EP0167081B1 - Matériau d'enregistrement photographique à l'halogénure d'argent - Google Patents

Matériau d'enregistrement photographique à l'halogénure d'argent Download PDF

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Publication number
EP0167081B1
EP0167081B1 EP85107790A EP85107790A EP0167081B1 EP 0167081 B1 EP0167081 B1 EP 0167081B1 EP 85107790 A EP85107790 A EP 85107790A EP 85107790 A EP85107790 A EP 85107790A EP 0167081 B1 EP0167081 B1 EP 0167081B1
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Prior art keywords
particles
cellulose
particle size
layer
weight
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EP85107790A
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German (de)
English (en)
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EP0167081A3 (en
EP0167081A2 (fr
Inventor
Wolfgang Dr. Himmelmann
Fritz Dr. Nittel
Rudolf Dr. Meyer
Lothar Dr. Rosenhahn
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/95—Photosensitive materials characterised by the base or auxiliary layers rendered opaque or writable, e.g. with inert particulate additives
    • 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
    • Y10S430/151—Matting or other surface reflectivity altering material

Definitions

  • the invention relates to a photographic silver halide recording material which, in an outer transparent layer attached to the front and / or back, dispersed in a hydrophilic colloid, contains particles of cellulose ether dicarboxylic acid semiesters with a particle size of less than 10 ⁇ m which are soluble in alkaline processing liquids.
  • the hydrophilic colloids usually contained in the outer layers of silver halide photographic materials e.g. As gelatin, lead to an increase in the stickiness of the recording materials at high atmospheric humidity and higher temperatures, so that such recording materials, for example after packaging in a stack, easily stick together. This tendency to stick between different parts of the recording material or between the recording material and other materials which come into contact with it leads to numerous difficulties in the camera, in the production, processing, projection or storage of the recording material.
  • DE-OS 2758767 discloses a photographic light-sensitive material which has an outer light-insensitive gelatin layer which contains colloidal silica particles with a size of 7 to 120 nm and a polymer latex, the particles of which are 30 to 80 nm in size. This gelatin layer gives the photographic material increased fracture and dimensional stability.
  • a disadvantage of such a photographic material is that the additives reduce the transparency of the layers and, particularly at higher humidities (for example more than 85% RH) and temperatures around 35 to 40 ° C., sensitometrically disadvantageous contact spots when rolled up of the materials cannot be avoided.
  • polymer particles with a particle diameter of 5 to 0.01 ⁇ m can be produced by emulsion polymerization if the amount of the emulsifier (surface-active agent), the polymerization temperature and the stirring conditions are suitably controlled.
  • the procedure is e.g. B. by H. Reinhard, “Dispersions of synthetic high polymers •, Part 11, page 3 ff., Springer Verlag or by F. Hölscher in the corresponding Part I, page 31 ff. In this way, however, only particles can be produced whose average size differs by at least 2 f Lm, that is to say which have a relatively non-uniform particle size.
  • Mechanical pulverization, followed by classification according to particle sizes gives polymer particles with a broad particle size distribution, the shape of which is not spherical but rather completely irregular.
  • Spherical polymer particles can be prepared by dissolving a polymer in a water-immiscible organic solvent and spraying the solution from a fine nozzle into an aqueous medium under high pressure. So far, there is generally no viable, economical method for producing uniform polymer particles with a particle size within the range from 1 to 10 ⁇ m.
  • Fine-particle polymer particles can also be produced by dispersing.
  • one or more polymers are dissolved in a solvent which is insoluble or essentially immiscible in water and has a lower boiling point than water or forms an azeotropic mixture with water having a lower boiling point than water.
  • the polymer solution is dispersed in an aqueous medium as a dispersing agent in the form of droplets, the viscosity and surface tension being adjusted in a suitable manner and the solvent being removed from the droplets to form fine polymer particles.
  • These particles can be separated off by subsequent centrifugation and drying in the form of a powder (DE-OS 2 522 692).
  • Preformed water-insoluble polymer particles with a relatively narrow particle size distribution which are suitable as matting agents for photographic layers, can be obtained by suspension copolymerization of maleic anhydride and 1-olefins (DE-OSen 2501 124, 2 919 822 and 3 144 793).
  • the process leads to particles which are obtained with sufficient uniformity with regard to the particle size, but the particles are insoluble in alkali. They therefore remain on the surface after the processing of the photographic material and thus increase the granularity of the light-sensitive material.
  • the known graft polymers which are soluble in alkaline medium and are based on methacrylic acid and methyl methacrylate based on copolymers of styrene-maleic acid as the graft base have the disadvantage that, in the absence of gelatin, they partially dissolve at pH values around 6.2-6.5 in the absence of gelatin. Since the small particles in particular dissolve, the entire size distribution of the particles changes and forces them to use larger quantities. The viscosity of the casting solution increases and must therefore be continuously monitored. The premature dissolution of the particles is particularly disadvantageous if additives, such as silica sols, are added to the casting solution which are alkaline due to their preparation and for the purpose of stabilizing the solutions.
  • the use of the known alkali-soluble matting particles leads to difficulties during pouring and drying, because the matting particles can already be dissolved at the pH of the emulsion layers.
  • the alkali-soluble matting particles are generally protected by the fact that the pH value decreases continuously when the particles are dissolved. Then a certain pH value can be set that is favorable for the particles. If, however, the casting solutions or the layer structure have a pH value above 6.5 and the buffer capacity is large, then the particles dissolve increasingly without the aforementioned favorable pH value being reached, i. H. the desired matting effect is lost.
  • the invention has for its object to develop a photographic material whose outer layers have no tendency to stickiness, which have a high gloss and high transparency after processing of the photographic material, and whose casting solutions are stable at pH values up to 7.
  • the invention relates to a photographic silver halide recording material which, in an outer transparent layer attached to the front and / or back, dispersed in a hydrophilic colloid in alkaline processing liquids, contains soluble particles with a particle size of less than 10 ⁇ m, and which is characterized in that the layer Contains 10-500 mg / m 2 spherical transparent particles of a hydroxyalkyl-alkylcellulose-dicarboxylic acid semiester with a particle size of 0.5-8 ⁇ m and a particle size distribution of up to ⁇ 2 ⁇ m.
  • hydroxyalkyl-alkyl cellulose dicarboxylic acid esters used in the outer layer of the recording material of the invention - hereinafter referred to as «cellulose derivatives for short - are insoluble in gelatin-containing casting solutions at pH values below 7, but dissolve slightly above pH 8. The increase in solubility occurs within a small pH interval above pH 7.2.
  • dicarboxylic acid monoesters examples are esters of phthalic acid, tetrahydrophthalic acid or hexahydrophthalic acid.
  • these dicarboxylic acid monoesters are mixed via one of their carboxyl groups with mixed ethers of cellulose, e.g. B. hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxyethyl ethyl cellulose or hydroxypropyl ethyl cellulose, esterified.
  • the content of dicarboxylic acid monoesters in the cellulose derivatives should be adjusted in accordance with the hydrophobizing effect of the cellulose ethers so that the desired solubility is achieved in alkaline solution.
  • the compounds can be produced in a simple manner by the process given in DE-OS 2841 164.
  • the cellulose derivatives are used in an amount of 10 to 500 mg / m 2 , preferably 80 to 150 mg / m 2 , per layer.
  • Particularly suitable cellulose derivatives have e.g. B.
  • phthaloyl is used here and below for the grouping ⁇ CO ⁇ C 6 H 5 ⁇ COOH.
  • So-called stabilizers can be added to the cellulose derivatives introduced into the outer layers of the photographic material.
  • R stands for one of the monounsaturated aliphatic radicals -C 12 H 23 , ⁇ C 15 H 29 or ⁇ C 18 H 35 , the formation of which can be explained by multiple additions of propylene.
  • the stabilizers can be added to the casting solutions of the outer layers before the dispersing process, in amounts of 1 to 30% by weight and preferably 2.5 to 10% by weight. based on the solids content of cellulose derivative.
  • hydroxypropylmethyl cellulose hexahydrophthalic acid half-ester compound A
  • compound A hydroxypropylmethyl cellulose hexahydrophthalic acid half-ester
  • the particle size obtained is 1-4 ⁇ m.
  • the excess methylene chloride is now removed at 40 ° C. with slow stirring.
  • the dispersion is then filtered through a filter with a pore size of 10 ⁇ m and solidified in a cooling dish. 1,200 g of dispersion contain approximately 100 g of cellulose derivative.
  • the particle size varies between 1 and 4 ⁇ m. The distribution of the particle size is shown in Figure 1.
  • FIGS. 1, 2, 4 and 5 show the frequency distribution of the particle diameters of the cellulose derivatives indicated as the frequency density (1 / ⁇ ,) corresponding to the individual particle diameters ( ⁇ m). Each of the representations also contains the associated cumulative frequency curve (integral distribution).
  • FIG. 3 shows an electron microscopic image of the cellulose derivative particles in a magnification of 10,000 times
  • the cellulose derivative particles of the dispersions have a spherical shape and are transparent. They are obtained in particle sizes of 1-7 ⁇ m and preferably 1-5 ⁇ m.
  • the cellulose derivatives must be free of microgels. This can be demonstrated by dissolving the particles in a 1% aqueous Na 2 CO 3 solution and determining the microgel content in the solution using an ultracentrifuge.
  • hydrophilic colloids z. B the following compounds are used: proteins such as gelatin, gelatin derivatives, e.g. B. acetylated gelatin, phthaloyl gelatin or succinyl gelatin, albumin, casein, gum arabic, agar agar, alginic acid, cellulose derivatives z.
  • hydrophilic colloids amphoteric polymeric electrolytes, such as gelatin, gelatin derivatives, casein and other protein compounds, have a particularly pronounced effect.
  • the hydrophilic colloids can also be used individually or in combination.
  • Preferred colloids include gelatin, gelatin derivatives, casein and other protein compounds.
  • the colloid is advantageously used in an amount of about 1 to about 15% by weight, preferably in an amount of 5 to 10% by weight, in each case based on the weight of the dispersion.
  • a further 0.1 to 1% by weight of surface-active agents can be added to the aqueous solutions containing the dispersion.
  • suitable surfactants are saponin and other compounds of natural origin, nonionic surfactants such as polyalkylene oxides, glycerol compounds such as monoglycerides or glycidol compounds, anionic surfactants with one or more acid groups, such as e.g. B. one or more carboxylic acid, sulfonic acid, phosphoric acid, sulfonic acid ester or phosphoric acid ester groups.
  • suitable surface active agents are described in US Pat. Nos.
  • surfactants can also be used alone or in the form of combinations.
  • Particularly suitable compounds are those with an OSO s M group, such as. B. sulfonate esters of ordinary alcohols of the general formula RO-SO 3 M or R ⁇ (OCH 2 CH 2 ) n ⁇ OSO 3 M (wherein R is an alkyl group with 8 to 30 carbon atoms, M is an alkali metal or ammonium ion and n is a positive whole Number of up to 20) and alkylbenzenesulfonic acid compounds with the general formula wherein R 'is hydrogen or an alkyl group having 1 to 18 carbon atoms, R "is an alkyl group having 1 to 18 carbon atoms, M is an alkali metal or ammonium ion, m is a positive integer from 0 to 20 and n is 3 or 4.
  • the dispersions containing the cellulose derivatives can either be added directly to the photographic casting solutions for the outer layer or the cellulose derivative particles can be isolated in the form of pastes as a solid residue by centrifugation.
  • the cellulose derivatives are photographically inert and do not change the granularity of the recording material if they are added to the layers in the appropriate amount of 10 to 500 mg / m 2 .
  • the advantageous surface roughening achieved with the cellulose derivatives of the invention can be further improved by adding colloidal silica in the form of a hydrosol to the casting composition containing the cellulose derivatives before it is applied to the surface of the photographic material.
  • colloidal silica in the form of a hydrosol to the casting composition containing the cellulose derivatives before it is applied to the surface of the photographic material.
  • Good results are obtained with commercially available hydrosols with a particle size of 50 to 150 nm, which are added to the casting composition in amounts of 0.5 to 2 parts by weight, based on 1 part by weight of the hydrophilic colloid.
  • the silica particles introduced with the hydrosol differ by orders of magnitude from the cellulose derivatives of the invention and are therefore not involved in their specific action.
  • the proportion of the silica particles in the overall effect is merely that they further suppress the already slight tendency of the surface layers produced by the process of the invention to form gloss spots or color spots.
  • the coating compositions used to produce the outer layers of the invention may optionally contain further additives which h eit take on the desired surface finish no influence.
  • further additives which h eit take on the desired surface finish no influence. Examples include: very fine-grained (0 ⁇ 0.1 ⁇ m) latices of hard polymers such as polystyrene, polymethyl methacrylate. Further very fine-grained (particle diameter ⁇ 0.1 w m) latices of soft homopolymers and copolymers such as polyethylacrylate, polyacrylate butyl ester ethyl acrylate or latices of polyether or polyester polyurethanes, as described in the journal Research Dischlosure, Dec. 1978, Industrial Opportunities Ltd.
  • the polymers can the layers in amounts of up to 50 wt .-%. based on the dry content of hydrophilic colloid.
  • the outer layers of the invention can be used to add the hardener to the gelatin layers of the photographic material.
  • the hardening agent reaches the deeper layers by diffusion.
  • B. harden a color photographic multilayer material in one step.
  • fast-acting hardening agents are particularly common for this method of working. Examples of such curing agents are N-carbamoyl and N-carbamoyloxypyidinium compounds (US Pat. No. 3,880,665), sulfo group-containing N-carbamoyipyridinium compounds in the form of the free betaines or their metal salts (US Pat. No.
  • the cellulose derivatives used according to the invention can advantageously be used in the protective or surface layers of black and white photographic materials, in color materials and in the so-called non-curling layers of roll and small picture films or flat films.
  • the cellulose derivatives in the form of their dispersions are stirred into this composition.
  • casting compositions are produced as comparative samples which, instead of the cellulose derivatives according to the invention, contain the following known matting agents, not according to the invention, in an amount of 4 g each:
  • the casting compositions are applied with a casting machine to an uncured color negative film as the top cover layer (wet application 50 g g composition per m 2 ) and the layer at 25 ° C and 60% rel. Humidity dried.
  • the cover layers form a dry layer of 0.6-0.7 g / m 2.
  • the color negative film used has a conventional structure.
  • a red-sensitized silver halide layer with emulsified cyan color coupler, an intermediate layer, a green-sensitized silver halide layer with a purple coupler, a yellow filter layer and a blue-sensitized yellow coupler-containing silver halide layer are applied in succession to a cellulose triacet base.
  • the intermediate layers consist of gelatin and a casting aid, the yellow filter layer also contains yellow colloidal silver.
  • the layer thicknesses of the layers containing silver halide are between 5 and 6 ⁇ m, those of the intermediate layer 1-2 ⁇ m.
  • the film is cast without curing agent and cured by overlaying the top coat composition.
  • Test 1 shiny spots.
  • the samples are cut into 5 cm 2 large pieces and conditioned for 2 days at 30 ° C and 90% humidity. The samples are then stored under pressure on the layer side against the back for one day. Then the samples are torn apart and the size of the bonded surface is estimated (bare spots in the surface).
  • a film 35 mm wide and 125 cm long is wound into a film cartridge and 7 days at 90% RH. F. and 35 ° C stored.
  • the pulling force (g) is then determined and registered when the film is pulled out of the cartridge.
  • the maximum value is shown in the table below. In practice, the pull-out force should not exceed 300 g.
  • the film stored according to test 2 is developed photographically and checked for visible defects which have arisen as a result of storage, pressure and moisture. The number and size of the differently sized colored spots is evaluated in%, based on the area tested. A film with a suitable protective layer should show less than 5% yellow spots.
  • the graininess of a photographic image is caused by the color grain developed and by dispersions and matting agents, especially in the top layers. It is determined by determining the u-D value with a 29 ⁇ m pinhole as described by J.H. Altmann in Appl. Optics, Volume 3, (1964) pages 35-38. The graininess of 1.8 is a value sought in photography.
  • the reflection (in%) of a light beam on the layer surface is determined.
  • a gelatin layer containing no dispersed particles shows 100% reflection.
  • the effect of the cellulose derivatives according to the invention can be increased by adding colloidal silica in the form of SiO 2 hydrosols or by adding a latex of a hard polymer or copolymer with a glass transition temperature of over 40 ° C. and a particle size of less than 0.5 ⁇ m, such as polymethyl methacrylate , to increase the protective layer composition.
  • Sodium polystyrene sulfonic acid or a copolymer of the structure is added as a viscosity-increasing agent
  • top layer compositions are produced:
  • the pH of the solutions is 6.5-7; the wet application 50 g / m 2 .
  • the hardening agent corresponds to the formula
  • the top layer solution is poured onto an uncured color negative film and dried.
  • Glossy spots and color spots can practically be completely avoided by combining the cellulose derivatives according to the invention with silica sol or latex such as samples B and C.
  • the solvent mixture is slowly evaporated off over 2 hours with gentle stirring. After filtering through a filter cloth, particles with a particle size mixture of 1-5 wm are obtained. The largest particles have a size of 10 to 15 ⁇ m. The particles have a grained porous surface and are opaque.
  • the cellulose derivatives do not dissolve at a pH below 7. This is particularly advantageous for casting solutions which have to be digested for a long time and have a pH of 6.5-7 because certain components contribute pH values less than 6.5 not stable are.
  • the particles according to the invention differ from the comparison particles further in this. that they are clear and have a smooth surface.
  • sample 3-B are more resistant to the formation of glossy spots than the particles of the comparative sample.
  • the cartridge pull-out force is the lowest with sample 3-B.
  • the granularity of sample 3-B is as low as that of sample 3-C without a matting agent.
  • the properties of sample 3-B are thus clearly superior to those of the comparative sample.
  • Dispersion 3-A and Dispersion 3 are diluted 1: 100 with buffer solutions.
  • the buffer solutions have pH values of 5.5, 6.0, 6.5, 7.0, 7.5 and 8.0.
  • the particles of dispersion 3-A are already dissolved at pH 6.2 and have therefore lost their effect as matting and anti-adhesive.
  • the particles of dispersion 3 according to the invention are completely stable up to pH 7 and do not dissolve. Your application will be greatly favored.
  • the particles according to the invention are therefore insensitive to pH settings in the casting solution, which represents a considerable advantage.

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Claims (5)

1. Matériel photographique d'enregistrement à l'halogénure d'argent qui, dans une couche transparente externe appliquée sur le côté avant et/ou arrière, contient des particules dispersées dans un colloïde hydrophile, solubles dans les liquides de traitement alcalins, d'une dimension de particule inférieure à 10 µm, caractérisé en ce que la couche contient à l'état dispersé 10 à 500 mg/m2 de particules transparentes en forme de billes, d'un semiester d'acide dicarboxylique d'hydroxyalcoylalcoyl-cellulose ayant une dimension de particule de 0.5 à 8 µm et une distribution des dimensions de particule allant jusqu'à ± 2 µm.
2. Matériel selon la revendication 1, caractérisé en ce qu'il contient un semiester d'acide dicarboxylique d'hydroxyalcoyl-alcoyl-cellulose avec le groupement
Figure imgb0047
dans lequel
A représente un radical glucose de cellulose,
R1 un radical hydroxyalcoyle ayant 2 à 4 atomes de carbone,
R2 un radical alcoyle ayant 1 à 3 atomes de carbone,
R3 le radical monoacylé d'un acide benzène-dicarboxylique ou d'un tel acide sous la forme partiellement ou totalement hydrogénée,
m = 0,2-1,0
n = 0,8-2,0 et
p = 0,5-1,5

en l'occurrence m :0 n 0 p et la somme m + n + p étant au plus de 3.
3. Matériel selon la revendication 1, caractérisé en ce que le semiester d'acide dicarboxylique d'hydroxyalcoyl-alcoyl-cellulose est un semiester d'acide hexahydrophtalique d'hydroxypropylméthyl- cellulose ou un semiester d'acide phtalique d'hydroxypropyl-méthyl-cellulose.
4. Matériel selon les revendications 1 et 2, caractérisé en ce que la couche contient en plus de la silice colloïdale d'une dimension de particule inférieure à 0,15 µm en une quantité de 0,5 à 2 parties en poids par partie en poids du colloïdale hydrophile.
5. Matériel selon les revendications 1 à 3, caractérisé en ce que la couche contient en plus des particules d'un homo- ou copolymère ayant une température de transition vitreuse d'au moins 40 °C et une dimension de particule inférieure à 0,1 µm, en une quantité allant jusqu'à 50 % en poids par rapport au colloïde hydrophile.
EP85107790A 1984-07-06 1985-06-24 Matériau d'enregistrement photographique à l'halogénure d'argent Expired EP0167081B1 (fr)

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DE19843424893 DE3424893A1 (de) 1984-07-06 1984-07-06 Photographisches silberhalogenidaufzeichnungsmaterial
DE3424893 1984-07-06

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EP0167081A2 EP0167081A2 (fr) 1986-01-08
EP0167081A3 EP0167081A3 (en) 1987-03-18
EP0167081B1 true EP0167081B1 (fr) 1988-07-27

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FR2180465A1 (en) * 1972-04-18 1973-11-30 Kodak Pathe Antistatic, antihalo compsns - for photographic products
US3816136A (en) * 1972-07-17 1974-06-11 Eastman Kodak Co Photographic element and process of developing
US4514131A (en) * 1983-01-10 1985-04-30 Godwin Sr James P Automatic self-locking roll back carrier for a vehicle

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DE3424893A1 (de) 1986-02-06
JPS6132050A (ja) 1986-02-14
EP0167081A3 (en) 1987-03-18
EP0167081A2 (fr) 1986-01-08
US4603102A (en) 1986-07-29
JPH0519696B2 (fr) 1993-03-17
DE3564044D1 (en) 1988-09-01

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