EP0379893B1 - Colour-photographic recording material containing an emulsified compound providing colour - Google Patents
Colour-photographic recording material containing an emulsified compound providing colour Download PDFInfo
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- EP0379893B1 EP0379893B1 EP90100495A EP90100495A EP0379893B1 EP 0379893 B1 EP0379893 B1 EP 0379893B1 EP 90100495 A EP90100495 A EP 90100495A EP 90100495 A EP90100495 A EP 90100495A EP 0379893 B1 EP0379893 B1 EP 0379893B1
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- color
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- recording material
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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
- G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
- G03C7/3882—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific polymer or latex
Definitions
- the invention relates to a color photographic recording material which, in association with at least one light-sensitive silver halide emulsion layer, contains an emulsified, comparatively hydrophilic coloring compound.
- Hydrophilic color couplers and other coloring compounds are generally added to the photographic coating solutions in the form of an aqueous or aqueous-alcoholic solution.
- the required amounts of alkali are used in the preparation of the solutions, provided that the coupler is not already present in water-soluble form as the alkali salt.
- Hydrophilic color couplers are often characterized by particularly high coupling speeds and are therefore very desirable in the production of highly sensitive color photographic recording materials.
- When incorporating Hydrophilic compounds from aqueous-alkaline solution in photographic layers have serious disadvantages, insofar as the high salt content in the emulsion caused by the neutralization of the alkaline solutions causes poor flatness and high brittleness of the materials.
- the casting solutions generally have to be diluted strongly with water in order to compensate for the increase in viscosity caused by the reaction of the sulfo groups or carboxyl groups with the amino groups of the gelatin.
- this method makes it difficult to produce layers with a desired high packing density on color couplers or other coloring compounds.
- hydrophobic coloring compounds are used and these are incorporated in an emulsified form into the photographic coating solutions in a known manner using high-boiling organic solvents, so-called oil formers.
- oil formers are phthalic acid esters, such as dibutyl phthalate or di-n-nonyl phthalate, and phosphoric acid esters, such as tricresyl phosphate; the oil formers mentioned are comparatively hydrophobic and therefore usually very well suited for incorporating hydrophobic substances.
- the suitability of an oil producer is expressed in that the coloring compound in the relevant oil former has the highest possible solubility and a low tendency to crystallize.
- Coloring compounds are occasionally used because of their special properties, which in the aforementioned hydrophobic oil formers still have a certain, in many cases still sufficient, but nevertheless reduced solubility and have a clearly hydrophilic character. Such coloring compounds are referred to below as "comparatively hydrophilic".
- the reduced solubility in the hydrophobic oil formers manifests itself in an increased tendency to crystallize and affects the technical production of the O / W emulsion (oil in water) of the coloring compounds on the one hand, and on the other hand their use in low-binder layers, for example in layers with no more than 40% by weight gelatin, particularly noticeable. If the O / W emulsions are produced on an industrial scale and a co-solvent used is removed rapidly, for example at a rate of more than 30 g / s, crystallization often occurs. In addition, the comparatively hydrophilic coloring compounds mentioned are obviously not sufficiently diffusion-resistant in many cases when using the conventional hydrophobic oil formers, and this disadvantage is particularly evident when used in layers with little binder.
- the invention has for its object to provide new oil formers for coloring compounds, especially for comparatively hydrophilic coloring compounds. It has now been found that polypropylene oxides with an OH group content of between 1 and 3% by weight are suitable.
- the present invention relates to a color photographic recording material with at least one silver halide emulsion layer, which is associated with a coloring compound incorporated with the aid of an oil former, characterized in that the oil former contains at least 30% by weight of a polypropylene oxide with an OH content of 1-3 % By weight.
- the polypropylene oxide used according to the invention as an oil former can be produced by reacting water or monohydric or polyhydric alcohols with propylene oxide (PO), water with about 20-50 times the amount by weight of PO and the alcohol in question, depending on the molecular weight and value, with about 10 - 100 times the molar amount of PO are reacted to set an OH content of 1-3% by weight.
- PO propylene oxide
- the molecular weight of the polypropylene oxide a statistical distribution over the entirety of the molecules is generally obtained.
- Examples of monohydric or polyhydric alcohols to be used are ethanol, propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, 1,2- and 1,3-propylene glycol, glycerol, tetramethylolethane, pentaerythritol, trimethylolpropane.
- Examples of compounds according to the invention are given below.
- the molar amount of PO which has been reacted with 1 mol of water or mono- or polyhydric alcohol is given.
- emulsions of coloring compounds can be produced in a manner known per se.
- these are generally O / W emulsions (oil-in-water emulsions) in which the oily phase contains the coloring compound to be emulsified, at least one polypropylene oxide (oil former) according to the invention, optionally an auxiliary solvent and further optionally an emulsifying auxiliary, and the aqueous phase usually contains a suitable binder, for example gelatin.
- the auxiliary solvent is normally removed again in the course of the preparation of the emulsate.
- the oil former according to the invention can also be used in the form of a mixture.
- hydrophilic oil formers such as, for example, long-chain aliphatic substituted succinic acid esters of the like, as described for example in DE-A 1 772 192, can also be used.
- the proportion of polypropylene oxides according to the invention in the total amount of oil former should not be less than 30% by weight.
- coloring compounds of all kinds can be incorporated into photographic layers. These are generally non-diffusing compounds that can be colored or colorless. Under the conditions of photographic development, a dye is formed from such compounds, either by releasing an optionally pre-formed colored residue as a diffusing dye or by chromogenic coupling with the oxidation product of a color developer. In the latter case, there are color couplers, e.g. Yellow coupler, magenta coupler or cyan coupler.
- the color couplers can be 4-equivalent couplers, but also 2-equivalent couplers.
- the latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point, which is split off during the coupling.
- the 2-equivalent couplers include those that are colorless, as well as 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 (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products.
- the 2-equivalent couplers also include those couplers which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue (e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic activity unfolds, for example as a development inhibitor or accelerator.
- Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.
- DIR, DAR or FAR couplers Since with DIR, DAR or FAR couplers the effectiveness of the residue released during coupling is mainly desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable which give essentially colorless products on coupling (DE-A-15 47 640).
- the cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).
- the oil formers according to the invention are used with particular advantage to incorporate those compounds which, as explained at the outset, are referred to as "comparatively hydrophilic". These are in particular compounds that contain one or more -SO2-NH groups and / or phenolic hydroxyl groups in their molecule. Examples of such compounds are couplers C-26, M-2, M-8, M-19, M-20, M-21, Y-3, Y-7 and Y-13. By virtue of such groupings, the coloring compounds have an increased solubility in the alkaline processing baths usually used, so that an undesired diffusion into adjacent layers cannot normally be completely prevented during processing. The less binder the individual layers contain, the more this undesirable effect occurs.
- the comparatively hydrophilic coloring compounds are obviously less soluble in the commonly used hydrophobic oil formers, which manifests itself in an increased tendency to crystallize. If, on the other hand, the comparatively hydrophilic coloring compounds are incorporated with the help of the oil formers according to the invention, then not only the tendency towards crystallization but also the tendency to diffuse is significantly reduced. When using the oil formers according to the invention, it is therefore possible to reduce the proportion by weight of the binder in a layer containing at least one coloring compound and optionally silver halide to 40% or less.
- color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the silver color bleaching process.
- Suitable supports for the production of color photographic materials are e.g. Films and foils of semi-synthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and paper laminated with a baryta layer or ⁇ -olefin polymer layer (e.g. polyethylene).
- These carriers can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light.
- the surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer. Layer supports with a light-reflecting surface are preferred.
- the color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.
- Essential constituents of the photographic emulsion layers are binders, light-sensitive silver halide and coloring compounds, eg color couplers.
- Gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers.
- Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers.
- Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates.
- Semi-synthetic gelatin substitutes are usually modified natural products.
- Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives, which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers, are examples of this.
- the binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents.
- functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
- the gelatin which is preferably used can be obtained by acidic or alkaline digestion. Oxidized gelatin can also be used. The production such gelatins are described, for example, in The Science and Technology of Gelatine, edited by AG Ward and A. Courts, Academic Press 1977, page 295 ff.
- the gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
- the silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide.
- the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide.
- silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions with a high chloride content are used up to pure silver chloride emulsions.
- It can be predominantly compact crystals, which are, for example, regularly cubic or octahedral or can have transitional forms.
- platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain.
- the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, for example 12: 1 to 30: 1.
- the silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as e.g. Doping of the individual grain areas are different.
- the average grain size of the emulsions is preferably between 0.2 ⁇ m and 2.0 ⁇ m, the grain size distribution can be either homodisperse or heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ⁇ 30%.
- Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
- the photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
- the photographic emulsions can be spectrally sensitized using methine dyes or other dyes.
- Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
- Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromides.
- the differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it.
- the red-sensitive layers are cyan couplers
- the green-sensitive layers are magenta couplers
- the blue-sensitive layers are yellow couplers.
- the couplers or other compounds can be incorporated into silver halide emulsion layers and other layers in such a way that a solution, a dispersion or an emulsion is first prepared from the compound in question and then added to the casting solution for the layer in question.
- the selection of the suitable solvent or dispersing agent depends on the solubility of the compound.
- Hydrophobic compounds can be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-0 043 037.
- suitable oil formers which can be used in addition to the polypropylene oxides according to the invention are dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl tri-ethyl-tri-ethylhexyl tri-ethyl-tri-ethyl-tri-ethyl-tri-ethyl-trihydrate, tri-2-ethylhexyl tri-ethyl-tri-ethyl-tri-ethyl-tri-ethylate -2-ethylhexylphenyl phosphate, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylbenz
- the non-light-sensitive intermediate layers which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.
- Suitable agents which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), chapters VII, 17 842 (Feb. 1979) and 18 716 (Nov. 1979), page 650 and in EP A-0 069 070, 0 098 072, 0 124 877 and 0 125 522.
- the photographic recording material can furthermore contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives for improving the dye, coupler and white stabilization and for reducing the color fog, plasticizers (latices), Contain biocides.
- Examples are aryl-substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), cinnamic acid ester compounds (US-A-3 705 805 and 3,707,375), butadiene compounds (US-A-4,045,229) or benzoxazole compounds (US-A-3,700,455).
- Ultraviolet absorbing couplers such as ⁇ -naphthol type cyan couplers
- ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.
- Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.
- Suitable whiteners are e.g. in Research Disclosure 17,643 (Dec. 1978), Chapter V, in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763.
- binder layers in particular the most distant layer from the support, but also occasionally intermediate layers, especially if they are the most distant layer from the support during manufacture, may contain photographically inert particles of inorganic or organic nature, e.g. as a matting agent or as a spacer (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).
- photographically inert particles of inorganic or organic nature e.g. as a matting agent or as a spacer (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).
- the average particle diameter of the spacers is in particular in the range from 0.2 to 10 ⁇ m.
- the spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath.
- suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
- Additives to improve dye, coupler and whiteness stability and to reduce the color fog can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromans, spiroindanes , p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
- the layers of the photographic material can be hardened with the usual hardening agents.
- Suitable curing agents include formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen contain (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207) divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3,5 triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2 732 316 and US
- the hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened, or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.
- the last-mentioned curing agents which react very quickly with gelatin are, for example, carbamoylpyridinium salts which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin with the formation of peptide bonds and crosslinking of the gelatin.
- Coupler emulsions are produced according to the following general emulsification instructions.
- the oil phase is emulsified into the aqueous phase with a mixed siren. After the addition is complete, the mixture is post-homogenized at 50 bar using a high-pressure homogenizer.
- auxiliary solvent ethyl acetate
- solvent evaporator evaporating between 30 and 50 g of ethyl acetate per second.
- connection W-1 was used as the white coupler.
- a color photographic recording material was produced by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene.
- the quantities given relate to 1 m2.
- the corresponding amounts of AgNO3 are given.
- the oil formers and yellow couplers used in the blue-sensitive layer are given in Tables 2 and 3.
- the processing baths were produced according to the following recipes:
- Table 2 shows the percent yellow secondary density obtained after green exposure, based on a magenta density of 1.0.
- the relevant value is also given in brackets in the first line, which was obtained for CPM and K-4 with a material which differed only in layer 2 by a gelatin content of 50% by weight. It is clear that when the oil formers according to the invention are used, the gelatin content in layer 2 can be reduced to values below 40% by weight without the yellow secondary density being disadvantageously increased by undesirable diffusion of the yellow coupler into the magenta layer.
- the percentage magenta density obtained after blue exposure is given.
- the value given in brackets in the first line means the magenta secondary density of a corresponding material which has a gelatin content of 50% by weight in layer 2. It is again clear that the reduction in the gelatin content in layer 2 also has a disadvantageous effect on the undesirable diffusion of the magenta coupler and that, surprisingly, this disadvantageous effect can be suppressed in the yellow layer when the oil former according to the invention is used.
- Example 2 Various of the materials defined in Example 2 in connection with Table 2 with the yellow coupler K-4 were exposed and processed and then exposed to a radiation of 1.5 ⁇ 107 lxh in a Xenotest device.
- the percentage decrease in the yellow density was determined for different initial densities once in the yellow color separation wedge and once in the neutral wedge and is given in Table 4 (values of the neutral wedge in brackets).
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Description
Die Erfindung betrifft ein farbfotografisches Aufzeichnungsmaterial, das zugeordnet zu mindestens einer lichtempfindlichen Silberhalogenidemulsionsschicht eine emulgierte vergleichsweise hydrophile farbgebende Verbindung enthält.The invention relates to a color photographic recording material which, in association with at least one light-sensitive silver halide emulsion layer, contains an emulsified, comparatively hydrophilic coloring compound.
Hydrophile Farbkuppler und sonstige farbgebende Verbindungen werden im allgemeinen in Form einer wäßrigen oder wäßrig-alkoholischen Lösung den fotografischen Gießlösungen zugesetzt. Bei der Herstellung der Lösungen bedient man sich der erforderlichen Mengen Alkali, sofern der Kuppler nicht bereits in wasserlöslischer Form als Alkalisalz vorliegt. Hydrophile Farbkuppler zeichnen sich vielfach durch besonders hohe Kupplungsgeschwindigkeiten aus und sind daher sehr erwünscht bei der Herstellung hochempfindlicher farbfotografischer Aufzeichnungsmaterialien. Jedoch treten bei der Einarbeitung von hydrophilen Verbindungen aus wäßrig-alkalischer Lösung in fotografischen Schichten schwerwiegende Nachteile auf, insofern als der durch die Neutralisation der alkalischen Lösungen bedingte hohe Salzgehalt in der Emulsion eine schlechte Planlage und hohe Brüchigkeit der Materialien bewirkt. Weiterhin müssen die Gießlösungen in der Regel stark mit Wasser verdünnt werden, um den durch Reaktion der Sulfogruppen oder Carboxylgruppen mit den Aminogruppen der Gelatine bedingten Anstieg der Viskosität auszugleichen. Hieraus resultiert ein relativ hoher Naßauftrag der Schichten beim Beguß, was wiederum einen hohen Aufwand bei der Trocknung der Schichten erfordert. Außerdem sind nach dieser Methode Schichten mit einer erwünscht hohen Packungsdichte an Farbkupplern oder anderen farbgebenden Verbindungen nur schwer herstellbar.Hydrophilic color couplers and other coloring compounds are generally added to the photographic coating solutions in the form of an aqueous or aqueous-alcoholic solution. The required amounts of alkali are used in the preparation of the solutions, provided that the coupler is not already present in water-soluble form as the alkali salt. Hydrophilic color couplers are often characterized by particularly high coupling speeds and are therefore very desirable in the production of highly sensitive color photographic recording materials. However, when incorporating Hydrophilic compounds from aqueous-alkaline solution in photographic layers have serious disadvantages, insofar as the high salt content in the emulsion caused by the neutralization of the alkaline solutions causes poor flatness and high brittleness of the materials. Furthermore, the casting solutions generally have to be diluted strongly with water in order to compensate for the increase in viscosity caused by the reaction of the sulfo groups or carboxyl groups with the amino groups of the gelatin. This results in a relatively high wet application of the layers during casting, which in turn requires a great deal of effort in drying the layers. In addition, this method makes it difficult to produce layers with a desired high packing density on color couplers or other coloring compounds.
Die geschilderten Schwierigkeiten werden vermieden, wenn hydrophobe farbgebende Verbindungen verwendet werden und diese in emulgierter Form in bekannter Weise unter Verwendung hochsiedender organischer Lösungsmittel, sogenannter Ölbildner, in die fotografischen Gießlösungen eingearbeitet werden. Die Methode ist beispielsweise in US-A-2 322 027 beschrieben. Als Ölbildner kommen bevorzugt Phthalsäureester, wie Dibutylphthalat oder Di-n-nonylphthalat, und Phosphorsäureester, wie Trikresylphosphat zur Anwendung; die genannten Ölbildner sind vergleichsweise hydrophob und daher zur Einarbeitung hydrophober Substanzen meistens sehr gut geeignet. Die Eignung eines Ölbildners drückt sich darin aus, daß die farbgebende Verbindung in dem betreffenden Ölbildner eine möglichst hohe Löslichkeit und eine geringe Kristallisationstendenz aufweist. Gelegentlich werden farbgebende Verbindungen aufgrund besonderer Eigenschaften verwendet, die zwar in den erwähnten hydrophoben Ölbildnern noch eine gewisse, in vielen Fällen noch ausreichende, aber dennoch reduzierte Löslichkeit haben und einen deutlich hydrophilen Charakter aufweisen. Solche farbgebenden Verbindungen, werden nachfolgend als "vergleichsweise hydrophil" bezeichnet.The difficulties described are avoided if hydrophobic coloring compounds are used and these are incorporated in an emulsified form into the photographic coating solutions in a known manner using high-boiling organic solvents, so-called oil formers. The method is described for example in US-A-2 322 027. Preferred oil formers are phthalic acid esters, such as dibutyl phthalate or di-n-nonyl phthalate, and phosphoric acid esters, such as tricresyl phosphate; the oil formers mentioned are comparatively hydrophobic and therefore usually very well suited for incorporating hydrophobic substances. The suitability of an oil producer is expressed in that the coloring compound in the relevant oil former has the highest possible solubility and a low tendency to crystallize. Coloring compounds are occasionally used because of their special properties, which in the aforementioned hydrophobic oil formers still have a certain, in many cases still sufficient, but nevertheless reduced solubility and have a clearly hydrophilic character. Such coloring compounds are referred to below as "comparatively hydrophilic".
Die reduzierte Löslichkeit in den hydrophoben Ölbildnern äußert sich in einer erhöhten Kristallisationstendenz und macht sich einerseits bei der technischen Herstellung der O/W-Emulsion (Öl in Wasser) der farbgebenden Verbindungen, andererseits bei deren Verwendung in bindemittelarmen Schichten, z.B. in Schichten mit nicht mehr als 40 Gew.-% Gelatine, besonders störend bemerkbar. Wenn die O/W-Emulsionen in technischem Maßstab hergestellt werden und dabei ein verwendetes Hilfslösungsmittel rasch, z.B. mit einer Geschwindigkeit von mehr als 30 g/s, entfernt wird, tritt häufig Kristallisation ein. Die erwähnte vergleichsweise hydrophilen farbgebenden Verbindungen sind außerdem bei Verwendung der üblichen hydrophoben Ölbildner in vielen Fällen offensichtlich nicht ausreichend diffusionsfest und dieser Nachteil tritt besonders bei Verwendung in bindemittelarmen Schichten zutage.The reduced solubility in the hydrophobic oil formers manifests itself in an increased tendency to crystallize and affects the technical production of the O / W emulsion (oil in water) of the coloring compounds on the one hand, and on the other hand their use in low-binder layers, for example in layers with no more than 40% by weight gelatin, particularly noticeable. If the O / W emulsions are produced on an industrial scale and a co-solvent used is removed rapidly, for example at a rate of more than 30 g / s, crystallization often occurs. In addition, the comparatively hydrophilic coloring compounds mentioned are obviously not sufficiently diffusion-resistant in many cases when using the conventional hydrophobic oil formers, and this disadvantage is particularly evident when used in layers with little binder.
Der Erfindung liegt die Aufgabe zugrunde neue Ölbildner für farbgebende Verbindungen, insbesondere für vergleichsweise hydrophile farbgebende Verbindungen, anzugeben. Es wurde nun gefunden, daß hierfür Polypropylenoxide mit einem Gehalt an OH-Gruppen zwischen 1 und 3 Gew.-% geeignet sind.The invention has for its object to provide new oil formers for coloring compounds, especially for comparatively hydrophilic coloring compounds. It has now been found that polypropylene oxides with an OH group content of between 1 and 3% by weight are suitable.
Gegenstand der vorliegenden Erfindung ist ein farbfotografisches Aufzeichnungsmaterial mit mindestens einer Silberhalogenidemulsionsschicht, der eine mit Hilfe eines Ölbildners eingearbeitete farbgebende Verbindung zugeordnet ist, dadurch gekennzeichnet, daß der Ölbildner zu mindestens 30 Gew.-% aus einem Polypropylenoxid mit einem OH-Gehalt von 1-3 Gew.-% besteht.The present invention relates to a color photographic recording material with at least one silver halide emulsion layer, which is associated with a coloring compound incorporated with the aid of an oil former, characterized in that the oil former contains at least 30% by weight of a polypropylene oxide with an OH content of 1-3 % By weight.
Das erfindungsgemäß als Ölbildner verwendete Polypropylenoxid kann hergestellt werden durch Umsetzung von Wasser oder ein- oder mehrwertigen Alkoholen mit Propylenoxid (PO), wobei Wasser mit etwa der 20 - 50-fachen Gewichtsmenge PO und der betreffende Alkohol je nach Molgewicht und Wertigkeit mit etwa der 10 - 100-fachen Molmenge PO umgesetzt werden um einen OH-Gehalt von 1-3 Gew.-% einzustellen. Hierbei werden hinsichtlich des Molekulargewichtes des Polypropylenoxids in der Regel eine statistische Verteilung über die Gesamtheit der Moleküle erhalten.The polypropylene oxide used according to the invention as an oil former can be produced by reacting water or monohydric or polyhydric alcohols with propylene oxide (PO), water with about 20-50 times the amount by weight of PO and the alcohol in question, depending on the molecular weight and value, with about 10 - 100 times the molar amount of PO are reacted to set an OH content of 1-3% by weight. With regard to the molecular weight of the polypropylene oxide, a statistical distribution over the entirety of the molecules is generally obtained.
Beispiele für einzusetzende ein- oder mehrwertige Alkohole sind Ethanol, Propanol, Isopropanol, n-Butanol, Isobutanol, Ethylenglykol, 1,2- und 1,3-Propylenglykol, Glycerin, Tetramethylolethan, Pentaerythrit, Trimethylolpropan.Examples of monohydric or polyhydric alcohols to be used are ethanol, propanol, isopropanol, n-butanol, isobutanol, ethylene glycol, 1,2- and 1,3-propylene glycol, glycerol, tetramethylolethane, pentaerythritol, trimethylolpropane.
Beispiele erfindungsgemäßer Verbindungen (Polypropylenoxide) sind im folgenden angegeben. Es ist jeweils die Molmenge PO angegeben, die mit 1 mol Wasser bzw. ein- oder mehrwertigerm Alkohol umgesetzt wurden.
Eine ausführliche Darstellung der Verwendung von Polyethylenoxid-Addukten in der Fotografie mit vielen Literaturzitaten findet sich bei Nikolaus Schönfeldt, Grenzflächenaktive Ethylenoxid-Addukte, Wissenschaftliche Verlagsgesellschaft mbH Stuttgart, 1976, Seiten 826-829.A detailed description of the use of polyethylene oxide adducts in photography with many references can be found in Nikolaus Schönfeldt, interfacially active ethylene oxide adducts, Wissenschaftliche Verlagsgesellschaft mbH Stuttgart, 1976, pages 826-829.
Unter Verwendung der erfindungsgemäßen Polypropylenoxide als Ölbildner lassen sich in sonst an sich bekannter Weise Emulgate von farbgebenden Verbindungen herstellen. Hierbei handelt es sich im allgemeinen um O/W-Emulsionen (Öl- in Wasser-Emulsionen) bei denen die ölige Phase die zu emulgierende farbgebende Verbindung, mindestens ein erfindungsgemäßes Polypropylenoxid (Ölbildner), gegebenenfalls ein Hilfslösungsmittel sowie weiter gegebenenfalls ein Emulgierhilfsmittel, und die wäßrige Phase in der Regel ein geeignetes Bindemittel, beispielsweise Gelatine, enthält. Das Hilfslösungsmittel wird normalerweise im Verlauf der Herstellung des Emulgates wieder entfernt. Der erfindungsgemäße Ölbildner kann auch in Form eines Gemisches eingesetzt werden. Auch können herkömmliche Ölbildner, wie Trikresylphthalat (TKP) oder Dibutylphthalat (DBP) und ähnliche, auch hydrophilere Ölbildner wie beispielsweise langkettig aliphatisch substituierte Bernsteinsäurehalbester dergleichen wie beispielsweise in DE-A 1 772 192 beschrieben, mit verwendet werden. Jedoch soll der Anteil an erfindungsgemäßen Polypropylenoxiden an der Gesamtmenge an Ölbildner nicht weniger als 30 Gew.-% betragen.Using the polypropylene oxides according to the invention as oil formers, emulsions of coloring compounds can be produced in a manner known per se. These are generally O / W emulsions (oil-in-water emulsions) in which the oily phase contains the coloring compound to be emulsified, at least one polypropylene oxide (oil former) according to the invention, optionally an auxiliary solvent and further optionally an emulsifying auxiliary, and the aqueous phase usually contains a suitable binder, for example gelatin. The auxiliary solvent is normally removed again in the course of the preparation of the emulsate. The oil former according to the invention can also be used in the form of a mixture. Conventional oil formers, such as tricresyl phthalate (TKP) or dibutyl phthalate (DBP) and similar, even more hydrophilic oil formers such as, for example, long-chain aliphatic substituted succinic acid esters of the like, as described for example in DE-A 1 772 192, can also be used. However, the proportion of polypropylene oxides according to the invention in the total amount of oil former should not be less than 30% by weight.
Mit Hilfe der erfindungsgemäßen Ölbildner können farbgebende Verbindungen aller Art in fotografische Schichten eingearbeitet werden. Hierbei handelt es sich in der Regel um nicht diffundierende Verbindungen, die farbig oder farblos sein können. Unter den Bedingungen der fotografischen Entwicklung wird aus solchen Verbindungen ein Farbstoff gebildet und zwar entweder durch Freisetzen eines gegebenenfalls vorgebildeten farbigen Restes als diffundierender Farbstoff oder aber durch chromogene Kupplung mit dem Oxidationsprodukt eines Farbentwicklers. Im letzteren Fall handelt es sich um Farbkuppler, z.B. Gelbkuppler, Magentakuppler oder Cyankuppler.With the help of the oil formers according to the invention, coloring compounds of all kinds can be incorporated into photographic layers. These are generally non-diffusing compounds that can be colored or colorless. Under the conditions of photographic development, a dye is formed from such compounds, either by releasing an optionally pre-formed colored residue as a diffusing dye or by chromogenic coupling with the oxidation product of a color developer. In the latter case, there are color couplers, e.g. Yellow coupler, magenta coupler or cyan coupler.
Farbkuppler zur Erzeugung des blaugrünen Teilfarbenbildes sind in der Regel Kuppler vom Phenol- oder α-Naphtholtyp; geeignete Beispiele hierfür sind
- C-1:
- R¹, R₂ = H;
- C-2:
- R¹ = -NHCOOCH₂-CH(CH₃)₂; R² = H;
R³ = -(CH₂)₃-OC₁₂H₂₅ - C-3:
- R¹ = H; R² = -OCH₂-CH₂-SO₂CH₃; R³ =-C₁₆H₃₃
- C-4:
- R¹ = H; R² = -OCH₂-CONH-(CH₂)₂-OCH₃;
- C-5:
- R¹, R² = H;
- C-6:
- R¹, R² = H;
- C-7:
- R¹ = H; R² = Cl; R³ = -C(C₂H₅)₂-C₂₁H₄₃
- C-8:
- R¹ = H; R² = -O-CH₂-CH₂-S-CH(COOH)-C₁₂H₂₅
R³ = Cyclohexyl - C-9:
- R¹ = -C₄H₉; R² = H; R³ = -CN; R⁴ = Cl
- C-10:
- R¹ = -C₄H₉; R² = H; R³ = H; R⁴ = -SO₂CHF₂
- C-11:
- R¹ = -C₄H₉;
- C-12:
- R¹ = C₂H₅; R², R³ = H; R⁴ = -SO₂CH₃
- C-13:
- R¹ = -C₄H₉; R², R³ = H; R⁴ = -SO₂-C₄H₉
- C-14:
- R¹ = -C₄H₉; R² = H; R³ = -CN; R⁴ = -CN
- C-15:
- R¹ = -C₄H₉; R₂, R₃ = H; R⁴ = -SO₂-CH₂-CHF₂
- C-16:
- R¹ = -C₂H₅; R₂, R₃ = H; R₄ = -SO₂CH₂-CHF-C₃H₇
- C-17:
- R¹ = -C₄H₉; R₂, R₃ = H; R₄ = F
- C-18:
- R¹ = -C₄H₉; R₂, R₃ = H; R₄ = -SO₂CH₃
- C-19:
- R¹ = -C₄H₉; R₂, R₃ = H; R₄ = -CN
- C-20:
- R¹ = -CH₃; R² = -C₂H₅; R³, R⁴ = -C₅H₁₁-t
- C-21:
- R¹ = -CH₃; R² = H; R³, R⁴ = -C₅H₁₁-t
- C-22:
- R¹, R² = -C₂H₅; R³, R⁴ = -C₅H₁₁-t
- C-23:
- R¹ = -C₂H₅; R² = -C₄H₉; R³, R⁴ = -C₅H₁₁-t
- C-24:
- R¹ = -C₂H₅; R² = -C₄H₉; R³, R⁴ = C₄H₉-t
- C-25:
- R¹, R² = -C₅H₁₁-t; R³ = -C₄H₉; R⁴ = H; R⁵ = -C₃F₇
- C-26:
- R¹ = -NHSO₂-C₄H₉; R² = H; R³ = -C₁₂H₂₅; R⁴ = Cl;
R⁵ = Phenyl - C-27:
- R¹, R² = -C₅H₁₁-t; R² = Cl, R³ = -C₃H₇-i; R⁴ = Cl;
R⁵ = Pentafluorphenyl - C-28:
- R¹ = -C₅H₁₁-t; R² = Cl; R³ = -C₆H₁₃; R⁴ = Cl;
R⁵ = -2-Chlorphenyl
- C-1:
- R¹, R₂ = H;
- C-2:
- R¹ = -NHCOOCH₂-CH (CH₃) ₂; R² = H;
R³ = - (CH₂) ₃-OC₁₂H₂₅ - C-3:
- R1 = H; R² = -OCH₂-CH₂-SO₂CH₃; R³ = -C₁₆H₃₃
- C-4:
- R1 = H; R² = -OCH₂-CONH- (CH₂) ₂-OCH₃;
- C-5:
- R1, R2 = H;
- C-6:
- R1, R2 = H;
- C-7:
- R1 = H; R² = Cl; R³ = -C (C₂H₅) ₂-C₂₁H₄₃
- C-8:
- R1 = H; R² = -O-CH₂-CH₂-S-CH (COOH) -C₁₂H₂₅
R³ = cyclohexyl - C-9:
- R¹ = -C₄H₉; R² = H; R³ = -CN; R⁴ = Cl
- C-10:
- R¹ = -C₄H₉; R² = H; R³ = H; R⁴ = -SO₂CHF₂
- C-11:
- R¹ = -C₄H₉;
- C-12:
- R¹ = C₂H₅; R², R³ = H; R⁴ = -SO₂CH₃
- C-13:
- R¹ = -C₄H₉; R², R³ = H; R⁴ = -SO₂-C₄H₉
- C-14:
- R¹ = -C₄H₉; R² = H; R³ = -CN; R⁴ = -CN
- C-15:
- R¹ = -C₄H₉; R₂, R₃ = H; R⁴ = -SO₂-CH₂-CHF₂
- C-16:
- R¹ = -C₂H₅; R₂, R₃ = H; R₄ = -SO₂CH₂-CHF-C₃H₇
- C-17:
- R¹ = -C₄H₉; R₂, R₃ = H; R₄ = F
- C-18:
- R¹ = -C₄H₉; R₂, R₃ = H; R₄ = -SO₂CH₃
- C-19:
- R¹ = -C₄H₉; R₂, R₃ = H; R₄ = -CN
- C-20:
- R¹ = -CH₃; R² = -C₂H₅; R³, R⁴ = -C₅H₁₁-t
- C-21:
- R¹ = -CH₃; R² = H; R³, R⁴ = -C₅H₁₁-t
- C-22:
- R¹, R² = -C₂H₅; R³, R⁴ = -C₅H₁₁-t
- C-23:
- R¹ = -C₂H₅; R² = -C₄H₉; R³, R⁴ = -C₅H₁₁-t
- C-24:
- R¹ = -C₂H₅; R² = -C₄H₉; R³, R⁴ = C₄H₉-t
- C-25:
- R¹, R² = -C₅H₁₁-t; R³ = -C₄H₉; R⁴ = H; R⁵ = -C₃F₇
- C-26:
- R¹ = -NHSO₂-C₄H₉; R² = H; R³ = -C₁₂H₂₅; R⁴ = Cl;
R⁵ = phenyl - C-27:
- R¹, R² = -C₅H₁₁-t; R² = Cl, R³ = -C₃H₇-i; R⁴ = Cl;
R⁵ = pentafluorophenyl - C-28:
- R¹ = -C₅H₁₁-t; R² = Cl; R³ = -C₆H₁₃; R⁴ = Cl;
R⁵ = -2-chlorophenyl
Farbkuppler zur Erzeugung des purpurnen Teilfarbenbildes sind in der Regel Kuppler vom Typ des 5-Pyrazolons, des Indazolons oder der Pyrazoloazole; geeignete Beispiele hierfür sind
- M-1:
-
- M-2:
-
- M-3:
- R¹ = -C₁₃H₂₇; R² = H
- M-4:
- R¹ = -OC₁₆H₃₃; R² = H
- M-5:
- R¹ = -C₁₃H₂₇;
- M-6:
-
- M-7:
- R¹ = -C₉H₁₉;
- M-8:
-
- M-9:
-
- M-10:
-
- M-11:
-
- M-12:
-
- M-13:
-
- M-14:
-
- M-15:
-
- M-16:
-
- M-17:
-
- M-18:
-
- M-19:
-
- M-20:
-
- M-21:
-
- M-22:
-
- M-1:
-
- M-2:
-
- M-3:
- R¹ = -C₁₃H₂₇; R² = H
- M-4:
- R¹ = -OC₁₆H₃₃; R² = H
- M-5:
- R¹ = -C₁₃H₂₇;
- M-6:
-
- M-7:
- R¹ = -C₉H₁₉;
- M-8:
-
- M-9:
-
- M-10:
-
- M-11:
-
- M-12:
-
- M-13:
-
- M-14:
-
- M-15:
-
- M-16:
-
- M-17:
-
- M-18:
-
- M-19:
-
- M-20:
-
- M-21:
-
- M-22:
-
Farbkuppler zur Erzeugung des gelben Teilfarbenbildes sind in der Regel Kuppler mit einer offenkettigen Ketomethylengruppierung, insbesondere Kuppler vom Typ des α-Acylacetamids; geeignete Beispiele hierfür sind α-Benzoylacetanilidkuppler und α-Pivaloylacetanilidkuppler der Formeln
- Y-1:
- R¹ = -C₄H₉-t;
- Y-2:
- R¹ = -C₄H₉-t;
R⁵ = -SO₂NHCH₃ - Y-3:
- R¹ = -C₄H₉-t;
R⁴ = H; R⁵ = -NHSO₂-C₁₆H₃₃ - Y-4:
- R¹ = -C₄H₉-t;
R⁴ = H; R⁵ = -COOC₁₂H₂₅ - Y-5:
- R¹ = -C₄H₉-t;
R⁴ = H; - Y-6:
- R¹ = -C₄H₉-t;
- Y-7:
- R¹ = -C₄H₉-t;
R⁴ = H; R⁵ = -NHSO₂-C₁₆H₃₃ - Y-8:
- R¹ = -C₄H₉-t;
- Y-9:
- R¹ = -C₄H₉-t;
R⁴ = H; R⁵ = -SO₂NHCOC₂H₅ - Y-10:
- R¹ = -C₄H₉-t;
- Y-11:
- R¹ = -C₄H₉-t;
- Y-12:
- R¹ = -C₄H₉-t;
- Y-13:
- R¹ = -C₄H₉-t;
R⁵ = -SO₂NHCH₃ - Y-14:
- R¹ = -C₄H₉-t;
- Y-15:
-
- Y-16:
-
- Y-17:
-
- Y-18:
-
- Y-19:
-
- Y-20:
-
- Y-21:
-
- Y-1:
- R¹ = -C₄H₉-t;
- Y-2:
- R¹ = -C₄H₉-t;
R⁵ = -SO₂NHCH₃ - Y-3:
- R¹ = -C₄H₉-t;
R⁴ = H; R⁵ = -NHSO₂-C₁₆H₃₃ - Y-4:
- R¹ = -C₄H₉-t;
R⁴ = H; R⁵ = -COOC₁₂H₂₅ - Y-5:
- R¹ = -C₄H₉-t;
R⁴ = H; - Y-6:
- R¹ = -C₄H₉-t;
- Y-7:
- R¹ = -C₄H₉-t;
R⁴ = H; R⁵ = -NHSO₂-C₁₆H₃₃ - Y-8:
- R¹ = -C₄H₉-t;
- Y-9:
- R¹ = -C₄H₉-t;
R⁴ = H; R⁵ = -SO₂NHCOC₂H₅ - Y-10:
- R¹ = -C₄H₉-t;
- Y-11:
- R¹ = -C₄H₉-t;
- Y-12:
- R¹ = -C₄H₉-t;
- Y-13:
- R¹ = -C₄H₉-t;
R⁵ = -SO₂NHCH₃ - Y-14:
- R¹ = -C₄H₉-t;
- Y-15:
-
- Y-16:
-
- Y-17:
-
- Y-18:
-
- Y-19:
-
- Y-20:
-
- Y-21:
-
Bei den Farbkupplern kann es sich um 4-Äquivalentkuppler, aber auch um 2-Äquivalentkuppler handeln. Letztere leiten sich von den 4-Äquivalentkupplern dadurch ab, daß sie in der Kupplungsstelle einen Substituenten enthalten, der bei der Kupplung abgespalten wird. Zu den 2-Äquivalentkupplern sind solche zu rechnen, die farblos sind, als auch solche, die eine intensive Eigenfarbe aufweisen, die bei der Farbkupplung verschwindet bzw. durch die Farbe des erzeugten Bildfarbstoffes ersetzt wird (Maskenkuppler), und die Weißkuppler, die bei Reaktion mit Farbentwickleroxidationsprodukten im wesentlichen farblose Produkte ergeben. Zu den 2-Äquivalentkupplern sind ferner solche Kuppler zu rechnen, die in der Kupplungsstelle einen abspaltbaren Rest enthalten, der bei Reaktion mit Farbentwickleroxidationsprodukten in Freiheit gesetzt wird und dabei entweder direkt oder nachdem aus dem primär abgespaltenen Rest eine oder mehrere weitere Gruppen abgespalten worden sind (z.B. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), eine bestimmte erwünschte fotografische Wirksamkeit entfaltet, z.B. als Entwicklungsinhibitor oder -accelerator. Beispiele für solche 2-Äquivalentkuppler sind die bekannten DIR-Kuppler wie auch DAR-bzw. FAR-Kuppler.The color couplers can be 4-equivalent couplers, but also 2-equivalent couplers. The latter are derived from the 4-equivalent couplers in that they contain a substituent in the coupling point, which is split off during the coupling. The 2-equivalent couplers include those that are colorless, as well as 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 (mask coupler), and the white couplers that react with color developer oxidation products yield essentially colorless products. The 2-equivalent couplers also include those couplers which contain a cleavable residue in the coupling site, which is released upon reaction with color developer oxidation products and thereby either directly or after one or more further groups have been cleaved from the primarily cleaved residue ( e.g. DE-A-27 03 145, DE-A-28 55 697, DE-A-31 05 026, DE-A-33 19 428), a certain desired photographic activity unfolds, for example as a development inhibitor or accelerator. Examples of such 2-equivalent couplers are the known DIR couplers as well as DAR or. FAR coupler.
Da bei den DIR-, DAR- bzw. FAR-Kupplern hauptsächlich die Wirksamkeit des bei der Kupplung freigesetzten Restes erwünscht ist und es weniger auf die farbbildenden Eigenschaften dieser Kuppler ankommt, kommen auch solche DIR-, DAR- bzw. FAR-Kuppler in Frage, die bei der Kupplung im wesentlichen farblose Produkte ergeben (DE-A-15 47 640).Since with DIR, DAR or FAR couplers the effectiveness of the residue released during coupling is mainly desired and the color-forming properties of these couplers are less important, such DIR, DAR or FAR couplers are also suitable which give essentially colorless products on coupling (DE-A-15 47 640).
Der abspaltbare Rest kann auch ein Ballastrest sein, so daß bei der Reaktion mit Farbentwickleroxidationsprodukten Kupplungsprodukte erhalten werden, die diffusionsfähig sind oder zumindest eine schwache bzw. eingeschränkte Beweglichkeit aufweisen (US-A-4 420 556).The cleavable residue can also be a ballast residue, so that upon reaction with color developer oxidation products coupling products are obtained which are diffusible or at least have a weak or restricted mobility (US Pat. No. 4,420,556).
Mit besonderem Vorteil werden die erfindungsgemäßen Ölbildner zur Einarbeitung solcher Verbindungen verwendet, die - wie eingangs erläutert - als "vergleichsweise hydrophil" bezeichnet werden. Das sind insbesondere Verbindungen, die in ihrem Molekül eine oder auch mehrere -SO₂-NH-Gruppierungen und/oder phenolische Hydroxylgruppen enthalten. Beispiele solcher Verbindungen sind die Kuppler C-26, M-2, M-8, M-19, M-20, M-21, Y-3, Y-7 und Y-13. Vermöge solcher Gruppierungen weisen die farbgebenden Verbindungen in den üblicherweise verwendeten alkalischen Verarbeitungsbädern eine erhöhte Löslichkeit auf, so daß sich während der Verarbeitung eine unerwünschte Diffusion in benachbarte Schichten normalerweise nicht ganz unterbinden läßt. Dieser unerwünschte Effekt tritt umso stärker auf, je weniger Bindemittel die einzelnen Schichten enthalten.The oil formers according to the invention are used with particular advantage to incorporate those compounds which, as explained at the outset, are referred to as "comparatively hydrophilic". These are in particular compounds that contain one or more -SO₂-NH groups and / or phenolic hydroxyl groups in their molecule. Examples of such compounds are couplers C-26, M-2, M-8, M-19, M-20, M-21, Y-3, Y-7 and Y-13. By virtue of such groupings, the coloring compounds have an increased solubility in the alkaline processing baths usually used, so that an undesired diffusion into adjacent layers cannot normally be completely prevented during processing. The less binder the individual layers contain, the more this undesirable effect occurs.
Hinzu kommt, daß möglicherweise aufgrund der -SO₂-NH-Gruppen bzw. phenolischen Hydroxylgruppen die vergleichsweise hydrophilen farbgebenden Verbindungen offensichtlich weniger gut in den üblicherweise verwendeten hydrophoben Ölbildnern löslich sind, was sich in einer erhöhten Kristallisationstendenz äußert. Wenn hingegen die vergleichsweise hydrophilen farbgebenden Verbindungen mit Hilfe der erfindungsgemäßen Ölbildner eingearbeitet werden, dann ist nicht nur die Kristallisationstendenz, sondern auch die Diffusionsneigung deutlich reduziert. Bei Anwendung der erfindungsgemäßen Ölbildner ist es daher möglich, den Gewichtsanteil des Bindemitteln in einer mindestens eine farbgebende Verbindung und gegebenenfalls Silberhalogenid enthaltenden Schicht auf 40 % oder weniger zu reduzieren.In addition, because of the -SO₂-NH groups or phenolic hydroxyl groups, the comparatively hydrophilic coloring compounds are obviously less soluble in the commonly used hydrophobic oil formers, which manifests itself in an increased tendency to crystallize. If, on the other hand, the comparatively hydrophilic coloring compounds are incorporated with the help of the oil formers according to the invention, then not only the tendency towards crystallization but also the tendency to diffuse is significantly reduced. When using the oil formers according to the invention, it is therefore possible to reduce the proportion by weight of the binder in a layer containing at least one coloring compound and optionally silver halide to 40% or less.
Besonders bevorzugte Beispiele von vergleichsweise hydrophilen farbgebenden Verbindungen sind 2-Äquivalent-Gelbkuppler, z.B. die folgenden:
- K-1:
-
- K-2:
- R = -C₂H₅ Fp. 173°C
- K-3:
- R = -C₃H₇ Fp. 116°C
- K-1:
-
- K-2:
- R = -C₂H₅ mp 173 ° C
- K-3:
- R = -C₃H₇ mp 116 ° C
Beispiele für farbfotografische Materialien sind Farbnegativfilme, Farbumkehrfilme, Farbpositivfilme, farbfotografisches Papier, farbumkehrfotografisches Papier, farbempfindliche Materialien für das Farbdiffusionstransfer-Verfahren oder das Silberfarb-Bleichverfahren.Examples of color photographic materials are color negative films, color reversal films, color positive films, color photographic paper, color reversal photographic paper, color sensitive materials for the color diffusion transfer process or the silver color bleaching process.
Geeignete Träger zur Herstellung farbfotografischer Materialien sind z.B. Filme und Folien von halbsynthetischen und synthetischen Polymeren, wie Cellulosenitrat, Celluloseacetat, Cellulosebutyrat, Polystyrol, Polyvinylchlorid, Polyethylenterephthalat und Polycarbonat und mit einer Barytschicht oder α-Olefinpolymerschicht (z.B. Polyethylen) laminiertes Papier. Diese Träger können mit Farbstoffen und Pigmenten, beispielsweise Titandioxid, gefärbt sein. Sie können auch zum Zwecke der Abschirmung von Licht schwarz gefärbt sein. Die Oberfläche des Trägers wird im allgemeinen einer Behandlung unterzogen, um die Adhäsion der fotografischen Emulsionsschicht zu verbessern, beispielsweise einer Corona-Entladung mit nachfolgendem Antrag einer Substratschicht. Schichtträger mit lichtreflektierender Oberfläche sind bevorzugt.Suitable supports for the production of color photographic materials are e.g. Films and foils of semi-synthetic and synthetic polymers such as cellulose nitrate, cellulose acetate, cellulose butyrate, polystyrene, polyvinyl chloride, polyethylene terephthalate and polycarbonate and paper laminated with a baryta layer or α-olefin polymer layer (e.g. polyethylene). These carriers can be colored with dyes and pigments, for example titanium dioxide. They can also be colored black for the purpose of shielding light. The surface of the support is generally subjected to a treatment in order to improve the adhesion of the photographic emulsion layer, for example a corona discharge with subsequent application of a substrate layer. Layer supports with a light-reflecting surface are preferred.
Die farbfotografischen Materialien enthalten üblicherweise mindestens je eine rotempfindliche, grünempfindliche und blauempfindliche Silberhalogenidemulsionsschicht sowie gegebenenfalls Zwischenschichten und Schutzschichten.The color photographic materials usually contain at least one red-sensitive, green-sensitive and blue-sensitive silver halide emulsion layer and, if appropriate, intermediate layers and protective layers.
Wesentliche Bestandteile der fotografischen Emulsionsschichten sind Bindemittel, lichtempfindliches Silberhalogenid und farbgebende Verbindungen, z.B. Farbkuppler.Essential constituents of the photographic emulsion layers are binders, light-sensitive silver halide and coloring compounds, eg color couplers.
Als Bindemittel wird vorzugsweise Gelatine verwendet. Diese kann jedoch ganz oder teilweise durch andere synthetische, halbsynthetische oder auch natürlich vorkommende Polymere ersetzt werden. Synthetische Gelatineersatzstoffe sind beispielsweise Polyvinylalkohol, Poly-N-vinylpyrrolidon, Polyacrylamide, Polyacrylsäure und deren Derivate, insbesondere deren Mischpolymerisate. Natürlich vorkommende Gelatineersatzstoffe sind beispielsweise andere Proteine wie Albumin oder Casein, Cellulose, Zucker, Stärke oder Alginate. Halbsynthetische Gelatineersatzstoffe sind in der Regel modifizierte Naturprodukte. Cellulosederivate wie Hydroxyalkylcellulose, Carboxymethylcellulose und Phthalylcellulose sowie Gelatinederivate, die durch Umsetzung mit Alkylierungs- oder Acylierungsmitteln oder durch Aufpfropfung von polymerisierbaren Monomeren erhalten worden sind, sind Beispiele hierfür.Gelatin is preferably used as the binder. However, this can be replaced in whole or in part by other synthetic, semi-synthetic or naturally occurring polymers. Synthetic gelatin substitutes are, for example, polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylamides, polyacrylic acid and their derivatives, in particular their copolymers. Naturally occurring gelatin substitutes are, for example, other proteins such as albumin or casein, cellulose, sugar, starch or alginates. Semi-synthetic gelatin substitutes are usually modified natural products. Cellulose derivatives such as hydroxyalkyl cellulose, carboxymethyl cellulose and phthalyl cellulose and gelatin derivatives, which have been obtained by reaction with alkylating or acylating agents or by grafting on polymerizable monomers, are examples of this.
Die Bindemittel sollen über eine ausreichende Menge an funktionellen Gruppen verfügen, so daß durch Umsetzung mit geeigneten Härtungsmitteln genügend widerstandsfähige Schichten erzeugt werden können. Solche funktionellen Gruppen sind insbesondere Aminogruppen, aber auch Carboxylgruppen, Hydroxylgruppen und aktive Methylengruppen.The binders should have a sufficient amount of functional groups so that enough resistant layers can be produced by reaction with suitable hardening agents. Such functional groups are in particular amino groups, but also carboxyl groups, hydroxyl groups and active methylene groups.
Die vorzugsweise verwendete Gelatine kann durch sauren oder alkalischen Aufschluß erhalten sein. Es kann auch oxidierte Gelatine verwendet werden. Die Herstellung solcher Gelatinen wird beispielsweise in The Science and Technology of Gelatine, herausgegeben von A.G. Ward und A. Courts, Academic Press 1977, Seite 295 ff beschrieben. Die jeweils eingesetzte Gelatine soll einen möglichst geringen Gehalt an fotografisch aktiven Verunreinigungen enthalten (Inertgelatine). Gelatinen mit hoher Viskosität und niedriger Quellung sind besonders vorteilhaft.The gelatin which is preferably used can be obtained by acidic or alkaline digestion. Oxidized gelatin can also be used. The production such gelatins are described, for example, in The Science and Technology of Gelatine, edited by AG Ward and A. Courts, Academic Press 1977, page 295 ff. The gelatin used in each case should contain the lowest possible level of photographically active impurities (inert gelatin). High viscosity, low swelling gelatins are particularly advantageous.
Das als lichtempfindlicher Bestandteil in dem fotografischen Material befindliche Silberhalogenid kann als Halogenid Chlorid, Bromid oder Iodid bzw. Mischungen davon enthalten. Beispielsweise kann der Halogenidanteil wenigstens einer Schicht zu 0 bis 15 mol-% aus Iodid, zu 0 bis 100 mol-% aus Chlorid und zu 0 bis 100 mol-% aus Bromid bestehen. Im Falle von Farbnegativ- und Farbumkehrfilmen werden üblicherweise Silberbromidiodidemulsionen, im Falle von Farbnegativ- und Farbumkehrpapier üblicherweise Silberchloridbromidemulsionen mit hohem Chloridanteil bis zu reinen Silberchloridemulsionen verwendet. Es kann sich um überwiegend kompakte Kristalle handeln, die z.B. regulär kubisch oder oktaedrisch sind oder Übergangsformen aufweisen können. Vorzugsweise können aber auch plättchenförmige Kristalle vorliegen, deren durchschnittliches Verhältnis von Durchmesser zu Dicke bevorzugt wenigstens 5:1 ist, wobei der Durchmesser eines Kornes definiert ist als der Durchmesser eines Kreises mit einem Kreisinhalt entsprechend der projizierten Flache des Kornes. Die Schichten können aber auch tafelförmige Silberhalogenidkristalle aufweisen, bei denen das Verhältnis von Durchmesser zu Dicke wesentlich größer als 5:1 ist, z.B. 12:1 bis 30:1.The silver halide present as a light-sensitive component in the photographic material can contain chloride, bromide or iodide or mixtures thereof as the halide. For example, the halide content of at least one layer can consist of 0 to 15 mol% of iodide, 0 to 100 mol% of chloride and 0 to 100 mol% of bromide. In the case of color negative and color reversal films, silver bromide iodide emulsions are usually used; in the case of color negative and color reversal paper, silver chloride bromide emulsions with a high chloride content are used up to pure silver chloride emulsions. It can be predominantly compact crystals, which are, for example, regularly cubic or octahedral or can have transitional forms. However, platelet-shaped crystals can preferably also be present, the average ratio of diameter to thickness of which is preferably at least 5: 1, the diameter of a grain being defined as the diameter of a circle with a circle content corresponding to the projected area of the grain. However, the layers can also have tabular silver halide crystals in which the ratio of diameter to thickness is substantially greater than 5: 1, for example 12: 1 to 30: 1.
Die Silberhalogenidkörner können auch einen mehrfach geschichteten Kornaufbau aufweisen, im einfachsten Fall mit einem inneren und einem äußeren Kornbereich (core/shell), wobei die Halogenidzusammensetzung und/oder sonstige Modifizierungen, wie z.B. Dotierungen der einzelnen Kornbereiche unterschiedlich sind. Die mittlere Korngröße der Emulsionen liegt vorzugsweise zwischen 0,2 µm und 2,0 µm, die Korngrößenverteilung kann sowohl homo- als auch heterodispers sein. Homodisperse Korngrößenverteilung bedeutet, daß 95 % der Körner nicht mehr als ± 30% von der mittleren Korngröße abweichen.The silver halide grains can also have a multi-layered grain structure, in the simplest case with an inner and an outer grain area (core / shell), the halide composition and / or other modifications, such as e.g. Doping of the individual grain areas are different. The average grain size of the emulsions is preferably between 0.2 μm and 2.0 μm, the grain size distribution can be either homodisperse or heterodisperse. Homodisperse grain size distribution means that 95% of the grains do not deviate from the mean grain size by more than ± 30%.
Es können zwei oder mehrere Arten von Silberhalogenidemulsionen, die getrennt hergestellt werden, als Mischung verwendet werden.Two or more kinds of silver halide emulsions, which are prepared separately, can be used as a mixture.
Die fotografischen Emulsionen können Verbindungen zur Verhinderung der Schleierbildung oder zur Stabilisierung der fotografischen Funktion während der Produktion, der Lagerung oder der fotografischen Verarbeitung enthalten.The photographic emulsions may contain compounds to prevent fogging or to stabilize the photographic function during production, storage or photographic processing.
Die fotografischen Emulsionen können unter Verwendung von Methinfarbstoffen oder anderen Farbstoffen spektral sensibilisiert werdend. Besonders geeignete Farbstoffe sind Cyaninfarbstoffe, Merocyaninfarbstoffe und komplexe Merocyaninfarbstoffe.The photographic emulsions can be spectrally sensitized using methine dyes or other dyes. Particularly suitable dyes are cyanine dyes, merocyanine dyes and complex merocyanine dyes.
Eine Übersicht über die als Spektralsensibilisatoren geeigneten Polymethinfarbstoffe, deren geeignete Kombinationen und supersensibilisierend wirkenden Kombinationen enthält Research Disclosure 17643 (Dez. 1978) in Abteilung IV.Research Disclosure 17643 (Dec. 1978) in Division IV contains an overview of the polymethine dyes suitable as spectral sensitizers, their suitable combinations and combinations with a super-sensitizing effect.
Auf Sensibilisatoren kann verzichtet werden, wenn für einen bestimmten Spektralbereich die Eigenempfindlichkeit des Silberhalogenids ausreichend ist, beispielsweise die Blauempfindlichkeit von Silberbromiden.Sensitizers can be dispensed with if the intrinsic sensitivity of the silver halide is sufficient for a certain spectral range, for example the blue sensitivity of silver bromides.
Den unterschiedlich sensibilisierten Emulsionsschichten werden nicht diffundierende monomere oder polymere Farbkuppler zugeordnet, die sich in der gleichen Schicht oder in einer dazu benachbarten Schicht befinden können. Gewöhnlich werden den rotempfindlichen Schichten Cyankuppler, den grünempfindlichen Schichten Magentakuppler und den blauempfindlichen Schichten Gelbkuppler zugeordnet.The differently sensitized emulsion layers are assigned non-diffusing monomeric or polymeric color couplers, which can be located in the same layer or in a layer adjacent to it. Usually, the red-sensitive layers are cyan couplers, the green-sensitive layers are magenta couplers and the blue-sensitive layers are yellow couplers.
Die Einarbeitung der Kuppler oder anderer Verbindungen in Silberhalogenidemulsionsschichten und andere Schichten kann in der Weise erfolgen, daß zunächst von der betreffenden Verbindung eine Lösung, eine Dispersion oder eine Emulsion hergestellt und dann der Gießlösung für die betreffende Schicht zugefügt wird. Die Auswahl des geeigneten Lösungs- oder Dispersionsmittel hängt von der jeweiligen Löslichkeit der Verbindung ab.The couplers or other compounds can be incorporated into silver halide emulsion layers and other layers in such a way that a solution, a dispersion or an emulsion is first prepared from the compound in question and then added to the casting solution for the layer in question. The selection of the suitable solvent or dispersing agent depends on the solubility of the compound.
Hydrophobe Verbindungen können unter Verwendung von hochsiedenden Lösungsmitteln, sogenannten Ölbildnern, in die Gießlösung eingebracht werden. Entsprechende Methoden sind beispielsweise in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 und EP-A-0 043 037 beschrieben.Hydrophobic compounds can be introduced into the casting solution using high-boiling solvents, so-called oil formers. Corresponding methods are described for example in US-A-2 322 027, US-A-2 801 170, US-A-2 801 171 and EP-A-0 043 037.
Beispiele für geeignete Ölbildner, die neben den erfindungsgemäßen Polypropylenoxiden verwendet werden können, sind Dibutylphthalat, Dicyclohexylphthalat, Di-2-ethylhexylphthalat, Decylphthalat, Triphenylphosphat, Tricresylphosphat, 2-Ethylhexyldiphenylphosphat, Tricyclohexylphosphat, Tri-2-ethylhexylphosphat, Tridecylphosphat, Tributoxyethylphosphat, Trichlorpropylphosphat, Di-2-ethylhexylphenylphosphat, 2-Ethylhexylbenzoat, Dodecylbenzoat, 2-Ethylhexyl-p-hydroxybenzoat, Diethyldodecanamid, N-Tetradecylpyrrolidon, Isostearylalkohol, 2,4-Di-t-amylphenol, Dioctylacelat, Glycerintributyrat, Isostearyllactat, Trioctylcitrat, N,N-Dibutyl-2-butoxy-5-t-octylanilin, Paraffin, Dodecylbenzol und Diisopropylnaphthalin.Examples of suitable oil formers which can be used in addition to the polypropylene oxides according to the invention are dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl tri-ethyl-tri-ethylhexyl tri-ethyl-tri-ethyl-tri-ethyl-tri-ethyl-trihydrate, tri-2-ethylhexyl tri-ethyl-tri-ethyl-tri-ethyl-tri-ethylate -2-ethylhexylphenyl phosphate, 2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl p-hydroxybenzoate, diethyldodecanamide, N-tetradecylpyrrolidone, isostearyl alcohol, 2,4-di-t-amylphenol, dioctylacelate, tri-trearyl, n-trityl nitrate, n-tri-nitylate, n-trityl-n-tritylate -2-butoxy-5-t-octylaniline, paraffin, dodecylbenzene and diisopropylnaphthalene.
Die in der Regel zwischen Schichten unterschiedlicher Spektralempfindlichkeit angeordneten nicht lichtempfindlichen Zwischenschichten können Mittel enthalten, die eine unerwünschte Diffusion von Entwickleroxidationsprodukten aus einer lichtempfindlichen in eine andere lichtempfindliche Schicht mit unterschiedlicher spektraler Sensibilisierung verhindern.The non-light-sensitive intermediate layers, which are generally arranged between layers of different spectral sensitivity, can contain agents which prevent undesired diffusion of developer oxidation products from one light-sensitive layer into another light-sensitive layer with different spectral sensitization.
Geeignete Mittel, die auch Scavenger oder EOP-Fänger genannt werden, werden in Research Disclosure 17 643 (Dez. 1978), Kapitel VII, 17 842 (Feb. 1979) und 18 716 (Nov. 1979), Seite 650 sowie in EP-A-0 069 070, 0 098 072, 0 124 877 und 0 125 522 beschrieben.Suitable agents, which are also called scavengers or EOP-catchers, are described in Research Disclosure 17 643 (Dec. 1978), chapters VII, 17 842 (Feb. 1979) and 18 716 (Nov. 1979), page 650 and in EP A-0 069 070, 0 098 072, 0 124 877 and 0 125 522.
Das fotografische Aufzeichnungsmaterial kann weiterhin UV-Licht absorbierende Verbindungen, Weißtöner, Abstandshalter, Filterfarbstoffe, Formalinfänger, Lichtschutzmittel, Antioxidantien, Dmin-Farbstoffe, Zusätze zur Verbesserung der Farbstoff-, Kuppler- und Weißenstabilisierung sowie zur Verringerung des Farbschleiers, Weichmacher (Latices), Biocide enthalten.The photographic recording material can furthermore contain UV light-absorbing compounds, whiteners, spacers, filter dyes, formalin scavengers, light stabilizers, antioxidants, D min dyes, additives for improving the dye, coupler and white stabilization and for reducing the color fog, plasticizers (latices), Contain biocides.
UV-Licht absorbierende Verbindungen sollen einerseits die Bildfarbstoffe vor dem Ausbleichen durch UV-reiches Tageslicht schützen und andererseits als Filterfarbstoffe das UV-Licht im Tageslicht bei der Belichtung absorbieren und so die Farbwiedergabe eines Films verbessern. Üblicherweise werden für die beiden Aufgaben Verbindungen unterschiedlicher Struktur eingesetzt. Beispiele sind arylsubstituierte Benzotriazolverbindungen (US-A-3 533 794), 4-Thiazolidonverbindungen (US-A-3 314 794 und 3 352 681), Benzophenonverbindungen (JP-A-2784/71), Zimtsäureesterverbindungen (US-A-3 705 805 und 3 707 375), Butadienverbindungen (US-A-4 045 229) oder Benzoxazolverbindungen (US-A-3 700 455).Compounds that absorb UV light are intended on the one hand to protect the image dyes from fading by UV-rich daylight and, on the other hand, as filter dyes to absorb the UV light in daylight upon exposure and thus improve the color rendering of a film. Connections of different structures are usually used for the two tasks. Examples are aryl-substituted benzotriazole compounds (US-A-3 533 794), 4-thiazolidone compounds (US-A-3 314 794 and 3 352 681), benzophenone compounds (JP-A-2784/71), cinnamic acid ester compounds (US-A-3 705 805 and 3,707,375), butadiene compounds (US-A-4,045,229) or benzoxazole compounds (US-A-3,700,455).
Es können auch ultraviolettabsorbierende Kuppler (wie Blaugrünkuppler des α-Naphtholtyps) und ultraviolettabsorbierende Polymere verwendet werden. Diese Ultraviolettabsorbentien können durch Beizen in einer speziellen Schicht fixiert sein.Ultraviolet absorbing couplers (such as α-naphthol type cyan couplers) and ultraviolet absorbing polymers can also be used. These ultraviolet absorbents can be fixed in a special layer by pickling.
Für sichtbares Licht geeignete Filterfarbstoffe umfassen Oxonolfarbstoffe, Hemioxonolfarbstoffe, Styrylfarbstoffe, Merocyaninfarbstoffe, Cyaninfarbstoffe und Azofarbstoffe. Von diesen Farbstoffen werden Oxonolfarbstoffe, Hemioxonolfarbstoffe und Merocyaninfarbstoffe besonders vorteilhaft verwendet.Filter dyes suitable for visible light include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are used particularly advantageously.
Geeignete Weißtöner sind z.B. in Research Disclosure 17 643 (Dez. 1978), Kapitel V, in US-A-2 632 701, 3 269 840 und in GB-A-852 075 und 1 319 763 beschrieben.Suitable whiteners are e.g. in Research Disclosure 17,643 (Dec. 1978), Chapter V, in US-A-2,632,701, 3,269,840 and in GB-A-852,075 and 1,319,763.
Bestimmte Bindemittelschichten, insbesondere die vom Träger am weitesten entfernte Schicht, aber auch gelegentlich Zwischenschichten, insbesondere, wenn sie während der Herstellung die vom Träger am weitesten entfernte Schicht darstellen, können fotografisch inerte Teilchen anorganischer oder organischer Natur enthalten, z.B. als Mattierungsmittel oder als Abstandshalter (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dez. 1978), Kapitel XVI).Certain binder layers, in particular the most distant layer from the support, but also occasionally intermediate layers, especially if they are the most distant layer from the support during manufacture, may contain photographically inert particles of inorganic or organic nature, e.g. as a matting agent or as a spacer (DE-A-33 31 542, DE-A-34 24 893, Research Disclosure 17 643, (Dec. 1978), Chapter XVI).
Der mittlere Teilchendurchmesser der Abstandshalter liegt insbesondere im Bereich von 0,2 bis 10 µm. Die Abstandshalter sind wasserunlöslich und können alkaliunlöslich oder alkalilöslich sein, wobei die alkalilöslichen im allgemeinen im alkalischen Entwicklungsbad aus dem fotografischen Material entfernt werden. Beispiele für geeignete Polymere sind Polymethylmethacrylat, Copolymere aus Acrylsäure und Methylmethacrylat sowie Hydroxypropylmethylcellulosehexahydrophthalat.The average particle diameter of the spacers is in particular in the range from 0.2 to 10 μm. The spacers are water-insoluble and can be alkali-insoluble or alkali-soluble, the alkali-soluble ones generally being removed from the photographic material in the alkaline development bath. Examples of suitable polymers are polymethyl methacrylate, copolymers of acrylic acid and methyl methacrylate and hydroxypropyl methyl cellulose hexahydrophthalate.
Zusätze zur Verbesserung der Farbstoff-, Kuppler- und Weißenstabilität sowie zur Verringerung des Farbschleiers (Research Disclosure 17 643 (Dez. 1978), Kapitel VII) können den folgenden chemischen Stoffklassen angehören: Hydrochinone, 6-Hydroxychromane, 5-Hydroxycumarane, Spirochromane, Spiroindane, p-Alkoxyphenole, sterische gehinderte Phenole, Gallussäurederivate, Methylendioxybenzole, Aminophenole, sterisch gehinderte Amine, Derivate mit veresterten oder veretherten phenolischen Hydroxylgruppen, Metallkomplexe.Additives to improve dye, coupler and whiteness stability and to reduce the color fog (Research Disclosure 17 643 (Dec. 1978), Chapter VII) can belong to the following chemical substance classes: hydroquinones, 6-hydroxychromanes, 5-hydroxycoumarans, spirochromans, spiroindanes , p-alkoxyphenols, sterically hindered phenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, sterically hindered amines, derivatives with esterified or etherified phenolic hydroxyl groups, metal complexes.
Verbindungen, die sowohl eine sterisch gehinderte Amin-Partialstruktur als auch eine sterisch gehinderte Phenol-Partialstruktur in einem Molekül aufweisen (US-A-4 268 593), sind besonders wirksam zur Verhinderung der Beeinträchtigung von gelben Farbbildern als Folge der Entwicklung von Wärme, Feuchtigkeit und Licht. Um die Beeinträchtigung von purpurroten Farbbildern, insbesondere als Folge der Einwirkung von Licht, zu verhindern, sind Spiroindane (JP-A-159 644/81) und Chromane, die durch Hydrochinondiether oder -monoether substituiert sind (JP-A-89 835/80) besonders wirksam.Compounds which have both a hindered amine partial structure and a hindered phenol partial structure in one molecule (US-A-4,268,593) are particularly effective in preventing the deterioration of yellow color images as a result of the development of heat, moisture and light. In order to prevent the deterioration of purple color images, in particular as a result of exposure to light, spiroindanes (JP-A-159 644/81) and chromanes which are substituted by hydroquinone diethers or monoethers (JP-A-89 835/80 ) particularly effective.
Die Schichten des fotografischen Materials können mit den üblichen Härtungsmitteln gehärtet werden. Geeignete Härtungsmittel sind z.B. Formaldehyd, Glutaraldehyd und ähnliche Aldehydverbindungen, Diacetyl, Cyclopentadion und ähnliche Ketonverbindungen, Bis-(2-chlorethylharnstoff), 2-Hydroxy-4,6-dichlor-1,3,5-triazin und andere Verbindungen, die reaktives Halogen enthalten (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 und GB-A-1 167 207) Divinylsulfonverbindungen, 5-Acetyl-1,3-diacryloylhexahydro-1,3,5-triazin und andere Verbindungen, die eine reaktive Olefinbindung enthalten (US-A-3 635 718, US-A-3 232 763 und GB-A-994 869); N-Hydroxymethylphthalimid und andere N-Methylolverbindungen (US-A-2 732 316 und US-A-2 586 168); Isocyanate (US-A-3 103 437); Aziridinverbindungen (US-A-3 017 280 und US-A-2 983 611); Säurederivate (US-A-2 725 294 und US-A-2 725 295); Verbindungen vom Carbodiimidtyp (US-A-3 100 704); Carbamoylpyridiniumsalze (DE-A-22 25 230 und DE-A-24 39 551); Carbamoyloxypyridiniumverbindungen (DE-A-24 08 814); Verbindungen mit einer Phosphor-Halogen-Bindung (JP-A-113 929/83); N-Carbonyloximid-Verbindungen (JP-A-43353/81); N-Sulfonyloximido-Verbindungen (US-A-4 111 926), Dihydrochinolinverbindungen (US-A-4 013 468), 2-Sulfonyloxypyridiniumsalze (JP-A-110 762/81), Formamidiniumsalze (EP-A-0 162 308), Verbindungen mit zwei oder mehr N-Acyloximino-Gruppen (US-A-4 052 373), Epoxyverbindungen (US-A-3 091 537), Verbindungen vom Isoxazoltyp (US-A-3 321 313 und US-A-3 543 292); Halogencarboxyaldehyde, wie Mucochlorsäure; Dioxanderivate, wie Dihydroxydioxan und Di-chlordioxan; und anorganische Härter, wie Chromalaun und Zirkonsulfat.The layers of the photographic material can be hardened with the usual hardening agents. Suitable curing agents include formaldehyde, glutaraldehyde and similar aldehyde compounds, diacetyl, cyclopentadione and similar ketone compounds, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,5-triazine and other compounds, the reactive halogen contain (US-A-3 288 775, US-A-2 732 303, GB-A-974 723 and GB-A-1 167 207) divinyl sulfone compounds, 5-acetyl-1,3-diacryloylhexahydro-1,3,5 triazine and other compounds containing a reactive olefin bond (US-A-3 635 718, US-A-3 232 763 and GB-A-994 869); N-hydroxymethylphthalimide and other N-methylol compounds (US-A-2 732 316 and US-A-2 586 168); Isocyanates (US-A-3 103 437); Aziridine compounds (US-A-3 017 280 and US-A-2 983 611); Acid derivatives (US-A-2 725 294 and US-A-2 725 295); Carbodiimide type compounds (US-A-3 100 704); Carbamoylpyridinium salts (DE-A-22 25 230 and DE-A-24 39 551); Carbamoyloxypyridinium compounds (DE-A-24 08 814); Compounds with a phosphorus-halogen bond (JP-A-113 929/83); N-carbonyloximide compounds (JP-A-43353/81); N-sulfonyloximido compounds (US-A-4 111 926), dihydroquinoline compounds (US-A-4 013 468), 2-sulfonyloxypyridinium salts (JP-A-110 762/81), formamidinium salts (EP-A-0 162 308) , Compounds having two or more N-acyloximino groups (US-A-4 052 373), epoxy compounds (US-A-3 091 537), isoxazole-type compounds (US-A-3 321 313 and US-A-3 543 292); Halocarboxyaldehydes such as mucochloric acid; Dioxane derivatives such as dihydroxydioxane and di-chlorodioxane; and inorganic hardeners such as chrome alum and zirconium sulfate.
Die Härtung kann in bekannter Weise dadurch bewirkt werden, daß das Härtungsmittel der Gießlösung für die zu härtende Schicht zugesetzt wird, oder dadurch, daß die zu härtende Schicht mit einer Schicht überschichtet wird, die ein diffusionsfähiges Härtungsmittel enthält.The hardening can be effected in a known manner by adding the hardening agent to the casting solution for the layer to be hardened, or by overlaying the layer to be hardened with a layer which contains a diffusible hardening agent.
Unter den aufgeführten Klassen gibt es langsam wirkende und schnell wirkende Härtungsmittel sowie sogenannte Soforthärter, die besonders vorteilhaft sind.There are slow-acting and fast-acting hardeners and so-called instant hardeners, which are particularly advantageous, in the classes listed.
Bei den letztgenannten mit Gelatine sehr schnell reagierenden Härtungsmitteln handelt es sich z.B. um Carbamoylpyridiniumsalze, die mit freien Carboxylgruppen der Gelatine zu reagieren vermögen, so daß letztere mit freien Aminogruppen der Gelatine unter Ausbildung von Peptidbindungen und Vernetzung der Gelatine reagieren.The last-mentioned curing agents which react very quickly with gelatin are, for example, carbamoylpyridinium salts which are able to react with free carboxyl groups of the gelatin, so that the latter react with free amino groups of the gelatin with the formation of peptide bonds and crosslinking of the gelatin.
Nach folgender allgemeiner Emulgiervorschrift werden Kuppleremulgate hergestellt.Coupler emulsions are produced according to the following general emulsification instructions.
- Wasser entsalzt
- 7,9 l
- Gelatine
- 0,55 kg
- Phenol (80%ig)
- 0,033 kg
Temperatur: 55°C
- Desalinated water
- 7.9 l
- gelatin
- 0.55 kg
- Phenol (80%)
- 0.033 kg
Temperature: 55 ° C
- Ethylacetat
- 2,4 kg
- Farbkuppler
- 1 kg
- Weißkuppler
- 0,02 kg
- Ölbildner
- 0,55 kg
- Dodecylbenzolsulfonat
- 0,017 kg
Temperatur: 55°C
- Ethyl acetate
- 2.4 kg
- Color coupler
- 1 kg
- White coupler
- 0.02 kg
- Oil producer
- 0.55 kg
- Dodecylbenzenesulfonate
- 0.017 kg
Temperature: 55 ° C
Die Ölphase wird mit einer Mischsirene in die wäßrige Phase einemulgiert. Nach beendeter Zugabe wird über einen Hochdruckhomogenisator bei 50 bar nachhomogenisiert.The oil phase is emulsified into the aqueous phase with a mixed siren. After the addition is complete, the mixture is post-homogenized at 50 bar using a high-pressure homogenizer.
Das Hilfslösungsmittel (Ethylacetat) wird über einen Lösungsmittelverdampfer entfernt, wobei pro Sekunde zwischen 30 und 50 g Ethylacetat abgedampft werden.The auxiliary solvent (ethyl acetate) is removed on a solvent evaporator, evaporating between 30 and 50 g of ethyl acetate per second.
Das Verhalten der so hergestellten Emulgate bei Digestion (40°C) bzw. Kühllagerung (3 Wochen, 4 - 6°C) ist in folgender Tabelle 1 angegeben. Es ist angegeben, welche Ölbildner und welche Farbkuppler verwendet wurden (Spalte 1 und 2). Ferner ist angegeben, nach welcher Zeit vollständige Kristallisation eingetreten war (Spalte 3), wie der Befund nach dreiwöchiger Kühllagerung und ansschließender Digestion war bzw. nach welcher Zeit Kristallisation eingetreten war (Spalte 5).The behavior of the emulsions produced in this way during digestion (40 ° C.) or cold storage (3 weeks, 4-6 ° C.) is given in Table 1 below. It is indicated which oil formers and which color couplers were used (columns 1 and 2). Furthermore, the time after complete crystallization had occurred (column 3), the results after three weeks of cold storage and subsequent digestion, and the time after which crystallization had occurred (column 5).
Als Weißkuppler wurde folgende Verbindung W-1 verwendet.
Ein farbfotografisches Aufzeichnungsmaterial wurde hergestellt, indem auf einen Schichtträger aus beidseitig mit Polyethylen beschichtetem Papier die folgenden Schichten in der angegebenen Reihenfolge aufgetragen wurden. Die Mengenangaben beziehen sich jeweils auf 1 m². Für den Silberhalogenidauftrag werden die entsprechenden Mengen AgNO₃ angegeben.A color photographic recording material was produced by applying the following layers in the order given to a support made of paper coated on both sides with polyethylene. The quantities given relate to 1 m². For the silver halide application, the corresponding amounts of AgNO₃ are given.
0,2 g Gelatine0.2 g gelatin
blauempfindliche Silberhalogenidemulsion (99,5 mol-% Chlorid, 0,5 mol-% Bromid, mittlerer Korndurchmesser 0,8 µm) aus 0,58 g AgNO₃ mit
- 0,685 g
- Gesamtgelatine
(aus Silberhalogenidemulsion und Kuppleremulgat) - 0,70 g
- Gelbkuppler wie in Tabellen 2 und 3 angegeben
- 0,15 g
- Weißkuppler wie in Tabellen 2 und 3 angegeben
- 0,32 g
- Ölbildner wie in Tabellen 2 und 3 angegeben
- 0.685 g
- Total gelatin
(from silver halide emulsion and coupler emulsate) - 0.70 g
- Yellow coupler as indicated in Tables 2 and 3
- 0.15 g
- White couplers as indicated in Tables 2 and 3
- 0.32 g
- Oil formers as indicated in Tables 2 and 3
- 1,1 g1.1 g
- Gelatinegelatin
- 0,06 g0.06 g
- 2,5-Dioctylhydrochinon2,5-dioctyl hydroquinone
- 0,06 g0.06 g
- DBPDBP
grünsensibilisierte Silberhalogenidemulsion (99,5 mol-% Chlorid, 0,5 mol-% Bromid, mittlerer Korndurchmesser 0,6 µm) aus 0,45 g AgNO₃, mit
- 1,08 g
- Gelatine
- 0,41 g
- Magenta M-3
- 0,08 g
- 2,5-Dioctylhydrochinon
- 0,5 g
- DBP
- 0,04 g
- TKP
- 1.08 g
- gelatin
- 0.41 g
- Magenta M-3
- 0.08 g
- 2,5-dioctyl hydroquinone
- 0.5 g
- DBP
- 0.04 g
- CPM
- 1,15 g1.15 g
- Gelatinegelatin
- 0,6 g0.6 g
-
UV-Absorber der Formel
- 0,045 g0.045 g
- 2,5-Dioctylhydrochinon2,5-dioctyl hydroquinone
- 0,04 g0.04 g
- TKPCPM
rotsensibilisierte Silberhalogenidemulsion (99,5 mol-% Chlorid, 0,5 mol-% Bromid, mittlerer Korndurchmesser 0,5 µm) aus 0,3 g AgNO₃, mit
- 0,75 g
- Gelatine
- 0,36 g
- Cyankuppler C-24
- 0,36 g
- TKP
- 0.75 g
- gelatin
- 0.36 g
- C-24 cyan coupler
- 0.36 g
- CPM
- 0,35 g0.35 g
- Gelatinegelatin
- 0,15 g0.15 g
- UV-Absorber wie in Schicht 5UV absorber as in layer 5
- 0,2 g0.2 g
- TKPCPM
- 0,9 g
- Gelatine
- 0,3 g
- Härtungsmittel
Carbamoylpyridinium-Verbindung
CAS Reg.-No. 65411-60-1
- 0.9 g
- gelatin
- 0.3 g
- Hardening agent
Carbamoyl pyridinium compound
CAS Reg.-No. 65411-60-1
Die in der blauempfindlichen Schicht verwendeten Ölbildner und Gelbkuppler sind in den Tabellen 2 und 3 angegeben.The oil formers and yellow couplers used in the blue-sensitive layer are given in Tables 2 and 3.
Die so hergestellten Materialien wurden hinter einem Keil der Abstufung und einem Grünfilter bzw. Blaufilter belichtet und dann in folgender Weise entwickelt:
Die Verarbeitungsbäder wurden nach den folgenden Ansatzrezepturen hergestellt:The processing baths were produced according to the following recipes:
- 900 ml
- Wasser
- 15 ml
- Benzylalkohol
- 15 ml
- Ethylenglykol
- 3 g
- Hydroxylaminsulfat
- 4,5 g
- 3-Methyl-4-amino-N-ethyl-N-(ßmethansulfonamidoethyl)-anilinsulfat
- 32 g
- Kaliumcarbonat sicc.
- 2 g
- Kaliumsulfit sicc.
- 0,6 g
- Kaliumbromid
- 1 g
- Dinatriumsalz der 1-Hydroxyethan-1,1-diphosphonsäure
mit Wasser auf 1 l auffüllen und auf pH 10,2 einstellen.
- 900 ml
- water
- 15 ml
- Benzyl alcohol
- 15 ml
- Ethylene glycol
- 3 g
- Hydroxylamine sulfate
- 4.5 g
- 3-methyl-4-amino-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate
- 32 g
- Potassium carbonate sicc.
- 2 g
- Potassium sulfite sicc.
- 0.6 g
- Potassium bromide
- 1 g
- Disodium salt of 1-hydroxyethane-1,1-diphosphonic acid
Make up to 1 l with water and adjust to pH 10.2.
- 700 ml
- Wasser
- 35 ml
- Ammoniaklösung (28 %ig)
- 30 g
- Ethylendiamin-N,N,N′,N′-tetraessigsäure
- 15 g
- Natriumsulfit sicc.
- 100 g
- Ammoniumthiosulfat sicc.
- 60 g
- Natrium-(ethylendiamintetraacetat)-eisen-(III)-komplex
mit Wasser auf 1 l auffüllen und auf pH 7 einstellen.
- 700 ml
- water
- 35 ml
- Ammonia solution (28%)
- 30 g
- Ethylenediamine-N, N, N ′, N′-tetraacetic acid
- 15 g
- Sodium sulfite sicc.
- 100 g
- Ammonium thiosulfate sicc.
- 60 g
- Sodium (ethylenediaminetetraacetate) iron (III) complex
Make up to 1 l with water and adjust to pH 7.
Nach der Entwicklung wurden die erhaltenen Farbkeile ausgemessen.After the development, the color wedges obtained were measured.
In Tabelle 2 ist die nach Grünbelichtung erhaltene prozentuale Gelbnebendichte angegeben, bezogen auf eine Magentadichte 1,0. Zum Vergleich ist ferner in der ersten Zeile in Klammern der betreffende Wert angegeben, der für TKP und K-4 erhalten wurde mit einem Material, das sich nur in der Schicht 2 durch einen Gelatinegehalt von 50 Gew.-% unterschied. Es wird deutlich, daß bei Anwendung der erfindungsgemäßen Ölbildner der Gelatinegehalt in der Schicht 2 auf Werte unter 40 Gew.-% vermindert werden kann, ohne daß durch unerwünschte Diffusion des Gelbkupplers in die Magentaschicht die gelbe Nebendichte nachteilig erhöht wird.Table 2 shows the percent yellow secondary density obtained after green exposure, based on a magenta density of 1.0. For comparison, the relevant value is also given in brackets in the first line, which was obtained for CPM and K-4 with a material which differed only in layer 2 by a gelatin content of 50% by weight. It is clear that when the oil formers according to the invention are used, the gelatin content in layer 2 can be reduced to values below 40% by weight without the yellow secondary density being disadvantageously increased by undesirable diffusion of the yellow coupler into the magenta layer.
In Tabelle 3 ist in analoger Weise die nach Blaubelichtung erhaltene prozentuale Magentanebendichte angegeben. Hier bedeutet der in Klammern angegebene Wert in der ersten Zeile die Magentanebendichte eines entsprechenden Materials, das in der Schicht 2 einen Gelatinegehalt von 50 Gew.-% hat. Es wird wiederum deutlich, daß die Reduzierung des Gelatinegehaltes in der Schicht 2 sich auch nachteilig auf die unerwünschte Diffusion des Magentakupplers auswirkt und daß überraschenderweise diese nachteilige Wirkung bei Anwendung des erfindungsgemäßen Ölbildners in der Gelbschicht unterdrückt werden kann.
Verschiedene der in Beispiel 2 in Verbindung mit Tabelle 2 definierten Materialien mit dem Gelbkuppler K-4 wurden belichtet und verarbeitet und anschließend in einem Xenotestgerät einer Bestrahlung mit 1,5 · 10⁷ lxh ausgesetzt. Die prozentuale Abnahme der Gelbdichte (Dichte des Gelbfarbstoffes) wurde für verschiedene Ausgangsdichten einmal im gelben Farbauszugskeil und einmal im Neutralkeil bestimmt und ist in Tabelle 4 angegeben (Werte des Neutralkeils in Klammern).
Claims (6)
- A colour photographic recording material comprising at least one silver halide emulsion layer with which a dye-producing compound incorporated with the aid of an oil former is associated, characterized in that at least 30% by weight of the oil former consists of a polypropylene oxide with an OH content of 1 to 3% by weight.
- A recording material as claimed in claim 1, characterized in that the polypropylene oxide is a reaction product of water or monohydric or polyhydric alcohols with propylene oxide.
- A recording material as claimed in claim 1, characterized in that the dye-producing compound contains at least one -SO₂-NH- group.
- A recording material as claimed in claim 3, characterized in that the dye-producing compound is a colour coupler.
- A recording material as claimed in claim 4, characterized in that the dye-producing compound is a 2-equivalent yellow coupler.
- A recording material as claimed in claim 1, characterized in that the percentage by weight of binder in the layer containing the polypropylene oxide is 40% or less.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3901903 | 1989-01-24 | ||
DE3901903 | 1989-01-24 |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0379893A2 EP0379893A2 (en) | 1990-08-01 |
EP0379893A3 EP0379893A3 (en) | 1990-12-05 |
EP0379893B1 true EP0379893B1 (en) | 1994-08-31 |
Family
ID=6372625
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP90100495A Expired - Lifetime EP0379893B1 (en) | 1989-01-24 | 1990-01-11 | Colour-photographic recording material containing an emulsified compound providing colour |
Country Status (2)
Country | Link |
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EP (1) | EP0379893B1 (en) |
DE (1) | DE59006926D1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US5491052A (en) * | 1992-03-13 | 1996-02-13 | Eastman Kodak Company | Yellow layer for color photographic elements |
DE69319161T2 (en) * | 1992-03-13 | 1999-02-11 | Eastman Kodak Co., Rochester, N.Y. | Yellow layer for color photographic paper |
US5426019A (en) * | 1993-12-30 | 1995-06-20 | Eastman Kodak Company | Color photographic element |
US5451497A (en) * | 1993-12-30 | 1995-09-19 | Eastman Kodak Company | Photographic dispersion having improved stability |
JPH0854716A (en) * | 1994-08-12 | 1996-02-27 | Konica Corp | Silver halide photographic sensitive material and its processing method |
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Publication number | Priority date | Publication date | Assignee | Title |
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DE1472768A1 (en) * | 1965-07-01 | 1969-03-27 | Agfa Gevaert Ag | Chemically sensitized photographic material |
JPS5224412B2 (en) * | 1971-08-25 | 1977-07-01 |
-
1990
- 1990-01-11 DE DE59006926T patent/DE59006926D1/en not_active Expired - Fee Related
- 1990-01-11 EP EP90100495A patent/EP0379893B1/en not_active Expired - Lifetime
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EP0379893A3 (en) | 1990-12-05 |
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