EP0019178B1 - Procédé pour la préparation de couches de matissement - Google Patents

Procédé pour la préparation de couches de matissement Download PDF

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Publication number
EP0019178B1
EP0019178B1 EP80102426A EP80102426A EP0019178B1 EP 0019178 B1 EP0019178 B1 EP 0019178B1 EP 80102426 A EP80102426 A EP 80102426A EP 80102426 A EP80102426 A EP 80102426A EP 0019178 B1 EP0019178 B1 EP 0019178B1
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EP
European Patent Office
Prior art keywords
weight
particles
copolymer
dispersion
particle size
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
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EP80102426A
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German (de)
English (en)
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EP0019178A2 (fr
EP0019178A3 (en
Inventor
Wolfgang Dr. Himmelmann
Rolf Dr. Brück
Wolfgang Dr. Sauerteig
Peter Dr. Kruck
Günther Dr. Kolb
Günter Dr. Sackmann
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Agfa Gevaert AG
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Agfa Gevaert AG
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Publication date
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Publication of EP0019178A2 publication Critical patent/EP0019178A2/fr
Publication of EP0019178A3 publication Critical patent/EP0019178A3/de
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Publication of EP0019178B1 publication Critical patent/EP0019178B1/fr
Expired legal-status Critical Current

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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
    • G03C1/76—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 method for producing matt outer layers of photographic recording materials which counteract the tendency of such materials to stick.
  • the surface layer of conventional silver halide photographic materials contains a hydrophilic colloid. e.g. Gelatin, as a binder.
  • a hydrophilic colloid e.g. Gelatin
  • the stickiness of such recording materials therefore increases at high atmospheric humidity, especially at 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 that come into contact with it results in the camera. there are numerous difficulties in producing, processing, projecting or storing the recording material.
  • the surface layer of the recording material by incorporating finely powdered inorganic compounds, such as silicon dioxide, magnesium oxide. Titanium dioxide or calcium carbonate, or organic compounds such as polymethyl methacrylate or cellulose acetate propionate. to mattify and thus reduce their stickiness.
  • finely powdered inorganic compounds such as silicon dioxide, magnesium oxide. Titanium dioxide or calcium carbonate, or organic compounds such as polymethyl methacrylate or cellulose acetate propionate.
  • DE-A-2 758 767 discloses a photographic light-sensitive material which has an outer light-sensitive 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, especially at higher humidities (> 85% RH) and temperatures around 35 to 40 ° C., it is not possible to avoid contact marks which are disadvantageous in terms of sensitometry when the materials are rolled up.
  • polymer particles with a particle diameter of 5 to 0.01 microns 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. by H. Reinhard, Dispersions of Synthetic High Polymers. Part 11, page 3 ff. Springer Verlag or by F. Hölscher in the corresponding part 1, page 31 ff. In this way, however, it is not easily possible to produce particles of uniform size of more than 2 ⁇ m.
  • Mechanical pulverization which is followed by classification according to particle sizes, gives polymer particles with a broad particle size distribution, the shape of which is not spherical but 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.
  • the particle size achieved is far from uniform and a device with a large volume is required. So far, there is generally no usable, economical method for producing 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 an oil phase in the form of droplets. adjusting the viscosity and surface tension in a suitable manner and removing the solvent from the droplets of the oil phase to form fine polymer particles.
  • These particles can be separated off by subsequent centrifuge separation and by drying in the form of a powder (DE-A-2 522 692).
  • a disadvantage of this process is that the particles have to be generated during the stirring process, ie are not preformed.
  • the particle size depends on the concentration of the polymer solution, the ratio between the polymer solution and the aqueous medium. the type and amount of the hydrophilic colloid, the temperature, stirring speed and the pH of the aqueous medium.
  • the low-boiling solvent must be carefully distilled off. so as not to destroy the particles.
  • suspension polymers with a particle diameter of 10-1000 ⁇ m. However, it is not possible to obtain particles with the desired diameter of 1 to 10 ⁇ m in the most homogeneous distribution possible.
  • GB-A-1 055 713 describes copolymers of styrene and ethylenically unsaturated carboxylic acids.
  • Carboxylic acid half-esters or carboxylic acid halamides are known as matting agents. They are used in an amount of 100-750 mg / m 2 layer. These matting agents have the disadvantage of dissolving in alkaline photographic baths, as a result of which their matting effect is lost for processed photographic materials.
  • US-A-4 094 848 describes a manufacturing process for porous polymer particles which are useful as matting agents for photographic materials. These are copolymers. which are based on vinyl monomers containing carboxyl groups.
  • the gelatin-containing emulsions contain approx. 12.5 percent by weight of the matting agent.
  • the matting agents have the same disadvantage as those described in GB-A-1 055 713, they are soluble in alkaline photographic baths and are therefore no longer available in a photographically processed recording material.
  • the invention has for its object to develop a process for the production of surface layers which contain insoluble matting particles in alkaline photographic baths, which reduce the stickiness of a photographic material and which, in particular with regard to the impression of the granularity of the photographic material, the disadvantages of the known matting particles do not cling.
  • the object is achieved with a method according to the preamble of claim 1. which is characterized in that the copolymer used is 1 to 15% by weight, preferably 5 to 10% by weight, based on the weight of the dispersion, of spherical particles of an essentially alternating and equimolecularly structured suspension copolymer composed of diisobutylene and maleic anhydride, which in the particle size range from 1 to 10 ⁇ m to 70 to 90% uniform grain diameter and that the particles are applied in an amount of 10 to 500 mg / m 2 .
  • the copolymer used is 1 to 15% by weight, preferably 5 to 10% by weight, based on the weight of the dispersion, of spherical particles of an essentially alternating and equimolecularly structured suspension copolymer composed of diisobutylene and maleic anhydride, which in the particle size range from 1 to 10 ⁇ m to 70 to 90% uniform grain diameter and that the particles are applied in an amount of 10 to 500 mg / m 2
  • the suspension copolymers used according to the invention are copolymers of diisobutylene and maleic anhydride, which are available in the presence of macromolecular dispersants in the form of fine powders with a uniform particle size. Details on this, in particular with regard to the production process, can be found in DE-A-2501 123. Please also refer to G. Sacklmann and G. Kolb, Angewandte Makromolekulare Chemie 1978, pages 141 to 156.
  • the copolymers used according to the invention are essentially alternating and equimolecular suspension copolymers of diisobutylene and maleic anhydride, which in the presence of a radical generator at temperatures of 30 to 200 C and pressures of 1 to 200 bar in an organic dispersion medium of diisobutylene or of diisobutylene and a solvent which is inert towards the monomers and which dissolves the diisobutylene but not the maleic anhydride Presence of 0.5 to 50 wt .-%, based on maleic anhydride used. of a dispersant soluble in the dispersing medium.
  • dispersants are reaction products of alternating copolymers of maleic anhydride and 1-olefins having 2 to 8 carbon atoms, of maleic anhydride and vinyl esters, of maleic anhydride and vinyl ethers, of maleic anhydride and vinyl aromatics with at least one primary, aliphatic, saturated or monoolefinically or unsaturated, linear branched monohydric alcohol with 6 to 22 carbon atoms or with at least one primary or secondary aliphatic. saturated, linear or branched monoamine with 6 to 22 carbon atoms or mixtures thereof.
  • copolymerization process gives copolymer powders which are readily filterable. which consist essentially of discrete spheres with particle diameters between 1 and 10 ⁇ m, and which have a very narrow particle size distribution.
  • the size of the particles formed and their size distribution can be controlled both by the type and by the amount of the dispersant used, the amount being particularly suitable as a control agent.
  • the average particle diameter of the copolymer particles decreases with increasing amount of dispersant. while the uniformity increases.
  • the average particle diameter of a suspension copolymer of maleic anhydride and diisobutylene which was produced with 3% by weight, based on the sum of the monomers copolymerizing in a molar ratio of 1: 1, about 10 ⁇ m, while when using 10% by weight disperser, particle sizes of approx. 3 ⁇ m and when using 20% by weight particle diameter of approx. 2 ⁇ m are obtained.
  • the uniformity of the particle size distribution "increases: with 3% by weight of dispersant there are relatively non-uniform particle sizes, with 10% by weight largely uniform particle sizes with little differences and with 20% by weight completely uniform particle sizes.
  • the uniformity the particle sizes can also be influenced by additional technical measures in the preparation of the copolymer, such as the shape of the stirrer used or the stirring speed.
  • the copolymers which can be prepared are of alternating and equimolecular structure and have degrees of polymerization between 20 and 1,000, preferably between 50 and 300, corresponding to molecular weights of about 4,000 to 200,000, preferably 10,000 to 60,000, determined by membrane osmometry.
  • the preferred copolymers have intrinsic viscosities of 0.05 to 0.70 dl / g. measured in dimethylformamide (DMF) at 25 ° C.
  • the mixture is heated to 75 ° C. while passing over a weak stream of nitrogen and stirring (220 rpm). 25% by volume of the following initiator solution (1) are then added:
  • the mixture is stirred at 90 ° C. for a further six hours.
  • the mixture is then cooled to room temperature and the resulting fine-particle copolymer suspension is suctioned off on the filter. Washed with fresh diisobutylene and dried to constant weight in a vacuum drying cabinet at 70 ° C.
  • the copolymer powders are slurried in a water: glycerol mixture (1: 1) and counted and measured with a light microscope with a phase contrast device at 1,000 ⁇ magnification.
  • hydrophilic colloids e.g. the following compounds are used: proteins, such as gelatin, gelatin derivatives, e.g. acetylated gelatin, phthaloyl gelatin or succinyl gelatin, albumin, casein, gum arabic, agar agar, alginic acid, cellulose derivatives e.g. Alkyl esters of carboxymethyl cellulose, preferably the methyl or ethyl esters, hydroxyethyl cellulose, carboxymethyl cellulose and the like. Synthetic polymers e.g.
  • polyvinyl alcohol polyvinyl pyrrolidone, polyacrylamide, salts of polyacrylic acid, salts of polymethacrylic acid, salts of polymaleic acid, salts of polystyroisulfonic acid, preferably the sodium or potassium salts and copolymers which contain at least one of the monomers of the polymers mentioned above.
  • hydrophilic colloids amphoteric polymeric electrolytes, such as gelatin, gelatin derivatives, casein and other protein compounds, have a particularly pronounced effect. They 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 used in an amount of 5 to 10 wt .-%, each based on the weight of the dispersion.
  • 0.1 to 1% by weight of surface-active agents are used as dispersants.
  • suitable surfactants are saponin and other compounds of natural origin, nonionic surfactants such as alkylene oxide, glycerin compounds such as monoglycerides, glycidol compounds and the like, anionic surfactants with one or more acid groups, e.g. one or more carboxylic acid. Sulfonic acid, phosphoric acid, sulfonic acid ester or phosphoric acid ester groups.
  • surfactants are described in US-A-2,271,623, 2,240,472, 2,288,226, 2,676,122, 2,676,924, 2,676,975, 2,691,566, 2,721,860, 2,730,498, 2,472,379 , 2 739 891, 3 068 101, 3 158 484, 3 201 253, 3 210 191, 3 294 540, 3 415 649, 3 441 413, 3 442 654, 3 475 174 and 3 545 974, in DE-A -1 942 665 and in GB-A-1 077 317 and 1 198 450 and in "Kaimen Kassi Zai no Gosei to Sono Ohyo" (Synthesis and Application of Surface Active Agent) by Ryohei Oda et al.
  • OS0 3 M group such as, for example, sulfonate esters of ordinary alcohols of the general formula R ⁇ O ⁇ SO 3 M or R ⁇ (OCH 2 CH 2 ) n OS0 3 M (where R is an alkyl group with 8 to 30 carbon atoms, M is an alkali metal or ammonium ion and n is a positive integer of up to 20) and alkylbenzenesulfonic acid compounds having 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.
  • R ' hydrogen or 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
  • the resulting dispersions of copolymers with a particle size of 1-10 ⁇ m, preferably 1.5-5 ⁇ m, are each 70-90% of the same size or as particles with the same grain diameter. Only 10-30% of the particles have a larger or smaller particle diameter.
  • the dispersions can either be added directly to the photographic coating solutions for the top protective layer or the particles can be isolated in the form of pastes as a solid residue by centrifugation. In this way, so-called “instant matting agents” are obtained, ie matting agents that can be stirred into any photographic casting solution without dispersing agents.
  • the compounds are photographically inert and do not change the granularity of the recording material, if they are used in the appropriate amount of 10-500 MGIM 2 surface.
  • the advantageous matting effect achieved by the method of the invention can thereby be further improved that the matting dispersion.
  • add colloidal silica in the form of a hydrosol before applying it to the surface of the photographic material, add colloidal silica in the form of a hydrosol.
  • Good results are obtained with commercially available hydrosols with a particle size of 1 to 150 nm, which are added to the matting dispersion 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 from the copolymer particles of the invention by size earthings and are therefore not involved in their specific action.
  • the proportion of the silica particles in the overall effect merely consists in the fact 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 casting compositions used to produce the surface layers can contain further additives which have no effect on the matting effect according to the invention.
  • examples include: very fine-grained ( ⁇ ⁇ 0.1 ⁇ m) latices of hard polymers such as polystyrene, polymethyl methacrylate.
  • very fine-grained (particle diameter ⁇ 0.1 ⁇ m) latices of soft homopolymers and copolymers such as polyethyl acrylate.
  • Polyacrylic acid butyl ester ethyl acrylate or latices of polyether or polyester polyurethanes as described in the journal Research disclosure, December 1978, Industrial Opportunities Ltd. Hampshire, UK. Page 27 (XII A), as well as compounds that increase conductivity as described in “Research Disclosure”. Dec. 1978, page 27 (XIII A).
  • copolymers 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 35 mm films or flat films.
  • the casting solutions were applied with a casting machine to an uncured color negative film as the top protective layer (wet application 50 g solution per m 2 ) and the layer at 25 ° C and 60% rel. Humidity dried.
  • the protective layers formed a dry layer of 0.6-0.7 g / m2.
  • the color negative film used had a conventional structure.
  • a red-sensitized silver halide layer with emulsified Blaugrun color component, an intermediate layer, a green-sensitized silver halide layer with a purple component, a yellow filter layer and a blue-sensitized yellow component-containing silver halide layer were successively applied to a cellulose triacet base.
  • the intermediate layers consisted of gelatin and a casting aid, the yellow filter layer also contained yellow colloidal silver.
  • the layer thicknesses of the layers containing halogen silver were between 5 and 6 ⁇ m, and those of the intermediate layer were 1-2 ⁇ m.
  • the film was cast without curing agent and cured by overlaying the top protective layer solution.
  • the samples were cut into 5 cm 2 pieces and conditioned for 2 days at 30 ° C and 90% humidity. The samples were then stored under pressure for one day against the back of the layer. Then the samples were torn apart and the size of the bonded surface was estimated (bare spots in the surface).
  • a film 35 mm wide and 125 cm long was wound into a film cartridge and stored for 7 days at 90% RH and 35 ° C.
  • the pull-out force (p) was then determined and registered when the film was pulled out of the cartridge.
  • the maximum value is shown in the table below specified. In practice, the pull-out force should not be higher than 300 p.
  • the film stored according to test 2 was developed photographically and checked for visible defects caused by storage, pressure and moisture. The number and size of the different sized stains was evaluated in% based on the tested area. A film with a suitable protective layer should show less than 5% yellow spots.
  • the graininess of a photographic image was caused by the color grain developed and by dispersions and matting agents, especially in the top layers. It was determined by determining the ⁇ -D value with a 29 ⁇ m pinhole as described by JH Altmann in Appl. Optics, Volum 3, (1964) pages 35-38. The graininess of 1.8 is a value sought in photography.
  • results summarized in the previous table show the overall advantageous properties of the matting particles of the invention. While some of the comparative samples in individual tests achieve results comparable to those of the matting samples of the present invention, the samples of the present invention alone provide consistently favorable results throughout all tests, including, and remarkably, the granularity test.
  • Example 2 As described in Example 1, the pastes were added to individual protective layer casting solutions and the casting solutions were applied to the layer side of a color negative film.
  • the protective layer casting solutions had the following composition:
  • Example 2 The test of the samples for effectiveness as a spacer (preventing the smooth contact between the protective layer and the back of a material lying in a stack or on the roll) was carried out according to the 4 methods given in Example 1.
  • a layer structure containing a protective layer without copolymer was used as comparative sample F.
  • the dry protective layers were 0.6-0.7 ⁇ m thick (about 0.6-0.7 g / m 2 application).
  • Sample f contains no copolymer 3.
  • the pull-out force (test 2) is therefore very high (strong adhesion).
  • the value of 300 p must not be exceeded. The sample is therefore unusable.
  • the copolymer particles of the invention act as spacers in an outstanding manner and independently of the film formers used as the dispersing medium.
  • the particles prevent the contact of an emulsion side with a back side of a wound photographic film material, since the matting material according to the invention partly projects beyond the surface of the protective layer.
  • a comparison of the amounts of particles present in the protective layer per unit area of the photographic material before and after color processing shows that the particles were not dissolved in the alkaline developer, i.e. the effect of the spacer is retained even after the material has been processed.
  • the effect of the copolymers according to the invention as a spacer can be increased by adding colloidal silica in the form of SiO 2 hydrosols to the protective layer composition.
  • the pH of the solutions was 6.5-7; the wet application 50 g / m 2 .
  • the hardening agent corresponds to the formula
  • the protective layer solutions were poured onto an uncured color negative film and dried.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Claims (5)

1. Procédé pour la production de couches extérieures mates de matériaux photographiques d'enregistrement aux halogénures d'argent, qui contiennent comme agent de matage des particules dispersées dans un liant d'un copolymère contenant des motifs anhydride maléique dans une gamme de dimensions de particules allant jusqu'à 10 µ, par application d'une dispersion des particules dans la solution aqueuse d'un colloïde hydrophile sur une des deux faces du matériau photographique d'enregistrement et séchage de la couche appliquée, caractérisé en ce que l'on utilise comme copolymère 1 à 15 % en poids, de préférence 5 à 10 % en poids, par rapport au poids de la dispersion, de particules sphériques d'un copolymère en suspension, de structure sensiblement alternée et équimoléculaire, de diisobutylène et d'anhydride maléique, qui présentent des diamètres uniformes pour 70 à 90 % dans le domaine de dimensions de particules de 1 à 101.1. et en ce que les particules sont appliquées en quantité de 10 à 500 mg/m2.
2. Procédé selon la revendication 1, caractérisé en ce que l'on ajoute à la dispersion avant l'application 0,1 à 1 % en poids, par rapport au poids de l'eau contenue dans la dispersion, d'une substance tensioactive.
3. Procédé selon les revendications 1 et 2, caractérisé en ce que l'on utilise la gélatine comme colloïde hydrophile.
4. Procédé selon les revendications 1 à 3, caractérisé en ce que le rapport molaire du copolymère de diisobutylène et d'anhydride maléique est de 1 : 1.
5. Procédé selon les revendications 1 à 4, caractérisé en ce que l'on ajoute à la dispersion, avant l'application, de l'acide silicique colloïdal sous forme d'un hydrosol d'une dimension de particules de 1 à 15 nm en quantité de 0,5 à 2 % en poids de particules d'acide silicique colloïdal pour une partie en poids du colloïde hydrophile.
EP80102426A 1979-05-16 1980-05-05 Procédé pour la préparation de couches de matissement Expired EP0019178B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19792919822 DE2919822A1 (de) 1979-05-16 1979-05-16 Verfahren zur herstellung von mattierungsschichten
DE2919822 1979-05-16

Publications (3)

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EP0019178A2 EP0019178A2 (fr) 1980-11-26
EP0019178A3 EP0019178A3 (en) 1981-05-27
EP0019178B1 true EP0019178B1 (fr) 1982-10-13

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US (1) US4287299A (fr)
EP (1) EP0019178B1 (fr)
JP (1) JPS55153934A (fr)
DE (2) DE2919822A1 (fr)

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JPS5858538A (ja) * 1981-10-02 1983-04-07 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPS5862649A (ja) * 1981-10-09 1983-04-14 Fuji Photo Film Co Ltd 帯電防止されたハロゲン化銀写真感光材料
JPS5862648A (ja) * 1981-10-09 1983-04-14 Fuji Photo Film Co Ltd 帯電防止されたハロゲン化銀写真感光材料
EP0080225B1 (fr) * 1981-11-23 1985-08-07 Agfa-Gevaert N.V. Méthode pour la préparation de dispersions aqueuses et stables de perles polymériques, ainsi que l'utilisation de ces dispersions dans des éléments photographiques
JPS58182636A (ja) * 1982-04-20 1983-10-25 Fuji Photo Film Co Ltd 感光性印刷版
JPS59149357A (ja) * 1983-02-15 1984-08-27 Konishiroku Photo Ind Co Ltd ハロゲン化銀写真感光材料
US4587199A (en) * 1983-07-11 1986-05-06 E. I. Du Pont De Nemours And Company Controlled roughening of a photosensitive composition
DE3331542A1 (de) * 1983-09-01 1985-03-21 Agfa-Gevaert Ag, 5090 Leverkusen Photographisches silberhalogenidaufzeichnungsmaterial
JPS60188942A (ja) * 1984-03-07 1985-09-26 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
JPH0642053B2 (ja) * 1985-10-16 1994-06-01 コニカ株式会社 ハロゲン化銀写真感光材料
EP0289023A3 (fr) * 1987-05-01 1990-08-29 Konica Corporation Matériau photographique à l'halogénure d'argent sensible à la lumière
US4857443A (en) * 1987-05-06 1989-08-15 Fuji Photo Film Co., Ltd. Photographic element with benzoguanamine-formaldehyde polymer particles
JP2681163B2 (ja) * 1988-07-07 1997-11-26 コニカ株式会社 ハロゲン化銀カラー写真感光材料
JPH0289631A (ja) * 1988-09-27 1990-03-29 Somar Corp ケミカルマットフィルム及びそれを用いた感光性フィルム
DE3930141A1 (de) * 1989-09-09 1991-03-21 Bayer Ag Vernetzte perlpolymerisate und ihre herstellung
DE4131142A1 (de) * 1991-09-19 1993-03-25 Bayer Ag Elektroviskose fluessigkeit
US5536627A (en) * 1995-03-21 1996-07-16 Eastman Kodak Company Photographic elements with improved cinch scratch resistance
EP2619628B1 (fr) * 2010-09-17 2014-03-26 Fujifilm Manufacturing Europe BV Papier photographique et son emploi dans un album photographique

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US3353958A (en) * 1964-01-24 1967-11-21 Du Pont Photographic compositions and process
DE1815944C3 (de) * 1968-12-20 1979-11-22 Agfa-Gevaert Ag, 5090 Leverkusen Antistatisches photographisches Material
JPS5028019B1 (fr) * 1969-08-13 1975-09-11
GB1452478A (en) * 1972-11-22 1976-10-13 Agfa Gevaert Process for homogeneously dispersing polymer particles in aqueous medium
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JPS51135958A (en) * 1975-05-20 1976-11-25 Fuji Photo Film Co Ltd Method of making fine powder polymer having pores
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JPS5229302A (en) * 1975-08-28 1977-03-05 Fuji Photo Film Co Ltd Photoosensitive printing plate

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EP0019178A2 (fr) 1980-11-26
EP0019178A3 (en) 1981-05-27
DE2919822A1 (de) 1980-11-27
JPS55153934A (en) 1980-12-01
DE3060938D1 (en) 1982-11-18
US4287299A (en) 1981-09-01
JPH0215853B2 (fr) 1990-04-13

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