Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
  • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/142—Dye mordant

Definitions

• the invention relates to a photographic recording material which contains crosslinked polymer latices in photographic light-sensitive and non-light-sensitive layers.
• Gelatin is generally used as a binder for photographic layers because of its advantageous properties as a protective colloid, as a dispersant and because of its chemical properties. Gelatin also has disadvantages as a photographic binder. So e.g. inadequate dimensional stability under changing climatic conditions, i.e. at different temperatures and humidity levels that are inherent in the layers formed from it.
• a disadvantage of these polymers is that they increase the viscosity of the coating solutions when mixed with gelatin, especially when the crosslinking agents required for layer hardening are added to the coating solutions. With the dwell times of the casting solutions that occur during the coating process, this leads to an increase in viscosity which makes a defined layer application per unit area impossible. Furthermore, linear high molecular weight polyacrylamides in aqueous solutions are so viscous that processing such solutions is associated with considerable difficulties.
• the object of the invention is to provide crosslinked polymer latices which are not susceptible to hydrolysis, which do not impair the sensitometric properties of color photographic materials and which are compatible with the customary binders and which can be prepared in a simple manner.
• the crosslinked polymer latices of the invention can always be used in an advantageous manner when it is necessary to use a synthetic binder and to avoid the disadvantages of a sharp increase in viscosity which is generally associated therewith. They are also suitable for introducing residues of photographically active agents in the form of substituents into a photographic layer.
• the structural unit characterized by the general formula represents the polymerized form of a low molecular weight carboxylic acid amide.
• Suitable monomeric carboxylic acid derivatives are those which are copolymerizable with the monomers M and V described below, e.g. Methacrylic acid, acrylic acid, crotonic acid, maleic acid or (vinylphenyl) acetic acid derivatives.
• R 2 and R 3 represent hydrogen, alkyl, aralkyl, aryl or a radical which has the function of a photographic building block, for example a color coupler, a UV absorber, a white coupler, a dye, a developer, a dye-releasing or releasing compound , an optical brightener, a metal ion donor, an antifoggant, a toner or a compound reactive with formalin.
• a color coupler for example a color coupler, a UV absorber, a white coupler, a dye, a developer, a dye-releasing or releasing compound , an optical brightener, a metal ion donor, an antifoggant, a toner or a compound reactive with formalin.
• R 2 or R 3 will generally be a radical with one of the functions mentioned. In principle, however, it is also possible for R 2 and R 3 together to represent such a radical.
• R 2 or R3 represents a color coupler residue which is capable of undergoing oxidative coupling with an oxidized p-phenylenediamine compound.
• oxidative coupling With oxidative coupling, the formation of a dye by reaction of the oxidized form, for example a phenylenediamine, with a nucleophile is closed understand.
• the precursor of a nucleophile for example a color coupler, becomes a nucleophile under development conditions, ie under alkaline conditions.
• R 2 or R 3 are color-coupling compounds which are contained as structural elements in conventional color couplers.
• the following color-coupling residues are mentioned as examples:
• R 2 or R 3 can also represent other residues of agents effective in the photographic layer, the following examples being mentioned:
• examples are those which are capable of fixing diffusing anionic dyes.
• a process that is of interest for example, for color diffusion processes or for determining filter dyes.
• Compounds which contain imidazolinium, pyridiium or tetraalkylammonium groups are particularly suitable for this purpose, examples of which are the above compounds C 9 , C 10 and C 12 .
• the polymer latices of the invention can advantageously also contain residues bonded to the nitrogen atom via an alkylene group, which stabilize the photographic material against UV light and / or oxidative degradation, as R 2 and R 3 .
• alkylene group which stabilize the photographic material against UV light and / or oxidative degradation
• R 2 and R 3 examples of such radicals are those denoted by C 1 to C 5 .
• radicals C 6 and C 7 are examples of radicals which complex metal ions and which, for example, enable metal complex dyes to be formed in photographic layers. Such residues preferably contain aminocarboxylic acid groups.
• V is the radical formed from a monomer which can be polymerized by addition polymerization and has at least two ethylenically unsaturated groups, the monomer corresponding to the following formula
• Particularly advantageous monomers for the formation of the units V are trivinylcyclohexane, divinylbenzene, tetraallyloxyethane, 1,4-butylene dimethacrylate. Two or more of the monomers mentioned can also be used side by side to form units V of the polymers according to the invention.
• a wide variety of monoethylenically unsaturated monomers copolymerizable with the customary monomers can be used for the units M.
• Monomers with conjugated ethylenically unsaturated bonds are also suitable for this purpose.
• Typical suitable monomers N are: ethylene, propylene, 1-butene, 4-methylpentene-1, styrene, ⁇ -methylstyrene, monoethylenically unsaturated esters of aliphatic acids, for example vinyl acetate, isopropenyl acetate, allyl acetate and the like; Esters of ethylenically unsaturated mono- and dicarboxylic acids, for example methyl methacrylate, ethyl acrylate, glycidyl acrylate, glycidyl methacrylate, butyl acrylate, cyanomethyl (meth) acrylate, nitrophenyl (meth) acrylate, carbomethoxymethyl (me
• Water-soluble monomers such as e.g. Acrylic acid, methacrylic acid, itaconic acid, maleic acid, acrylamido-2-methylpropanesulfonic acid, sulfoethyl methacrylate, N-vinyl pyrrolidone, vinyl pyridine or dimethylaminoethyl methacrylate.
• the grouping M can be formed not only from a single monomer, but also from various of the monomers mentioned.
• the latices according to the invention can be produced in various ways. According to a preferred production process, crosslinked polymer latices are used, which are converted into the polymeric amides in polymer-analogous reactions. Suitable starting compounds are e.g. Crosslinked (meth) acrylic ester latices which react with amines to form the polymeric amides according to the invention.
• the starting latices can be polymerized in a known manner by emulsion copolymerization of monomeric Esters with polyfunctional monomers, such as described in DE-OS 26 52 464, are prepared.
• monomeric esters which have a sufficient reactivity for the following stage to be performed in the aminolysis'.
• monomeric esters which are suitable for producing the crosslinked starting latices are (meth) acrylic acid methyl ester, cyanomethyl (meth) acrylate, nitrophenyl (meth) acrylate, carbomethoxymethyl (meth) acrylate, carboethoxymethyl (meth) acrylate or chloromethyl (meth) acrylate.
• Another production possibility is to start from crosslinked (meth) acrylic acid latices, as described in DE-OS 26 52 464. In this case it is necessary to activate the carboxylic acid groups before the reaction with the amines. opportunities for activating the carboxylic acid groups are known and are described, for example, in Houben-Weyl, volume 15/1 (1974), p. 28.
• the acid groups can also be activated by conversion into the acid halide or anhydride form.
• the reagents known from low molecular weight chemistry are suitable for this, such as thionyl chloride, phosphorus pentachloride, phosphorus trichloride or acetic anhydride.
• the crosslinked reactive starting latices are then reacted with amines to form the polymer latices according to the invention.
• the latices used as starting compounds can be present as aqueous dispersions. In those cases where the reactive starting latices can react with water, the starting latices are used as dispersions which contain organic, preferably polar, organic solvents as dispersants. It is often also expedient to use mixtures of water and organic solvent as dispersants.
• reaction conditions such as reaction time, temperature and the use of catalysts depend on the starting latex used.
• the reaction conditions can be chosen as they are known from the analogous reactions of linear uncrosslinked polymers or from low molecular weight chemistry. Descriptions of these possibilities can be found in Houben-Weyl, Volume 14/2 (1963), p. 738, Makromol. Chem., Rapid Connun. 1, 655 (1980), European Polymer Journal 15, 167 (1979), J. Polym. Sci. Chem. Ed. 12, 2453 (1974), J. Polym. Sci. Chem. Ed. 16, 1435 (1978), J. Polym. Sci.
• Suitable amines are ammonia or alkylamines, for example methylamine, dimethylamine, ethylamine, pro pylamine, or butylamine, arylamines, for example aniline, 4-methylaniline or optionally substituted aminophenols, aralkylamines, for example optionally substituted butylamines, aminocarboxylic acids, for example lysine or glycine, alkylenediamines, for example diaminoethane, diaminohexane or N, N'-dimethylaminopropylenediamine, hydroxyethanolamine, for example aminoethanolamine , Alkoxyalkylamines, for example methoxyethylamine, aminopyridines, for example 4-aminomethylpyridine or aminoalkylimidazoles, for example N-3-aminopropylimidazole, aminoureas, for example aminoethylurea, secondary cyclic amines in which R 2 and R
• the particles of the latices of the invention generally have diameters from 20 nm to 1 ⁇ m and preferably 30 to 300 nm.
• the latices are coated with the binders customary in photographic materials such as e.g. Gelatin, polyvinyl alcohol, carboxymethyl cellulose or hydroxyethyl cellulose are compatible and form transparent layers when mixed.
• the latices can be cleaned by the processes known to the person skilled in the art, for example by flakes or redispers yaw, by dialysis, by ultrafiltration or by mixing with gelatin, pasta and water.
• the latices can be stabilized by wetting agents. Often, however, stabilization by adding wetting agents is not necessary, especially if the latices contain ionic groups such as carboxyl or sulfonyl groups or quaternary ammonium groups.
• the latices are generally used as aqueous dispersions. If the preparation is carried out in a non-aqueous medium, the solvent is removed by known methods, e.g. by distillation, dialysis, ultrafiltration or by flaking and redispersing.
• the latices are generally mixed with natural or synthetic binders such as gelatin or other hydrophilic macromolecular substances.
• the amount of latex added is usually 20 to 85% by weight, preferably 50 to 85% by weight, based on the total amount of the binder used.
• the latices according to the invention are preferably used in a mixture with gelatin as a binder.
• the latices of the invention can advantageously be used in a wide variety of photographic materials, both in photosensitive and non-photosensitive layers of such materials.
• non-photosensitive Layers may be called receiving layers as used in diffusion transfer materials, further photographic auxiliary layers which are used in connection with light-sensitive layers.
• the latices can be used as a binder or for modifying the binder. They are also suitable as Ba - sis for polymer couplers or other polymeric excipients for use in a variety of radiation-sensitive materials, such as lithographic plates, photoresist materials and electrophotographic electrostatographic and radiographic materials.
• a mixture of 200 g of water, 2.5 g of a 30% by weight solution of the wetting agent as described for starting latex A, 29.4 g of carbomethoxymethyl acrylate and 1.2 g of divinylbenzene was heated to 75 ° C. under nitrogen. After stirring for 10 minutes, a solution of 0.3 g of potassium peroxodisulfate in 10 g of water and a solution of 0.3 g of sodium metabisulfite in 10 g of water were simultaneously added dropwise within one hour. After stirring for a further 3 hours at 75 ° C., the latex obtained was filtered. The solids content was 11.5% by weight.
• Latex 1 As described under Latex 1, the starting latices A to E were reacted with various amines. The reaction conditions and the degree of conversion are given in Table 1 below.
• the latices 3, 4, 9, 10 and 12 can be used as binder additives.
• the latices 1, 2, 5, 6, 7, 8, 11 and 13 are suitable for fixing metal ions such as Cu ++ , Zn ++ , Ni ++ while the latices 1, 2, 6, 8, 11 and 13 after quaternization with alkylating agents such as benzyl chloride, dimethyl sulfate, epichlorohydrin or chloroethanol, can also be used as mordants.
• a usgangslatex A (8.6 wt .-% aqueous dispersion) was mixed with 20 mol% (based on the Ester Disability Laboratory), KOH and stirred at 30 ° C. After 1 hour the pH of the latex had dropped to 7.5. It was then reacted with 2,4-dichloro-3-methyl-6- (5-aminopentylcarbonamido) phenol in water / acetonitrile as described for latex 2. After dialysis, a cross-linked latex with carboxylate and color coupling groups was obtained. The degree of conversion is 38% by weight, based on the color-coupling groups.
• the latex was then flocked by adding a cyclohexane / acetone mixture, the polymer was filtered off, washed and redispersed in water.
• the latex obtained contains the coupler residue R A. The conversion is determined by determining the acid number and is 55%.
• a 10 wt .-% aqueous binder solution consisting of a mixture of gelatin and linear high molecular weight polyacrylamide in a weight ratio of 10: 1 and 100 ml of a 0.2 wt .-% solution of the below.
• Hardening agent A in water was poured onto a cellulose triacetate base provided with an adhesive layer using a conventional cascade casting machine and dried.
• the curing agent A used has the formula
• the material was stored for 7 days at 30 ° C and 50% relative humidity.
• the wet scratch resistance (NKF) and the swelling factor (QF) were then measured.
• a metal tip of a defined size is passed over the wet layer and loaded with increasing weight.
• the wet scratch resistance is indicated by the weight at which the tip leaves a visible scratch mark on the layer.
• a high weight corresponds to a high wet scratch resistance.
• the swelling is after 10 minutes of treatment of a test strip in distilled water at 22 ° C gra measured vimetrically. It is characterized by the swelling factor:
• the example was repeated using the latices 6 and 12 according to the invention instead of polyacrylamide.
• the changes (in%) of swelling factor ( ⁇ QF) and wet scratch resistance ( ⁇ NKF) were determined using the following formulas:
• the layer properties are significantly improved by the compounds according to the invention compared to linear polymers.
• the resulting mordant samples were soaked for 2 minutes and placed in an aqueous dye solution of 0.05 g of the compound immersed in 100 ml of phosphate buffer (pH 13.5), 1, 2, 3 and 5 minutes.
• a strong coloring of the pickling layers was obtained after just 1 minute.
• the advantageous pickling ability of the pickling layers is shown by the fact that the dye cannot be removed even by washing for several hours.
• the example was made using a cyan dye of the formula and a purple dye of the formula repeated. These samples, too, can be washed for several hours without being discolored.
• the latices of the invention are compared to graft polymers on acrylamide as described in US Pat. No. 3,026,293.
• the viscosities of latex 11 according to the invention and of the copolymer mixture specified in Example 1 of US Pat. No. 3,026,293 were compared.
• the run-out times of the polymer dispersions set at 10% by weight from a DIN cup (4 mm nozzle) were used as a measure of the viscosity.
• the example shows the more favorable viscosity behavior of the latex of the invention compared to the polymer of US Pat. No. 3,026,293, which is composed of similar monomers.
• the latex 16 was admixed with a silver halide gelatin emulsion which was sensitized to red according to the color coupler introduced.
• the silver halide gelatin emulsion used consisted of 75 g of silver bromide iodide (iodide content 3 mol%) and 72 g of gelatin, based on 1 kg of emulsion.
• the emulsion thus prepared was applied to a cellulose triacetate layer support provided with an adhesive layer and dried.
• the sample was exposed using a sensitometer and then processed in the manner described below. Relative sensitivity and color yield were determined.
• a material was used which, instead of the latex according to the invention, contained 16 2,4-dichloro-3-methyl-6- (tridecylcarbonamido) phenol dissolved in tricresyl phosphate in the form of an emulsion.
• the relative sensitivity was determined using a sensitometer.
• the smaller number means higher sensitivity (3 units correspond to a DIN).
• the example shows that with the latexes containing color couplers according to the invention, higher sensitivities and color yields are obtained.

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• General Physics & Mathematics (AREA)
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• Spectroscopy & Molecular Physics (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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• 1982
  • 1982-05-06 DE DE19823217020 patent/DE3217020A1/de not_active Withdrawn
• 1983
  • 1983-04-23 EP EP83103982A patent/EP0093924B1/fr not_active Expired
  • 1983-04-23 DE DE8383103982T patent/DE3371819D1/de not_active Expired
  • 1983-05-04 CA CA000427420A patent/CA1248392A/fr not_active Expired
  • 1983-05-04 JP JP58077666A patent/JPS58214146A/ja active Pending
• 1984
  • 1984-09-10 US US06/648,616 patent/US4513080A/en not_active Expired - Fee Related

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