EP0225446B1 - Support photographique en papier résistant à l'eau - Google Patents

Support photographique en papier résistant à l'eau Download PDF

Info

Publication number
EP0225446B1
EP0225446B1 EP86113855A EP86113855A EP0225446B1 EP 0225446 B1 EP0225446 B1 EP 0225446B1 EP 86113855 A EP86113855 A EP 86113855A EP 86113855 A EP86113855 A EP 86113855A EP 0225446 B1 EP0225446 B1 EP 0225446B1
Authority
EP
European Patent Office
Prior art keywords
photographic paper
carrier according
carboxyl
paper carrier
modified polyvinyl
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
Application number
EP86113855A
Other languages
German (de)
English (en)
Other versions
EP0225446A1 (fr
Inventor
Alois-Bernhard Dr. Dipl.-Chem. Kerkhoff
Dietmar Dr. Dipl.-Chem. Bunke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Felix Schoeller Jr Foto und Spezialpapiere GmbH
Felex Schoeller Jr and GmbH and Co KG
Original Assignee
Felix Schoeller Jr Foto und Spezialpapiere GmbH
Felex Schoeller Jr and GmbH and Co KG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Felix Schoeller Jr Foto und Spezialpapiere GmbH, Felex Schoeller Jr and GmbH and Co KG filed Critical Felix Schoeller Jr Foto und Spezialpapiere GmbH
Priority to AT86113855T priority Critical patent/ATE46221T1/de
Publication of EP0225446A1 publication Critical patent/EP0225446A1/fr
Application granted granted Critical
Publication of EP0225446B1 publication Critical patent/EP0225446B1/fr
Expired legal-status Critical Current

Links

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
    • G03C1/775—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
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y10T428/277—Cellulosic substrate
    • 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
    • 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]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31993—Of paper
    • Y10T428/31996—Next to layer of metal salt [e.g., plasterboard, etc.]

Definitions

  • the invention relates to a paper support for photographic layers provided on both sides with a polyolefin coating.
  • the paper core of the photographic support according to the invention is also largely protected against the action of the photographic treatment solutions at the edges which are caused by the cutting and is essentially free of dirt on the edges from the treatment solutions.
  • baryta papers the surfaces of which were provided with so-called baryta layers, which consisted essentially of barium sulfate and gelatin, were previously used as carrier materials for the inclusion of photosensitive layers, in particular layers for black / white and color silver salt photography.
  • waterproof photographic supports In order to be able to meet the requirements placed on the photographic support materials by the new automatic rapid development processes, waterproof photographic supports have been described which have been coated on both surfaces with a hydrophobic polyolefin.
  • the upper polyolefin coating layer of the waterproof photographic support to which a photographic emulsion layer is to be applied usually contains a white pigment to increase the sharpness of the photographic image.
  • the paper substrates coated on both sides with polyolefin are basically protected in both areas against the effects of conventional photographic treatment liquids. This protection is only interrupted at the edges of the coated papers, and the liquids have access to the paper core there. Due to the natural absorbency of paper, they penetrate the edges of the paper core and cannot be completely removed even in subsequent washing steps. Since the liquids often contain substances that change color dark when exposed to air or exposure to light, penetrated photographic treatment liquids appear as darker discolored edges after a short time, which leads to a reduction in the value of the photographic material.
  • the base paper is usually provided with a strong hydrophobizing inner sizing by adding sizing agents to the pulp suspension during the production of the paper.
  • the object of the invention is therefore to provide a waterproof photographic support which is free from the disadvantages described, i.e. which, even when used in an automatic rapid development process, has no dirt on the edges and whose paper core has the internal strength required for use in photographic supports and secure adhesion of the polyolefin coating.
  • the photographic support according to the invention has a basic structure consisting of a base paper and a polyolefin coating layer which is provided on both surfaces and which contains the light-reflecting white pigment (especially in the front coating) and, if appropriate, color pigments, optical brighteners and / or other additives such as antistatic compounds, dispersing aids for the white pigment and may contain antioxidants.
  • the base paper is produced in a known manner using a paper machine.
  • the paper pulp suspension is sized using alkyl ketene dimers or fatty acids or fatty acid salts, epoxidized fatty acid amides or anhydrides of fatty acids and mixtures thereof.
  • the paper pulp suspension can also contain synthetic fibers, mineral or organic fillers, white pigment, dye or color pigment, optical brighteners, antioxidants and / or other additives customary in the production of photographic supports, e.g. setting resins.
  • Base papers of any basis weight and of any density can be used.
  • the base paper is impregnated (surface-sized) with a solution of carboxyl-modified polyvinyl alcohol.
  • a carboxyl-modified polyvinyl alcohol is understood to mean, for example, a vinyl alcohol croton or iso crotonic acid polymer or a vinyl alcohol acrylic or methacrylic acid copolymer.
  • the vinyl alcohol-crotonic acid copolymer is preferred.
  • the carboxyl-modified polyvinyl alcohols have a viscosity of 20 to 50 mPa s in 4% solution at room temperature.
  • the average molecular weight is 5,000 to 20,000, preferably 7,000 to 10,000.
  • the carboxyl-modified polyvinyl alcohols used according to the invention are used as an aqueous solution using the known and customary ones Application procedure applied.
  • the application amount is 0 to 10 g / m 2, preferably 1 to 4.5 5 g / m2. If the application quantity is less than 0.5 g / m 2 , sufficient impregnation of the paper core (base paper) is not achieved and the penetration of the photographic treatment solutions into the edges and the contamination of the edges by the photographic treatment solutions are not avoided to the desired extent.
  • the improvement in properties is not linearly related to the number of carboxyl groups, so that the maximum does not occur with the carboxyl-modified polyvinyl alcohol with the largest carboxyl group content. Rather, the optimum is only achieved if carboxyl-modified polyvinyl alcohols are used which contain a carboxyl group content of 1 to 7 mol%, preferably 2.5 to 3.5 mol%.
  • carboxyl-modified polyvinyl alcohols which contain a carboxyl group content of 1 to 7 mol%, preferably 2.5 to 3.5 mol%.
  • the effect according to the invention is already achieved if a sized paper produced in a known manner is impregnated with a solution of the polyvinyl alcohol containing carboxyl groups. According to a preferred embodiment of the invention, however, the effect according to the invention is enhanced if polyvalent cations are additionally introduced into the paper.
  • These compounds can be selected from the group of alkaline earth metal compounds, for example calcium or magnesium chloride, from the group of aluminum salts, for example aluminum sulfate or aluminum chloride, and from the compounds of the transition metals.
  • the polyvalent cations are preferably added to the aqueous coating solution. However, they can also be added to the cellulose suspension or incorporated into the base paper before the polyvinyl alcohol solution according to the invention is used. Or they can be applied in the form of an aftertreatment (e.g.
  • the polyvalent cation compounds are in a weight ratio of 1/10 to 5/1 to the carboxylated polyvinyl alcohol. If the weight ratio falls below the value of 1/10, the enhancement of the described effect is not achieved. An increase in the weight ratio to values above 5/1 brings no further improvement in the effect according to the invention.
  • aqueous coating solution can also contain optical brighteners, defoamers, pigments, water repellents or crosslinking aids, such as, for example, dimethylolurea or trimethylolmelamine.
  • the paper support is treated with an aqueous coating mixture of the following composition:
  • the application amount is 2 g / m 2.
  • Crotonic acid-modified polyvinyl alcohols with the following carboxyl group proportions are used:
  • the treated paper is dried and extrusion coated with polyethylene in the usual way.
  • the Paper is treated with the coating mixture used in Example 1.
  • the order quantity is 3 g / m 2 .
  • Crotonic acid-modified polyvinyl alcohols with the following carboxyl groups are used.
  • the treated paper is dried and extrusion coated in a conventional manner with polyethylene.
  • An approximately 140 g / m 2 heavy paper sized with 0.3% by weight alkyl ketene dimer, 1.6% by weight fatty acid soap and 0.5% by weight aluminum ions is treated with an aqueous coating mixture, which contains a crotonic acid-modified polyvinyl alcohol with a degree of saponification of 98.5% and a carboxyl group content of 3.1 mol% in the amount of 40 g / l.
  • compounds of the following polyvalent cations are added:
  • the application quantity is 1.5 g / m 2 .
  • the treated paper is dried and extrusion coated with polyethylene in the usual way.
  • the order quantity is 4.5 g / m 2 .
  • the treated paper is dried and coated with a polyethylene coating mixture of the following composition:
  • the paper is treated on both sides in a second size press with the following polyvinyl alcohol solution.
  • the treated paper is dried and extrusion coated with polyethylene in the usual way.
  • both sides are successively sprayed with the following saline solution via a nozzle system:
  • the application quantity is 1.5 g / m 2 in the size press and 1.0_g / M 2 when spraying.
  • the treated paper is dried and extrusion coated with polyethylene in the usual way. In this case, the test of the carrier material was only carried out after 1 week of storage.
  • a paper produced according to Example 1 is treated with an aqueous coating mixture of the following composition:
  • the application amount is 3 g / m 2.
  • the treated paper is dried and extrusion-coated with polyethylene in the usual way.
  • a paper sheet produced according to Example 2 of DOS 32 41 599 is treated with the coating mixture described there (the application amount is 3 g / m 2 ), then dried and extrusion-coated with polyethylene in the usual way.
  • a paper sheet produced according to Example 3 is treated with the coating mixture described in Comparative Example V1.
  • the order quantity is 3 g / m 2 .
  • the treated paper is dried and coated with polyethylene in the usual way.
  • a paper of 140 g / m 2 produced according to Example 3 is treated (surface-sized) with the following coating mixture:
  • the treated paper is dried and extrusion coated with polyethylene in the usual way.
  • a 175 g / m 2 paper produced according to Example 1 is treated with the following coating mixture:
  • the treated paper is dried and extrusion coated with polyethylene in the usual way.
  • the treated papers are coated with polyethylene and then subjected to the following tests.
  • Treated paper is understood here to mean paper which has undergone the treatment of the base paper by the coating mixtures in the form of applications on both sides by dipping processes (size press), spraying, applications on both sides by means of roller application systems, slot casters or the like.
  • Test 1 Testing the impregnated base paper During the test, the developer absorption is determined by the paper (modified Cobb test). 14 x 14 cm test pieces are cut out of the paper web, precisely weighed and clamped in a cylindrical test device. 100 ml of a commercially available photographic developer are placed in the cylinder, left to act for a period of 50 seconds and then poured off. The test specimen is erased and weighed immediately. The extent of developer uptake is given in g / m 2 .
  • the test piece is subjected to a simulated photographic development process with a commercial developer containing benzyl alcohol at a temperature of about 30 ° C and for a period of 25 minutes.
  • the penetration of the photographic treatment solutions is measured on both edges of the test piece with a measuring magnifier.
  • the measured values are given as edge penetration (KE) in mm.
  • the test is carried out according to the method specified in TAPPI RC 308 with the Internal Bond Impact Tester Model B.
  • the measured values are measured in 1/1000 feet x pounds and were converted to the SI unit Nm according to the following equation.
  • Equation: ftpd.1.356 Nm
  • Test 2.3 Determination of the adhesive force between the polyethylene coating layer and the impregnated paper core
  • the test is carried out with a tensile strength measuring device from AB Lorentzen & Wettre on 15 mm wide and 18 cm long test strips.
  • the pull-off angle is 180 °
  • the pull-off speed is 70 mm / min.
  • the measured values are given in mN / 15 mm.
  • Comparative example V5 demonstrates that a degree of saponification of 88% for the polyvinyl alcohol used is not sufficient to achieve the desired effect.

Landscapes

  • 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)

Claims (15)

1. Support photographique en papier résistant à l'eau, constitué d'un papier de base, encollé par l'utilisation d'un agent d'encollage hydrophobisant et traité par un mélange de revêtement aqueux contenant un poly-(alcool vinylique) modifié par un acide carboxylique, et comprenant aussi un revêtement de polyoléfine sur les deux faces, caractérisé en ce que le poly(alcool vinylique) modifié par un acide carboxylique est un copolymère d'un acide monocar- boxylique insaturé ayant une teneur en groupes carboxyle de 1,5 à 7% en moles, de préférence de 2,5 à 3,5% en moles, la partie alcool vinylique présentant un indice de saponification supérieur ou égal à 96%.
2. Support photographique en papier résistant à l'eau selon la revendication 1, caractérisé en ce que le poly(alcool vinylique) modifié par un acide carboxylique a une masse moléculaire moyenne de 5000 à 20 0000.
3. Support photographique en papier résistant à l'eau selon les revendications 1 et 2, caractérisé en ce que le poly(alcool vinylique) modifié par un acide carboxylique est un copolymère d'acide crotonique ou isocrotonique et d'alcool vinylique.
4. Support photographique en papier résistant à l'eau selon les revendications 1 et 2, caractérisé en ce que le poly(alcool vinylique) modifié par un acide carboxylique est un copolymère d'acide acrylique ou méthacrylique et d'alcool vinylique.
5. Support photographique en papier résistant à l'eau selon les revendications 1 et 2, caractérisé en ce que les solutions aqueuses des poly(alcools vinyliques) modifiés par un acide carboxylique ont à 20°C en solution aqueuse à 4% une viscosité de 20 à 50 mPa.s.
6. Support photographique en papier résistant à l'eau selon les revendications 1 à 5, caractérisé en ce que les poly(alcools vinyliques) modifiés par un acide carboxylique sont appliquées sur le noyau de papier en une quantité de 0,5 à 10 g/m2, de préférence de 1 à 4,5 g/m2.
7. Support photographique en papier résistant à l'eau selon les revendications 1 à 6, caractérisé en ce que le mélange aqueux de revêtement contient, outre le poly(alcool vinylique) modifié par un acide carboxylique, des composés comportant des cations polyvalents.
8. Support photographique en papier résistant à l'eau selon la revendication 7, caractérisé en ce que le composé comportant des cations polyvalents est un sel de métal alcalino-terreux, de préférence le chlorure de calcium ou le chlorure de magnésium.
9. Support photographique en papier résistant à l'eau selon la revendication 7, caractérisé en ce que le composé comportant des anions polyvalents est un sel d'aluminium, de préférence le sulfate d'aluminium ou le chlorure d'aluminium.
10. Support photographique en papier résistant à l'eau selon la revendication 7, caractérisé en ce que le composé comportant des cations polyvalents est un composé des métaux de transition.
11. Support photographique en papier résistant à l'eau selon la revendication 10, caractérisé en ce que le composé des métaux de transition est un composé du zirconium, de préférence le carbonate de zirconium et d'ammonium ou l'orthosulfate de zirconium.
12. Support photographique en papier résistant à l'eau selon la revendication 10, caractérisé en ce que le composé des métaux de transition est un composé du chrome, de préférence un complexe de chrome du type Werner.
13. Support photographique en papier résistant à l'eau selon la revendication 1, caractérisé en ce que le composé comportant des cations polyvalents fait avec le poly(alcool vinylique) modifié par un acide carboxylique un rapport pondéral de 1/10 à 5/1.
14. Support photographique en papier résistant à l'eau selon les revendications 1 à 6, caractérisé en ce que le papier de base contient des composés comportant des cations polyvalents.
15. Support photographique en papier résistant à l'eau selon les revendications 1 à 6, caractérisé en ce que le poly(alcool vinylique) modifié par un acide carboxylique est, après application sur le papier, traité à l'aide de cations polyvalents.
EP86113855A 1985-12-10 1986-10-07 Support photographique en papier résistant à l'eau Expired EP0225446B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86113855T ATE46221T1 (de) 1985-12-10 1986-10-07 Wasserfester fotografischer papiertraeger.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19853543597 DE3543597A1 (de) 1985-12-10 1985-12-10 Wasserfester fotografischer papiertraeger
DE3543597 1985-12-10

Publications (2)

Publication Number Publication Date
EP0225446A1 EP0225446A1 (fr) 1987-06-16
EP0225446B1 true EP0225446B1 (fr) 1989-09-06

Family

ID=6288090

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86113855A Expired EP0225446B1 (fr) 1985-12-10 1986-10-07 Support photographique en papier résistant à l'eau

Country Status (7)

Country Link
US (1) US4731291A (fr)
EP (1) EP0225446B1 (fr)
JP (1) JPH083608B2 (fr)
AT (1) ATE46221T1 (fr)
DE (2) DE3543597A1 (fr)
ES (1) ES2010652B3 (fr)
GR (1) GR3000239T3 (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3668995D1 (de) * 1986-07-22 1990-03-15 Schoeller F Jun Gmbh Co Kg Fotografischer papiertraeger und verfahren zu seiner herstellung.
ES2042657T3 (es) * 1988-07-28 1993-12-16 Schoeller Felix Jun Papier Soporte de papel fotografico resistente al agua.
US4988559A (en) * 1988-11-15 1991-01-29 Oji Paper Co., Ltd. Support sheet for photographic printing sheet
JP2659578B2 (ja) * 1989-02-06 1997-09-30 三菱製紙株式会社 写真用支持体
US5102730A (en) * 1990-02-20 1992-04-07 Andrews Paper & Chemical Co., Inc. Erasable reproduction material
JP2793898B2 (ja) * 1990-09-25 1998-09-03 富士写真フイルム株式会社 写真印画紙用支持体
DE69223601T2 (de) * 1991-08-19 1998-06-18 Eastman Kodak Co Photografisches papier mit geringer sauerstoffdurchlässigkeit
EP0664487B1 (fr) * 1993-12-08 1998-07-29 Fuji Photo Film Co., Ltd. Matériau photosensible à base de halogénures d'argent comprenant une couche photopolymérisable et une couche de revêtement, qui contient de l'alcool polyvinylique avec des groupes acides ou un sel de ce composé
US5464691A (en) * 1994-07-22 1995-11-07 Arizona Chemical Company Laminated barrier film
JP3311874B2 (ja) * 1994-10-14 2002-08-05 富士写真フイルム株式会社 平版印刷湿し水用組成物
JP3571192B2 (ja) * 1997-09-26 2004-09-29 ユニ・チャーム株式会社 変性ポリビニルアルコールを含有する水解性の清掃用シート
MX357920B (es) * 2013-01-10 2018-07-31 Rivera Carmona Dalila Papel de arte no transparente para bocetos que impide que las tintas transminen.

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4994275A (fr) * 1973-01-12 1974-09-06
DE2515823C2 (de) * 1975-04-11 1984-06-07 Felix Schoeller jr. GmbH & Co KG, 4500 Osnabrück Verfahren zur Herstellung eines durch Mikrowellenbehandlung zu trocknenden fotografischen Trägermaterials
JPS5684954A (en) * 1979-12-12 1981-07-10 Azona Kk Filmmpaper laminate and its manufacture
JPH0234371B2 (ja) * 1981-11-10 1990-08-02 Fuji Photo Film Co Ltd Shashiningashoshijitai
JPS59185690A (ja) * 1983-04-07 1984-10-22 Jujo Paper Co Ltd インクジエツト記録用紙
JPS60217357A (ja) * 1984-04-12 1985-10-30 Mitsubishi Paper Mills Ltd 写真用ポリエチレン被覆紙

Also Published As

Publication number Publication date
EP0225446A1 (fr) 1987-06-16
DE3543597C2 (fr) 1992-03-05
JPH083608B2 (ja) 1996-01-17
JPS62138848A (ja) 1987-06-22
DE3665505D1 (en) 1989-10-12
GR3000239T3 (en) 1991-03-15
US4731291A (en) 1988-03-15
ATE46221T1 (de) 1989-09-15
DE3543597A1 (de) 1987-06-11
ES2010652B3 (es) 1989-12-01

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