photographic recording material
DE3375230D1 (en) * 1982-12-03 1988-02-11 Ciba Geigy Ag Colour-photographic recording material
EP0111448B1 (fr) * 1982-12-08 1988-01-13 Ciba-Geigy Ag Matériel d'enregistrement photographique couleur
DE3377596D1 (en) * 1982-12-16 1988-09-08 Ciba Geigy Ag Colour-photographic recording material
DE3373720D1 (en) * 1982-12-16 1987-10-22 Ciba Geigy Ag Colour-photographic recording material
DE3375231D1 (en) * 1982-12-16 1988-02-11 Ciba Geigy Ag Colour-photographic recording material
JPS59124340A (ja) * 1982-12-30 1984-07-18 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
JPS60222853A (ja) * 1984-04-20 1985-11-07 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
EP0203746B2 (fr) * 1985-05-11 1994-08-24 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière
US4728599A (en) * 1985-12-02 1988-03-01 Eastman Kodak Company Sterically hindered phenolic ester photographic coupler dispersion addenda and photographic elements employing same
EP0256537B1 (fr) 1986-08-15 1992-12-30 Fuji Photo Film Co., Ltd. Epreuve couleur et méthode pour sa production
EP0382285B1 (fr) * 1989-02-08 1994-10-26 Agfa-Gevaert N.V. Matériau de toner en particules
US5449777A (en) * 1993-07-08 1995-09-12 Ciba-Geigy Corporation Phenolic s-triazines
JP3584119B2 (ja) 1996-04-05 2004-11-04 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
US7090969B1 (en) 2005-03-15 2006-08-15 Eastman Kodak Company Coupler and image dye light-stabilizing systems
WO2008076101A1 (fr) * 2006-12-18 2008-06-26 3M Innovative Properties Company Composition de résine (méth)acrylique et films fabriqués à partir de cette composition
JP4988383B2 (ja) * 2007-03-02 2012-08-01 スリーエム イノベイティブ プロパティズ カンパニー （メタ）アクリル系着色フィルム、マーキングフィルム、レセプターシート、及びその製造方法
JP5307378B2 (ja) * 2007-10-26 2013-10-02 スリーエム イノベイティブ プロパティズ カンパニー （メタ）アクリル系フィルムおよびこれを用いたマーキングフィルム
JP2009270062A (ja) 2008-05-09 2009-11-19 Fujifilm Corp 紫外線吸収剤組成物
CN112010800B (zh) * 2020-09-08 2021-11-16 宿迁联盛科技股份有限公司 一种含受阻酚的受阻胺光稳定剂及其制备方法和应用
CN112010799B (zh) * 2020-09-08 2022-03-25 宿迁联盛科技股份有限公司 一种受阻胺光稳定剂中间体及其制备方法和应用

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US2596926A (en) * 1949-12-16 1952-05-13 Gen Aniline & Film Corp Preparation of azine dye images
US3183219A (en) * 1963-10-29 1965-05-11 Polaroid Corp 2-benzoyl-5-methoxyphenyl acrylate and polymers thereof
JPS4920973B1 (fr) * 1970-05-28 1974-05-29
CH601232A5 (fr) * 1975-12-08 1978-06-30 Ciba Geigy Ag

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JPS5565954A (en) 1980-05-17
EP0011051A2 (fr) 1980-05-14
US4268593A (en) 1981-05-19
JPS5720617B2 (fr) 1982-04-30
DE2963689D1 (en) 1982-11-04
EP0011051A3 (en) 1980-05-28
CA1145605A (fr) 1983-05-03

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