EP2578416B1 - Procédé pour la décoration de la surface d'un film de polymère fluoriné - Google Patents
Procédé pour la décoration de la surface d'un film de polymère fluoriné Download PDFInfo
- Publication number
- EP2578416B1 EP2578416B1 EP20120186989 EP12186989A EP2578416B1 EP 2578416 B1 EP2578416 B1 EP 2578416B1 EP 20120186989 EP20120186989 EP 20120186989 EP 12186989 A EP12186989 A EP 12186989A EP 2578416 B1 EP2578416 B1 EP 2578416B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- film
- fluorinated polymer
- decorative pattern
- process according
- polymer
- 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.)
- Not-in-force
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1704—Decalcomanias provided with a particular decorative layer, e.g. specially adapted to allow the formation of a metallic or dyestuff layer on a substrate unsuitable for direct deposition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
- B44C1/1716—Decalcomanias provided with a particular decorative layer, e.g. specially adapted to allow the formation of a metallic or dyestuff layer on a substrate unsuitable for direct deposition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/17—Dry transfer
- B44C1/1712—Decalcomanias applied under heat and pressure, e.g. provided with a heat activable adhesive
- B44C1/172—Decalcomanias provided with a layer being specially adapted to facilitate their release from a temporary carrier
Definitions
- the present invention relates to a process for decorating the surface of a substrate consisting of a film of fluorinated polymer, in particular ETFE (ethylene tetrafluoroethylene).
- ETFE ethylene tetrafluoroethylene
- ETFE is a thermoplastic polymer that has high mechanical strength and corrosion resistance over a wide temperature range. ETFE has a melting point of 260°C, excellent chemical and dielectric properties, high resistance to chemical attack, and is fast against solar and ultraviolet radiation. Its structural formula is as follows:
- a layer of ETFE has a weight equal to only 60/70% of that of a glass plate of equal volume. Moreover, since it permits the use of more efficient application solutions, the unit weight per m 2 of a coating of ETFE may be only approx. 5% of that of a similar coating formed from glass and the associated carrying structure. Moreover, this material is self-cleaning owing to its anti-adhesive surface, flame-retardant and incombustible, as well as recyclable at the end of its useful life.
- ETFE has a wide range of service temperatures (from -200 to +150°C), low flammability, excellent electrical and mechanical properties, excellent resistance to solvents and to chemicals, extremely high resistance to external atmospheric agents, high transmission of light in the visible and UV, anti-adhesion properties, excellent tearing strength, low permeability and good resistance to radiation.
- ETFE can be processed using flat head extrusion technology, by means of which films can be produced in widths ranging from 500 to 2000 mm and thicknesses ranging from 13 to 300 ⁇ m, with tolerances on thickness not above 4%.
- the raw material in the form of granules is fed by gravity into the feed throat of an extruder, consisting of a thermostatically-controlled barrel, within which a screw of a suitable profile causes, by means of rotation, melting of the granules by friction, homogenizing the melt and increasing its pressure so as to drive it through a filter, for the purpose of separating extraneous and incompletely melted particles.
- an extruder consisting of a thermostatically-controlled barrel, within which a screw of a suitable profile causes, by means of rotation, melting of the granules by friction, homogenizing the melt and increasing its pressure so as to drive it through a filter, for the purpose of separating extraneous and incompletely melted particles.
- the melt Downstream of the filter, the melt enters a gear pump, having the purpose of generating a continuous flow free from pressure fluctuations, which allows uniform distribution of the flow of molten material inside channels of the extruder head, thus avoiding preferential paths that would involve non-uniformity of thicknesses.
- the head is characterized by a linear die head (slit for discharge of the molten material), the opening of which can be varied manually and roughly according to the thickness of film to be produced.
- the precise, fine regulation of the opening is performed during extrusion by a device that detects the film thickness continuously in real time and, as a function of the error detected relative to a predetermined set-point, sends correcting signals to a series of thermal bolts positioned corresponding to the die head, which by thermal expansion punctually alter the opening of the die head i.e. the slit for discharge of the molten polymer.
- the film of plastic material is supported on cooling rolls with gradually decreasing temperature, so that it is cooled and stabilized with respect to its dimensional characteristics.
- the films thus produced are of chemically inert material and therefore are not susceptible to chemical attack. They transmit sunlight in a percentage above 90% and are light, having a density of 1.72-1.78 kg/dm 3 .
- the characteristics of mechanical strength permit applications with ability to withstand loads and external stresses.
- ETFE offers designers, owing to its special properties, notable opportunities for developing modern solutions that combine lightness, durability, design and ecology.
- An ETFE film can also be coloured, by adding suitable pigments in the bulk (master batch) in the form of granules, which are supplied to the extruder in a suitable percentage relative to the base polymer. Moreover, the final film can retain a certain translucency, varying the colour of the light transmitted and extending the range of aesthetic and design possibilities.
- these screen-printed films are used as the external and/or internal surface of cushions inflated with air, which function as a coating element for the purpose of limiting insolation inside buildings, reflecting the luminous and solar radiation to the exterior.
- ETFE films can be joined together exclusively by heat-sealing. Consequently, the presence of deposits of aluminium on the surface greatly limits the possibility of welding two films together, in fact requiring "scraping" of the graphical patterns from the surfaces corresponding exactly to the welding lines.
- the decorations produced so far are not able to resist the action of external factors throughout the service life envisaged for the associated film. Therefore they must be "protected", in particular by using special embodiments for avoiding their dissolution.
- US 3018188 discloses a process for the decoration of the surface of a fluorinated polymer, comprising the stages of:
- the decorative pattern is achieved by a stamp that transfers predetermined regions of the foil to the surface. A 3-dimensionality of the pattern is not apparent.
- the final decorated object is not a fluorinated polymer film, but a structural part.
- the purpose of the present invention is therefore to provide a method for decorating the surface of a film of fluorinated polymer, obtaining improved results relative to those of the prior art.
- this purpose is achieved by means of a process for decorating the surface of a film of fluorinated polymer, comprising the steps of:
- the aforementioned second film is formed from a layer of extruded polymer material belonging to one of the following classes: polyesters, in particular PET, PBT, PTT, polypropylenes, polyamides, polyurethanes, polyvinyls, celluloses, lignin, or from several co-extruded layers, which may be identical or different, in particular celluloses, and the aforementioned film of fluorinated polymer is of ETFE, FEP, THV, MFA, ECTFE, PFA, PVDF or mixtures thereof, in particular of ETFE homopolymer or copolymer with one or more further, partially or fully fluorinated polymers.
- polyesters in particular PET, PBT, PTT, polypropylenes, polyamides, polyurethanes, polyvinyls, celluloses, lignin, or from several co-extruded layers, which may be identical or different, in particular celluloses
- the aforementioned film of fluorinated polymer is of ETFE
- the printing of the three-dimensional decorative pattern on one face of the second film takes place by a technique of rotogravure, flexography, screen-printing, offset or a combination thereof, which envisages the use of one or more engraved rollers.
- the aforementioned resins of the three-dimensional decorative pattern comprise at least one component selected from: cellulose acetate, cellulose acetobutyrate, cellulose nitrate, cellulose propionate, epoxides, melamine-formaldehyde, polyamides, polyamide-imides, polyacrylonitrile, polybutene-1, polybutyleneterephthalate, polycarbonate, polychlorotrifluoroethylene, polydiallylphthalate, polyethylene, chlorinated polyethylene, polyetherimide, polyetherketone, polyetheretherketone, polyethersulphones, polyethyleneterephthalate, phenolformaldehyde, polyimide, polyisobutylene, polymethacrylimide, polymethylmethacrylate, poly-4-methylpentene-1, polyoxymethylene, polyformaldehyde, polyacetal, polypropylene, polyphenyl ether, polyphenylene oxide, polyphenylene sulphide, polystyrene,
- the aforementioned resins of the three-dimensional decorative pattern comprise at least one organic pigment belonging to at least one of the classes nitroso, nitro, monoazo, diazo, stilbene, diphenylmethane, triphenylmethane, xanthene, acridine, quinoline, methine, thiazole, indamines, indophenol, azine, oxazine, thiazine, aminoketone, anthraquinone, indigoid, phthalocyanine and derivatives thereof, in particular a pigment of the class of pigments dispersed by sublichromia.
- the aforementioned film of fluorinated polymer is provided with additives for increasing the resistance of the aforementioned pigments to electromagnetic radiation.
- supply of thermal energy takes place by conduction, for example as a result of contact with a heated surface, convection and/or radiation, in such a way that the temperature is between 40 and 300°C.
- supply of thermal energy can take place in a calender or by direct contact with the heated surface of a press.
- the film of fluorinated polymer, onto the surface of which said decorative pattern has been transferred, preferably displays mechanical and chemical properties substantially corresponding to those of the film without the decorative pattern.
- the film of fluorinated polymer, onto the surface of which said decorative pattern has been transferred is welded to a further film of fluorinated polymer without removing the aforementioned decorative pattern, which is advantageously resistant to the action of rubbing with organic solvents that do not attack the fluorinated polymer per se.
- a cellulose film with a nominal thickness of 20 ⁇ m is printed with a three-dimensional decorative pattern by a rotogravure technique that envisages the use of a mixture of organic resins of the class of celluloses.
- the organic resins contain pigments of the class of those dispersed by sublichromia.
- the decorated cellulose film is then brought in contact with a film of ETFE and heated to a temperature of 220°C using a calender heated with diathermic oil. After intimate contact lasting approximately 25 seconds, the ETFE film has absorbed the pigments of the class of dispersed pigments and displays a decorated appearance, due to transfer of the decorative pattern onto its surface.
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Laminated Bodies (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Claims (12)
- Procédé pour décorer la surface d'un film de polymère fluoré, comportant les étapes suivantes :- imprimer un motif décoratif tridimensionnel sur une surface d'un deuxième film de polymère, en utilisant des résines,- mettre la surface décorée dudit deuxième film en contact avec au moins une surface dudit film de polymère fluoré, et apporter de l'énergie thermique à l'ensemble,- et détacher le deuxième film dudit film de polymère fluoré, sur la surface duquel a été transféré le motif décoratif.
- Procédé conforme à la revendication 1, pour lequel ledit deuxième film est constitué d'une couche extrudée d'un matériau polymère appartenant à l'une des classes suivantes : polyesters (en particulier PET, PBT, PTT), polypropylènes, polyamides, polyuréthanes, polyvinyliques, celluloses et lignines, ou de plusieurs couches co-extrudées, identiques ou différentes, en particulier de celluloses.
- Procédé conforme à la revendication 1 ou 2, pour lequel ledit film de polymère fluoré est un film d'ETFE, de FEP, de THV, de MFA, d'ECTFE, de PFA ou de PVDF, ou d'un mélange de ces polymères, et en particulier, un film d'homopolymère ou de copolymère ETFE et d'un ou de plusieurs autres polymère(s) partiellement ou totalement fluoré(s).
- Procédé conforme à l'une des revendications précédentes, dans lequel l'impression du motif décoratif tridimensionnel sur une surface du deuxième film de polymère est réalisée selon une technique de rotogravure, de flexographie, de sérigraphie ou d'impression offset ou une combinaison de ces techniques, où l'on a recours à un ou plusieurs cylindre(s) gravé(s).
- Procédé conforme à l'une des revendications précédentes, dans lequel les résines utilisées pour le motif décoratif tridimensionnel comprennent au moins un constituant choisi parmi les suivants : acétate de cellulose, acétobutyrate de cellulose, nitrate de cellulose, propionate de cellulose, résines époxy, résines mélamine-formaldéhyde, polyamides, poly(amide-imide), polyacrylonitrile, poly(but-1-ène), poly(butylène téréphtalate), polycarbonates, poly(chloro-trifluoroéthylène), poly(phtalate de diallyle), polyéthylène, polyéthylène chloré, poly-(éther imide), poly(éther cétone), poly(éther éther cétone), poly(éther sulfone), poly(éthylène téréphtalate), résines phénol-formaldéhyde, polyimides, polyisobutylène, polyméthacrylamide, poly(méthacrylate de méthyle), poly(4-méthyl-pent-1-ène), poly(oxyméthylène), polyformaldéhyde, polyacétals, polypropylène, poly(phényle éther), poly(phénylène oxyde), poly(phénylène sulfure), polystyrène, polysulfones, polythiophène, poly(tétrafluoroéthylène), polyuréthanes, poly(butyral de vinyle), poly(chlorure de vinyle), poly(chlorure de vinyle) chloré, poly(chlorure de vinylidène), poly(fluorure de vinylidène), poly(fluorure de vinyle), cellulose régénérée, silicones, résines urée-formaldéhyde, polyesters insaturés, poly(diméthyl-siloxane).
- Procédé conforme à l'une des revendications précédentes, dans lequel les résines utilisées pour le motif décoratif tridimensionnel comprennent au moins un pigment organique appartenant à au moins l'une des classes suivantes de colorants : nitrosés, nitrés, monoazoïques, bisazoïques, stilbéniques, du diphényl-méthane, du triphénylméthane, xanthéniques, d'acridine, quinoléines, méthiniques, thiazoles, indamines, indophénols, azines, oxazines, thiazines, amino-cétoniques, anthraquinoniques, indigoïdes, phtalocyanines, et leurs dérivés, et en particulier, un pigment de la classe des pigments dispersés pour sublichromie.
- Procédé conforme à la revendication 6, dans lequel ledit film de polymère fluoré contient des adjuvants servant à augmenter la stabilité desdits pigments aux rayonnements électromagnétiques.
- Procédé conforme à l'une des revendications précédentes, dans lequel l'énergie thermique est apportée par conduction, par exemple suite à la mise en contact avec une surface chauffée, par convection et/ou par irradiation, de manière à ce que la température soit portée à une valeur située entre 40 et 300 °C.
- Procédé conforme à la revendication 8, dans lequel l'apport d'énergie thermique est réalisé dans une calandre ou par contact direct avec la surface chauffée d'une presse.
- Procédé conforme à l'une des revendications précédentes, dans lequel le film de polymère fluoré sur la surface duquel a été transféré ledit motif décoratif possède des propriétés mécaniques et chimiques sensiblement correspondantes à celles du film dépourvu de motif décoratif.
- Procédé conforme à l'une des revendications précédentes, dans lequel le film de polymère fluoré sur la surface duquel a été transféré ledit motif décoratif est soudé à un autre film de polymère fluoré sans que ledit motif décoratif soit enlevé.
- Procédé conforme à l'une des revendications précédentes, dans lequel ledit motif décoratif du film de polymère fluoré résiste au frottement en présence de solvants organiques qui n'attaquent pas le polymère fluoré lui-même.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
IT000878A ITTO20110878A1 (it) | 2011-10-03 | 2011-10-03 | Procedimento per la decorazione della superficie di un film di polimero fluorurato |
Publications (3)
Publication Number | Publication Date |
---|---|
EP2578416A1 EP2578416A1 (fr) | 2013-04-10 |
EP2578416B1 true EP2578416B1 (fr) | 2014-07-30 |
EP2578416B8 EP2578416B8 (fr) | 2014-11-19 |
Family
ID=45955820
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP20120186989 Not-in-force EP2578416B8 (fr) | 2011-10-03 | 2012-10-02 | Procédé pour la décoration de la surface d'un film de polymère fluoriné |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP2578416B8 (fr) |
IT (1) | ITTO20110878A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106749837B (zh) * | 2016-12-01 | 2020-02-07 | 浩博(福建)新材料科技有限公司 | 一种导热聚甲基丙烯酰亚胺泡沫塑料的制备方法 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3018188A (en) * | 1958-04-10 | 1962-01-23 | Du Pont | Process for printing on fluorocarbon resin surfaces |
FR2555512B1 (fr) * | 1983-11-25 | 1987-07-03 | Toulemonde Nicolas | Procede d'impression offset sur supports plastiques |
JPH06127152A (ja) * | 1992-10-14 | 1994-05-10 | Kuraray Co Ltd | 転写方法 |
WO2007126714A1 (fr) * | 2006-04-03 | 2007-11-08 | Illinois Tool Works Inc | Feuille de séparation pour images décoratives |
-
2011
- 2011-10-03 IT IT000878A patent/ITTO20110878A1/it unknown
-
2012
- 2012-10-02 EP EP20120186989 patent/EP2578416B8/fr not_active Not-in-force
Also Published As
Publication number | Publication date |
---|---|
EP2578416B8 (fr) | 2014-11-19 |
ITTO20110878A1 (it) | 2013-04-04 |
EP2578416A1 (fr) | 2013-04-10 |
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