EP0052735B1 - White photographic paper support and method of producing the same - Google Patents
White photographic paper support and method of producing the same Download PDFInfo
- Publication number
- EP0052735B1 EP0052735B1 EP81108099A EP81108099A EP0052735B1 EP 0052735 B1 EP0052735 B1 EP 0052735B1 EP 81108099 A EP81108099 A EP 81108099A EP 81108099 A EP81108099 A EP 81108099A EP 0052735 B1 EP0052735 B1 EP 0052735B1
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- EP
- European Patent Office
- Prior art keywords
- alkaline earth
- earth metal
- base material
- film base
- photographic film
- 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
Links
- 238000000034 method Methods 0.000 title claims description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000011248 coating agent Substances 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 27
- 229920000098 polyolefin Polymers 0.000 claims abstract description 21
- -1 alkaline earth metal carbonate Chemical class 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 18
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 12
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 6
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000001095 magnesium carbonate Substances 0.000 claims abstract description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 4
- 239000000292 calcium oxide Substances 0.000 claims abstract description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000395 magnesium oxide Substances 0.000 claims abstract 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000203 mixture Substances 0.000 claims description 24
- 239000000049 pigment Substances 0.000 claims description 21
- 238000007765 extrusion coating Methods 0.000 claims description 10
- 230000003287 optical effect Effects 0.000 claims description 8
- 238000004040 coloring Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 238000001125 extrusion Methods 0.000 claims 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- 229920003002 synthetic resin Polymers 0.000 description 13
- 239000000057 synthetic resin Substances 0.000 description 13
- 239000000654 additive Substances 0.000 description 8
- 239000012463 white pigment Substances 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
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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
- G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
- G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/256—Heavy metal or aluminum or compound thereof
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/258—Alkali metal or alkaline earth metal or compound thereof
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/3188—Next to cellulosic
- Y10T428/31895—Paper or wood
- Y10T428/31899—Addition polymer of hydrocarbon[s] only
- Y10T428/31902—Monoethylenically unsaturated
Definitions
- the invention relates to a photographic support material consisting of paper and at least one titanium dioxide arranged on the paper in an amount between 10 and 20% by weight and optionally containing polyolefin layer containing color pigments and / or optionally optical brighteners, and to a method for producing a photographic support material.
- Waterproof photographic papers consist of a paper carrier with synthetic resin films applied on both sides and a light-sensitive coating consisting of one or more layers based on silver salts on one of the synthetic resin surfaces.
- the synthetic resin films lying on the base paper can, according to DE-B-1 447 815, be made of polyolefin, e.g. As polyethylene, exist and are layered on the paper by means of extrusion coating.
- polyolefin e.g. As polyethylene
- the synthetic resin film (front coating) arranged under the light-sensitive layers usually contains light-reflecting white pigment and optionally shading dyes, optical brighteners and / or other additives, such as lubricants and antistatic compounds.
- the synthetic resin film (back coating) arranged on the back can be pigmented or pigment-free and / or contain other additives which result from the respective use of the laminate as a photographic support.
- the most important component in the front coating between the base paper and light-sensitive layers is the light-reflecting white pigment in addition to the hydrophobic synthetic resin binder.
- This white pigment is not only decisive for the visual impression of a photographic image, but also for the imaging quality and the durability of the photographic image produced in the adjacent photographic layers.
- US-A-3 833 380 describes a rutile titanium dioxide as white pigment in a polyethylene layer because the UV light absorption of the rutile, which is known per se, has proven to be advantageous for the durability of color photographic images.
- DE-A-2 529 989 proposes the use of a special anatase titanium dioxide surface-treated with alumina hydrate because the whiteness is higher than that of the common rutile titanium dioxide according to US Pat. No. 3,833,380. And in US Pat. No. 4,185,480 the combined use of rutile titanium dioxide with anatase titanium dioxide is proposed because such a mixture advantageously combines the opacity, lightfastness and image sharpness inherent in the rutile with the higher whiteness inherent in the anatase and better compatibility with optical brighteners.
- DE-A-2 654 220 proposes e.g. B. the use of 5-40% calcium carbonate as white pigment, which leads to a reduction in production, due to its small particle diameter of less than 0.4 f.lm improve the surface properties and should make a special, the adhesion of photographic layers surface treatment superfluous.
- red or violet pigments are optionally mixed together with blue pigment into the polyolefin containing titanium dioxide.
- the titanium dioxide can also be replaced by other white pigments or combined with other white pigments. Precise information on how this is to be done cannot be found in this published specification.
- optical brighteners such as 2,5-di- (5-tert.butyl-benzoxazolyl-2 ') thiophene for pigmented image carrier layer has long been known.
- the pigmented and optionally nuanced and / or lightened white front layer applied by means of extrusion coating is usually surface-treated after it has solidified in order to ensure that photographic layers arranged thereon adhere well despite the hydrophobic nature of the synthetic resin.
- the corona treatment of the hydrophobic surface described in DE-A-1 447 611 is preferably used.
- a disadvantage of the pigmented front layers composed according to the prior art described is first of all that all the white pigments described, with the exception of the calcium carbonate used in DE-A-2 654 220, promote the degradation of the polyolefinic synthetic resin binder.
- degradation products cause severe corrosion on the die lips after just a few days to a maximum of 2 weeks. It is therefore necessary to regrind them at short intervals, otherwise the profile of the coating applied from the melt will become uneven and, in extreme cases, the surface will become contaminated.
- the object of the invention is therefore to provide a waterproof white photographic paper support which has the opacity and whiteness of a material coated with titanium dioxide in polyolefin, but avoids the disadvantages of this mixing system.
- the polyolefin layer additionally contains 0.1-5% by weight of an alkaline earth metal carbonate and / or 0.2-10% by weight of an alkaline earth metal oxide.
- Oxides and carbonates of calcium or magnesium are preferred, but the corresponding compounds of strontium and barium are also suitable as additives according to the invention for polyolefin coating compositions containing titanium dioxide for the extrusion coating of photographic papers.
- the paper base to be coated with a pigmented and stabilized polyolefin mixture according to the invention can be any photographic base paper which is either neutral sized using alkyl ketene dimer or has a known acidic size based on precipitated resin soaps, fatty acid soaps or fatty acid anhydrides.
- the base papers preferably also carry a sealing and / or adhesion-imparting surface sizing made from water-soluble or water-dispersible substances.
- the surface coating can contain antistatically active substances and, if appropriate, pigments and / or hydrophobizing additives and / or coloring additives.
- the base paper can be made exclusively from cellulose fibers or from mixtures of cellulose fibers with synthetic fibers. It can have a basis weight of 60-300 g / m z (preferably 70-200 g / m 2).
- the pigment-containing polyolefin coating composition can be applied to one or both sides of the paper. It consists essentially of a polyolefin, a titanium dioxide and the addition of an alkaline earth metal carbonate or oxide according to the invention. It can optionally contain optical brighteners and / or shading dyes and / or antioxidants and / or lubricants and is applied by means of extrusion coating at conventional temperatures of 280 to 330 ° C.
- the polyolefin is preferably polyethylene. Both high density and low density polyethylene can be used.
- the polyolefin resin can also be an ethylene copolymer or polypropylene.
- a photographic base paper weighing approx. 130 g / m 2 was coated with approx. 30 g / m 2 of a pigmented synthetic resin mixture on the front by means of extrusion coating.
- the composition of the mixture was
- the back was made with a mixture of about 30 g / m 2 overdrawn.
- a photographic base paper weighing approximately 130 g / m 2 was coated on both sides as in Example 2, with the difference that the front coating contained 0.5% by weight of strontium carbonate instead of magnesium carbonate.
- a photographic base paper weighing approximately 130 g / m 2 was coated on both sides as in Example 2, with the difference that the front coating contained 0.5% by weight of calcium oxide instead of magnesium carbonate.
- the back was coated with about 20 g / m 2 of the same polyethylene mixture as in Example 1.
- the back was coated with about 15 g / m 2 of the same polyethylene mixture as in Example 1.
- Examples 7 to 18 As comparisons to the resin-coated photographic paper supports described in Examples 1 to 6, corresponding coated paper supports were produced as Examples 7 to 18, which differed from the examples according to the invention only in that the pigmented coating mixture on the front was free from that contained in Examples 1 to 6 Alkaline earth metal oxide or alkaline earth metal carbonate.
- coated carrier materials were compared both with regard to their different running behavior in the extrusion coating and with regard to the homogeneity of the coloring of the front layer, and after a conventional corona treatment of the surface they were coated with a light-sensitive silver halide layer and processed into photographic images. The photographic images were compared for sharpness.
- Table 2 summarizes the main results of the tests. This clearly results in the superior quality of the coated photographic base papers produced according to the invention using mixtures of titanium dioxide with alkaline earth oxides or alkaline earth carbonates.
- FIGS. 1 to 3 shows white photographic support materials of the invention in various configurations.
- the reference numeral 1 designates the paper
- the reference numeral 2 the coating consisting of a polyolefin according to the invention, which is designed according to Examples 1 to 6.
- the reference number 3 is an adhesion-promoting layer, optionally with additives such as a brightener
- the reference number 4 denotes the light-sensitive layer or layers
- the reference number 5 also the back coating made of a polyolefin, which can be transparent or pigmented, for example with carbon black.
- the reference numeral 6 is a back stroke to make the photographic paper writable and / or to provide it with an antistatic finish.
- a primer 7 is provided between the polyolefin layer and the paper, which is applied directly to the paper to give it additional smoothing or to serve as an adhesion promoter.
- the reference numeral 8 is a backside coating, which serves here as an anti-curl layer, that is to prevent curling of the paper.
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Paper (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Die Erfindung betrifft ein fotografisches Trägermaterial, bestehend aus Papier und mindestens einer auf dem Papier angeordneten Titandioxid in einer Menge zwischen 10 und 20 Gew.-% sowie gegebenenfalls Farbpigmente und/oder gegebenenfalls optische Aufheller enthaltenden Polyolefinschicht sowie ein Verfahren zur Herstellung eines fotografischen Trägermaterials.The invention relates to a photographic support material consisting of paper and at least one titanium dioxide arranged on the paper in an amount between 10 and 20% by weight and optionally containing polyolefin layer containing color pigments and / or optionally optical brighteners, and to a method for producing a photographic support material.
Wasserfeste fotografische Papiere bestehen aus einem Papierträger mit auf beiden Seiten aufgebrachten Kunstharzfilmen und einem aus einer oder mehreren Schichten bestehenden, auf Silbersalze basierenden lichtempfindlichen Überzug auf einer der Kunstharzoberflächen.Waterproof photographic papers consist of a paper carrier with synthetic resin films applied on both sides and a light-sensitive coating consisting of one or more layers based on silver salts on one of the synthetic resin surfaces.
Die auf dem Basispapier liegenden Kunstharzfilme können gemäß DE-B-1 447 815 aus Polyolefin, z. B. Polyäthylen, bestehen und mittels Extrusionsbeschichtung auf das Papier geschichtet werden.The synthetic resin films lying on the base paper can, according to DE-B-1 447 815, be made of polyolefin, e.g. As polyethylene, exist and are layered on the paper by means of extrusion coating.
Der unter der bzw. den lichtempfindlichen Schichten angeordnete Kunstharzfilm (Vorderseitenbeschichtung) enthält üblicherweise lichtreflektierendes Weißpigment sowie gegebenenfalls Nuancierfarbstoffe, optischen Aufheller und/oder andere Zusätze, wie Gleitmittel und antistatisch wirkende Verbindungen.The synthetic resin film (front coating) arranged under the light-sensitive layers usually contains light-reflecting white pigment and optionally shading dyes, optical brighteners and / or other additives, such as lubricants and antistatic compounds.
Der auf der Rückseite angeordnete Kunstharzfilm (Rückseitenbeschichtung) kann pigmentiert oder pigmentfrei sein und/oder andere Zusätze enthalten, die sich aus der jeweiligen Verwendung des Laminates als fotografischer Träger ergeben.The synthetic resin film (back coating) arranged on the back can be pigmented or pigment-free and / or contain other additives which result from the respective use of the laminate as a photographic support.
Wichtigster Bestandteil in der zwischen Basispapier und lichtempfindlichen Schichten liegenden Vorderseitenbeschichtung ist neben dem hydrophoben Kunstharzbinder das lichtreflektierende Weißpigment. Dieses Weißpigment ist nicht nur bestimmend für den visuellen Eindruck eines fotografischen Bildes, sondern auch für die Abbildungsqualität und die Haltbarkeit des in den angrenzenden fotografischen Schichten erzeugten fotografischen Bildes.The most important component in the front coating between the base paper and light-sensitive layers is the light-reflecting white pigment in addition to the hydrophobic synthetic resin binder. This white pigment is not only decisive for the visual impression of a photographic image, but also for the imaging quality and the durability of the photographic image produced in the adjacent photographic layers.
US-A-3 833 380 beschreibt als Weißpigment in einer Polyäthylenschicht ein Rutil-Titandioxid, weil die an sich bekannte UV-Licht-Absorption des Rutils sich als vorteilhaft für die Haltbarkeit farbfotografischer Bilder erwies.US-A-3 833 380 describes a rutile titanium dioxide as white pigment in a polyethylene layer because the UV light absorption of the rutile, which is known per se, has proven to be advantageous for the durability of color photographic images.
DE-A-2 529 989 schlägt die Verwendung eines speziellen, mit Aluminiumoxidhydrat oberflächenbehandelten Anatas-Titandioxids vor, weil der Weißgrad höher ist als bei dem verbreiteten Rutil-Titandioxid gemäß US-A-3 833 380. Und in US-A-4185 480 wird die kombinierte Verwendung von Rutil-Titandioxid mit Anatas-Titandioxid vorgeschlagen, weil eine solche Mischung in vorteilhafter Weise die dem Rutil eigene Deckkraft, Lichtbeständigkeit und Abbildungsschärfe mit der dem Anatas eigenen höheren Weiße und besseren Verträglichkeit mit optischem Aufheller kombiniert.DE-A-2 529 989 proposes the use of a special anatase titanium dioxide surface-treated with alumina hydrate because the whiteness is higher than that of the common rutile titanium dioxide according to US Pat. No. 3,833,380. And in US Pat. No. 4,185,480 the combined use of rutile titanium dioxide with anatase titanium dioxide is proposed because such a mixture advantageously combines the opacity, lightfastness and image sharpness inherent in the rutile with the higher whiteness inherent in the anatase and better compatibility with optical brighteners.
Gegen manche Pigmente entwickelte sich ein Vorurteil, weil die beschriebenen Pigment-Überzugsmischungen nicht zu einem funktionsfähigen Produkt nachgearbeitet werden können. DE-A-2 654 220 schlägt z. B. die Verwendung von 5-40% Calciumcarbonat als Weißpigment vor, das zu einer Produktionsverbilligung führt, aufgrund seiner geringen Teilchendurchmesser von unter 0,4 f.lm die Oberflächeneigenschaften verbessern und eine besondere, die Haftung fotografischer Schichten vermittelnde Oberflächenbehandlung überflüssig machen soll.A prejudice against some pigments developed because the pigment coating mixtures described cannot be reworked into a functional product. DE-A-2 654 220 proposes e.g. B. the use of 5-40% calcium carbonate as white pigment, which leads to a reduction in production, due to its small particle diameter of less than 0.4 f.lm improve the surface properties and should make a special, the adhesion of photographic layers surface treatment superfluous.
Es ist ferner bekannt, den pigmentierten Kunstharzüberzug durch Zusatz von Farbpigmenten zu nuancieren. Durch solche Zusätze kann nicht nur ein gelbliches Aussehen des Überzuges kompensiert werden, was z. B. bei Verwendung von TiOz-Rutil wünschenswert ist, sondern es wird auch der Weißeindruck der Oberfläche dem jeweiligen Geschmack angepaßt. Schließlich können Zusätze von kleinen Mengen farbiger Pigmente auch dazu dienen, spezifische Farbfehler von fotografischen Schichten zu kompensieren.It is also known to nuance the pigmented synthetic resin coating by adding color pigments. Such additives can not only compensate for a yellowish appearance of the coating, which z. B. when using TiO z rutile is desirable, but it is also the white impression of the surface adapted to the particular taste. Finally, additions of small amounts of colored pigments can also serve to compensate for specific color errors in photographic layers.
Nach der DE-A-2 734 090 werden Rot- oder Violettpigmente gegebenenfalls gemeinsam mit Blaupigment in das Titandioxid enthaltende Polyolefin eingemischt. Das Titandioxid kann auch durch andere Weißpigmente ersetzt sein oder mit anderen Weißpigmenten kombiniert sein. Genaue Hinweise, wie das geschehen soll, sind dieser Offenlegungsschrift nicht entnehmbar.According to DE-A-2 734 090, red or violet pigments are optionally mixed together with blue pigment into the polyolefin containing titanium dioxide. The titanium dioxide can also be replaced by other white pigments or combined with other white pigments. Precise information on how this is to be done cannot be found in this published specification.
Auch der Zusatz sogenannter optischer Aufheller z. B. 2,5-Di-(5-tert.butyl-benzoxazolyl-2')-thiophen zur pigmentierten Bildträgerschicht ist seit langem bekannt.The addition of so-called optical brighteners such. B. 2,5-di- (5-tert.butyl-benzoxazolyl-2 ') thiophene for pigmented image carrier layer has long been known.
Die mittels Extrusionsbeschichtung aufgebrachte pigmentierte und gegebenenfalls nuancierte und/ oder aufgehellte weiße Vorderseitenschicht wird nach ihrer Verfestigung üblicherweise oberflächenbehandelt, um zu erreichen, daß darauf angeordnete fotografische Schichten trotz des hydrophoben Charakters des Kunstharzes gut haften. Vorzugsweise wird die in DE-A-1 447 611 beschriebene Coronabehandlung der hydrophoben Oberfläche angewandt.The pigmented and optionally nuanced and / or lightened white front layer applied by means of extrusion coating is usually surface-treated after it has solidified in order to ensure that photographic layers arranged thereon adhere well despite the hydrophobic nature of the synthetic resin. The corona treatment of the hydrophobic surface described in DE-A-1 447 611 is preferably used.
Nachteilig an den gemäß dem beschriebenen Stand der Technik zusammengesetzten pigmentierten Vorderseitenschichten ist zunächst, daß alle beschriebenen Weißpigmente mit Ausnahme des in der DE-A-2 654 220 benutzten Calciumcarbonates den Abbau des polyolefinischen Kunstharzbinders fördern. Während einer Extrusionsbeschichtung mittels Breitschlitzdüsen bewirken Abbauprodukte bereits nach wenigen Tagen bis maximal 2 Wochen starke Korrosionserscheinungen an den Düsenlippen. Deshalb ist es erforderlich, diese in kurzen Abständen nachzuschleifen, da andernfalls das Profil des aus der Schmelze aufgebrachten Überzuges ungleichmäßig wird und im Extremfall eine Verunreinigung der Oberfläche eintritt.A disadvantage of the pigmented front layers composed according to the prior art described is first of all that all the white pigments described, with the exception of the calcium carbonate used in DE-A-2 654 220, promote the degradation of the polyolefinic synthetic resin binder. During extrusion coating using slot dies, degradation products cause severe corrosion on the die lips after just a few days to a maximum of 2 weeks. It is therefore necessary to regrind them at short intervals, otherwise the profile of the coating applied from the melt will become uneven and, in extreme cases, the surface will become contaminated.
Eine andere Folge des ungünstigen Einflusses der verwendeten Weißpigmente ist, daß die Zerstö rung des Binders, z. B. Polyäthylen, auch nach Verarbeitung zu fotografischen Bildern fortschreitet.Another consequence of the unfavorable influence of the white pigments used is that the destruction of the binder, for. B. polyethylene, even after processing to photographic images.
Ein besonders gravierender Nachteil zeigt sich, wenn zusammen mit dem Weißpigment kleine Mengen farbiger Pigmente oder optischer Aufheller verarbeitet werden. Dann wird im extrudierten Film erkennbar, daß insbesondere bei Verwendung eines Titandioxids als Weißpigment bislang nicht erklärbare Inhomogenitäten in der Pigmentverteilung auftreten, die in Laufrichtung als Streifen unterschiedlicher Farbintensität und Dicke sichtbar sind. Es ist denkbar, daß aufgrund einer Oberflächenreaktion des Pigments mit dem Binder irreversible Agglomeriationen entstanden sind, es können aber auch durch den z. B. vom Ti02 ausgehenden Polymerabbau reaktive Knäuel entstanden sein, die zu sogenannten »Gelkörpern« führen. Entscheidend ist, daß im beschichteten Material eine unerwünschte Längsstreifigkeit sichtbar ist, der eine ungleichmäßige Pigmentverteilung zugrundeliegt, die bislang nicht sicher vermieden werden kann.A particularly serious disadvantage arises when small amounts of colored pigments or optical brighteners are processed together with the white pigment. Then it can be seen in the extruded film that, in particular when using a titanium dioxide as white pigment, previously inexplicable inhomogeneities occur in the pigment distribution, which are visible in the direction of travel as strips of different color intensity and thickness. It is conceivable that irreversible agglomerations have arisen due to a surface reaction of the pigment with the binder, but it can also be caused by the z. B. from the Ti0 2 starting polymer degradation reactive balls have arisen, which lead to so-called "gel bodies". It is crucial that an undesirable longitudinal streak is visible in the coated material, which is based on an uneven pigment distribution, which up to now could not be avoided with certainty.
Die hier beschriebenen Nachteile treten grundsätzlich bei allen in der Literatur beschriebenen Weißpigmenten auf (Ti02, Sbz03, Zr02, TiP207) mit Ausnahme von Calciumcarbonat. Calciumcarbonat ist jedoch wegen seines niedrigen Brechungsindex nicht als Pigment in fotografischen Trägern geeignet. Eine Folge des niedrigen Brechungsindex ist die im Vergleich zu Ti02 enthaltenden Trägern deutlich schlechtere Bildschärfe.The disadvantages described here basically occur with all white pigments described in the literature (Ti0 2 , Sb z 0 3 , Zr0 2 , TiP 2 0 7 ) with the exception of calcium carbonate. However, calcium carbonate is not suitable as a pigment in photographic supports because of its low refractive index. One consequence of the low refractive index is that the image sharpness is significantly poorer than that of carriers containing Ti0 2 .
Aufgabe der Erfindung ist es daher, einen wasserfesten weißen fotografischen Papierträger zu schaffen, der die Deckkraft und Weiße eines mit Titandioxid in Polyolefin beschichteten Materials hat, aber die Nachteile dieses Mischungssystems vermeidet. Insbesondere ist es Aufgabe der Erfindung, ein Verfahren zur Beschichtung vorzuschlagen, durch das Korrosion an den Düsenlippen der Breitschlitzdüse völlig vermieden und auch bei Verwendung beliebiger Zusätze von Nuancierfarbpigmenten eine streifenfreie homogene Beschichtung mit Titandioxid enthaltenden Polyolefinmischungen ermöglicht wird.The object of the invention is therefore to provide a waterproof white photographic paper support which has the opacity and whiteness of a material coated with titanium dioxide in polyolefin, but avoids the disadvantages of this mixing system. In particular, it is an object of the invention to propose a method for coating by which corrosion on the nozzle lips of the slot die is completely avoided and a streak-free homogeneous coating with titanium dioxide-containing polyolefin mixtures is made possible even with the use of any additives of shade pigments.
Diese Aufgabe wird bei einem Material der eingangs beschriebenen Art dadurch gelöst, daß die Polyolefinschicht zusätzlich 0,1-5 Gew--% eines Erdalkalimetallcarbonats und/oder 0,2-10 Gew.-% eines Erdalkalioxids enthält.This object is achieved in the case of a material of the type described at the outset in that the polyolefin layer additionally contains 0.1-5% by weight of an alkaline earth metal carbonate and / or 0.2-10% by weight of an alkaline earth metal oxide.
Bevorzugt sind Oxide und Carbonate des Calciums oder Magnesiums, aber auch die entsprechenden Verbindungen von Strontium und Barium eignen sich als erfindungsgemäße Zusätze zu Titandioxid enthaltenden Polyolefinüberzugsmassen für die Extrusionsbeschichtung von fotografischen Papieren.Oxides and carbonates of calcium or magnesium are preferred, but the corresponding compounds of strontium and barium are also suitable as additives according to the invention for polyolefin coating compositions containing titanium dioxide for the extrusion coating of photographic papers.
Die mit einer erfindungsgemäßen pigmentierten und stabilisierten Polyolefin-Mischung zu beschichtende Papierunterlage kann ein beliebiges fotografisches Basispapier sein, das entweder unter Verwendung von Alkylketendimer neutral geleimt ist oder eine bekannte saure Leimung auf der Basis von gefällten Harzseifen, Fettsäureseifen oder Fettsäureanhydriden hat. Vorzugsweise tragen die Basispapiere außerdem eine abdichtende und/oder Haftung vermittelnde Oberflächenleimung aus wasserlöslichen oder in Wasser dispergierbaren Substanzen. Der Oberflächenstrich kann gemäß DE-B-1 422 865 oder DE-A-2 326 759 antistatisch wirksame Substanzen sowie gegebenenfalls Pigmente und/oder hydrophobierende Zusätze und/oder färbende Zusätze enthalten. Das Basispapier kann ausschließlich aus Zellstoffasern oder aus Mischungen von Zellstoffasern mit synthetischen Fasern hergestellt sein. Es kann ein Flächengewicht von 60-300 g/mz (vorzugsweise 70-200 g/m2) haben.The paper base to be coated with a pigmented and stabilized polyolefin mixture according to the invention can be any photographic base paper which is either neutral sized using alkyl ketene dimer or has a known acidic size based on precipitated resin soaps, fatty acid soaps or fatty acid anhydrides. The base papers preferably also carry a sealing and / or adhesion-imparting surface sizing made from water-soluble or water-dispersible substances. According to DE-B-1 422 865 or DE-A-2 326 759, the surface coating can contain antistatically active substances and, if appropriate, pigments and / or hydrophobizing additives and / or coloring additives. The base paper can be made exclusively from cellulose fibers or from mixtures of cellulose fibers with synthetic fibers. It can have a basis weight of 60-300 g / m z (preferably 70-200 g / m 2).
Die Pigment enthaltende Polyolefinbeschichtungsmasse kann auf einer oder beiden Papierseiten aufgezogen sein. Sie besteht im wesentlichen aus einem Polyolefin, einem Titandioxid sowie dem erfindungsgemäßen Zusatz eines Erdalkalimetallcarbonats oder -oxids. Sie kann gegebenenfalls optischen Aufheller und/oder Nuancierlarbstoffe und/oder Antioxidantien und/oder Gleitmittel enthalten und wird mittels Extrusionsbeschichtung bei üblichen Temperaturen von 280 bis 330° C aufgezogen. Das Polyolefin ist vorzugsweise Polyäthylen. Es kann sowohl Polyäthylen mit hoher Dichte als auch solches mit niedriger Dichte verwendet werden. Das Polyolefinharz kann aber auch ein Äthylencopolymer oder Polypropylen sein.The pigment-containing polyolefin coating composition can be applied to one or both sides of the paper. It consists essentially of a polyolefin, a titanium dioxide and the addition of an alkaline earth metal carbonate or oxide according to the invention. It can optionally contain optical brighteners and / or shading dyes and / or antioxidants and / or lubricants and is applied by means of extrusion coating at conventional temperatures of 280 to 330 ° C. The polyolefin is preferably polyethylene. Both high density and low density polyethylene can be used. The polyolefin resin can also be an ethylene copolymer or polypropylene.
Die Erfindung wird anhand der nachfolgenden Beispiele näher beschrieben.The invention is described in more detail with reference to the following examples.
Ein ca. 130 g/m2 schweres fotografisches Basispapier wurde mittels Extrusionsbeschichtung vorderseitig mit ca. 30 g/m2 einer pigmentierten Kunstharzmischung überzogen. Die Zusammensetzung der Mischung war
Die Rückseite wurde mit ca. 30 g/m2 einer Mischung aus
Ein ca. 130 g/mz schweres fotografisches Basispapier wurde vorderseitig mit ca. 30 g/mz einer pigmentierten Kunstharzmischung überzogen. Die Zusammensetzung der Mischung war
Die Rückseite wurde wie im Beispiel 1 überzügen.The back was covered as in Example 1.
Ein ca. 130 g/m2 schweres fotografisches Basispapier wurde wie im Beispiel 2 beidseitig überzogen mit dem Unterschied, daß der Vorderseitenüberzug 0,5 Gew.-% Strontiumcarbonat anstelle von Magnesiumcarbonat enthielt.A photographic base paper weighing approximately 130 g / m 2 was coated on both sides as in Example 2, with the difference that the front coating contained 0.5% by weight of strontium carbonate instead of magnesium carbonate.
Ein ca. 130 g/m2 schweres fotografisches Basispapier wurde wie im Beispiel 2 beidseitig überzogen mit dem Unterschied, daß der Vorderseitenüberzug 0,5 Gew.-% Calciumoxid anstelle von Magnesiumcarbonat enthielt.A photographic base paper weighing approximately 130 g / m 2 was coated on both sides as in Example 2, with the difference that the front coating contained 0.5% by weight of calcium oxide instead of magnesium carbonate.
Ein ca. 100 g/m2 schweres fotografisches Basispapier wurde mittels Extrusionsbeschichtung vorderseitig mit ca. 20 g/m2 einer Kunstharzmischung überzogen. Die Zusammensetzung der Mischung war
Die Rückseite wurde mit ca. 20 g/m2 einer gleichen Polyäthylenmischung wie im Beispiel 1 überzogen.The back was coated with about 20 g / m 2 of the same polyethylene mixture as in Example 1.
Ein ca. 70 g/m2 schweres fotografisches Basispapier wurde mittels Extrusionsbeschichtung vorderseitig mit ca. 15 g/m2 einer Kunstharzmischung überzogen. Die Zusammensetzung der Mischung war:
Die Rückseite wurde mit ca. 15 g/m2 einer gleichen Polyäthylenmischung wie im Beispiel 1 überzogen.The back was coated with about 15 g / m 2 of the same polyethylene mixture as in Example 1.
Als Vergleiche zu den in den Beispielen 1 bis 6 beschriebenen kunstharzbeschichteten fotografischen Papierträgern wurden als Beispiele 7 bis 18 entsprechende beschichtete Papierträger hergestellt, die sich von den erfindungsgemäßen Beispielen nur dadurch unterschieden, daß die vorderseitige pigmentierte Überzugsmischung frei von dem in den Beispielen 1 bis 6 enthaltenen Erdalkalimetalloxid oder Erdalkalimetallcarbonat war.As comparisons to the resin-coated photographic paper supports described in Examples 1 to 6, corresponding coated paper supports were produced as Examples 7 to 18, which differed from the examples according to the invention only in that the pigmented coating mixture on the front was free from that contained in Examples 1 to 6 Alkaline earth metal oxide or alkaline earth metal carbonate.
Die beschichteten Trägermaterialien wurden sowohl hinsichtlich ihres unterschiedlichen Laufverhaltens bei der Extrusionsbeschichtung und hinsichtlich der Homogenität der Einfärbung der Vorderseitenschicht miteinander verglichen als auch nach üblicher Coronabehandlung der Oberfläche mit einer lichtempfindlichen Silberhalogenidschicht überzogen und zu fotografischen Bildern verarbeitet. Die fotografischen Bilder wurden bezüglich Bildschärfe miteinander verglichen.The coated carrier materials were compared both with regard to their different running behavior in the extrusion coating and with regard to the homogeneity of the coloring of the front layer, and after a conventional corona treatment of the surface they were coated with a light-sensitive silver halide layer and processed into photographic images. The photographic images were compared for sharpness.
In Tabelle 2 sind die wesentlichen Ergebnisse der Prüfungen zusammengestellt. Daraus ergibt sich eindeutig die überlegene Qualität der erfindungsgemäß unter Verwendung von Mischungen aus Titandioxid mit Erdalkalioxiden oder Erdalkalicarbonaten hergestellten beschichteten fotografischen Trägerpapiere.
Zur weiteren Erläuterung sind in der beigefügten Zeichnung mit Fig. 1 bis 3 weiße fotografische Trägermaterialien der Erfindung in verschiedener Ausgestaltung dargestellt. Das Bezugszeichen 1 bezeichnet das Papier, das Bezugszeichen 2 die aus einem Polyolefin gemäß der Erfindung bestehende Beschichtung, die gemäß den Beispielen 1 bis 6 ausgestaltet ist. Das Bezugszeichen 3 ist eine haftvermittelnde Schicht, gegebenenfalls mit Zusätzen wie einem Aufheller, das Bezugszeichen 4 bezeichnet die lichtempfindliche Schicht oder Schichten, das Bezugszeichen 5 die Rückseitenbeschichtung ebenfalls aus einem Polyolefin, das transparent oder pigmentiert sein kann, beispielsweise mit Ruß. Das Bezugszeichen 6 ist ein Rückseitenstrich, um das fotografische Papier beschreibbar zu machen und/oder antistatisch auszurüsten. In Fig. 3 ist zwischen der Polyolefinschicht und dem Papier noch ein Vorstrich 7 vorgesehen, der direkt auf das Papier aufgebracht ist, um diesem zusätzliche Glättung zu geben bzw. um als Haftvermittler zu dienen. Das Bezugszeichen 8 ist eine Rückseitenbeschichtung, die hier als Anticurlschicht dient, also ein Krümmen des Papiers verhindern soll.For further explanation, the accompanying drawing with FIGS. 1 to 3 shows white photographic support materials of the invention in various configurations. The
Claims (11)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT81108099T ATE11835T1 (en) | 1980-11-21 | 1981-10-09 | WHITE PHOTOGRAPHIC PAPER SUPPORT AND PROCESS FOR ITS MANUFACTURE. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3043864 | 1980-11-21 | ||
| DE19803043864 DE3043864A1 (en) | 1980-11-21 | 1980-11-21 | WHITE PHOTOGRAPHIC PAPER CARRIER AND METHOD FOR THE PRODUCTION THEREOF |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0052735A1 EP0052735A1 (en) | 1982-06-02 |
| EP0052735B1 true EP0052735B1 (en) | 1985-02-13 |
Family
ID=6117244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP81108099A Expired EP0052735B1 (en) | 1980-11-21 | 1981-10-09 | White photographic paper support and method of producing the same |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4396671A (en) |
| EP (1) | EP0052735B1 (en) |
| JP (1) | JPS57116339A (en) |
| AT (1) | ATE11835T1 (en) |
| DE (1) | DE3043864A1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3328463A1 (en) * | 1983-08-06 | 1985-02-21 | Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück | PHOTOGRAPHIC PAPER CARRIER |
| US4710186A (en) * | 1984-07-20 | 1987-12-01 | Personal Products Company | Clean and dry appearance facing |
| DE3435639A1 (en) * | 1984-09-28 | 1986-04-10 | Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück | PHOTOGRAPHIC CARRIER MATERIAL FOR BLACK / WHITE AND COLOR PHOTOGRAPHY |
| US4794071A (en) * | 1987-03-23 | 1988-12-27 | Eastman Kodak Company | Optically brightened photographic silver halide element with a polyolefin paper coated support |
| US4859539A (en) * | 1987-03-23 | 1989-08-22 | Eastman Kodak Company | Optically brightened polyolefin coated paper support |
| GB2217866B (en) * | 1988-04-15 | 1992-02-12 | Oji Paper Co | Thermal transfer image-receiving sheet |
| US5178936A (en) * | 1989-05-23 | 1993-01-12 | Oji Paper Co., Ltd. | Support sheet for photographic printing sheet |
| US5058531A (en) * | 1989-06-03 | 1991-10-22 | Akins Edward A | Feeder for animals |
| US5374508A (en) * | 1990-12-21 | 1994-12-20 | New Oji Paper Co., Ltd. | Support sheet for photographic printing sheet |
| EP0492887B1 (en) * | 1990-12-21 | 1997-08-27 | Oji Paper Co., Ltd. | Support sheet for photographic printing sheet |
| US5470652A (en) * | 1991-10-03 | 1995-11-28 | Oji Paper Co., Ltd | Support sheet for photographic printing paper and process for producing the sheet |
| JPH05269941A (en) * | 1992-01-27 | 1993-10-19 | Mitsubishi Paper Mills Ltd | Resin coated paper |
| US5262286A (en) * | 1992-07-31 | 1993-11-16 | Eastman Kodak Company | Reduction of yellow stain in photographic prints |
| GB2280191A (en) * | 1993-06-22 | 1995-01-25 | Ici Plc | Paint containing white opacifier |
| GB2279961A (en) * | 1993-06-22 | 1995-01-18 | Ici Plc | Paint containing white opacifier |
| US9857706B2 (en) | 2011-01-31 | 2018-01-02 | Hewlett-Packard Development Company, L.P. | Electrophotographic recording media |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1019664A (en) | 1961-09-18 | 1900-01-01 | ||
| NL290497A (en) | 1962-03-21 | |||
| GB971058A (en) | 1962-05-02 | 1900-01-01 | ||
| JPS4927046B1 (en) * | 1965-04-12 | 1974-07-15 | ||
| JPS594447B2 (en) * | 1972-12-28 | 1984-01-30 | 日石三菱株式会社 | synthetic paper |
| DE2326759C2 (en) | 1973-05-25 | 1984-03-08 | Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück | Waterproof photographic paper coated with thermoplastic resins |
| SE7414266L (en) * | 1973-11-15 | 1975-05-16 | Rhone Progil | |
| JPS516531A (en) | 1974-07-04 | 1976-01-20 | Fuji Photo Film Co Ltd | INGASHOSHI JITAI |
| JPS53117A (en) * | 1976-06-24 | 1978-01-05 | Mitsubishi Paper Mills Ltd | Photographic paper support |
| JPS5319021A (en) * | 1976-08-04 | 1978-02-21 | Fuji Photo Film Co Ltd | Substrate for photography |
| DE2654220A1 (en) * | 1976-11-30 | 1978-06-01 | Solvay Werke Gmbh | Coating photographic paper with filled polyolefin - using low pressure polyethylene contg. fine calcium carbonate by extrusion and calendering |
| JPS555830A (en) * | 1978-06-28 | 1980-01-17 | Fuji Photo Film Co Ltd | Ink jet type recording sheet |
| US4265960A (en) * | 1978-12-26 | 1981-05-05 | Mobil Oil Corporation | Films produced from LDPE encapsulated CaCO3 |
| JPS5942296B2 (en) * | 1980-08-01 | 1984-10-13 | 三菱製紙株式会社 | Manufacturing method for photographic supports |
-
1980
- 1980-11-21 DE DE19803043864 patent/DE3043864A1/en active Granted
-
1981
- 1981-06-25 US US06/277,113 patent/US4396671A/en not_active Expired - Fee Related
- 1981-10-09 EP EP81108099A patent/EP0052735B1/en not_active Expired
- 1981-10-09 AT AT81108099T patent/ATE11835T1/en not_active IP Right Cessation
- 1981-11-20 JP JP56185601A patent/JPS57116339A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| ATE11835T1 (en) | 1985-02-15 |
| DE3043864A1 (en) | 1982-07-08 |
| JPS57116339A (en) | 1982-07-20 |
| EP0052735A1 (en) | 1982-06-02 |
| DE3043864C2 (en) | 1987-09-10 |
| US4396671A (en) | 1983-08-02 |
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