EP0678398B1 - Mit Tinte für PVC gedrückte Gegenstände aus Polyolefnien und Verfahren zur Herstellung - Google Patents

Mit Tinte für PVC gedrückte Gegenstände aus Polyolefnien und Verfahren zur Herstellung Download PDF

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Publication number
EP0678398B1
EP0678398B1 EP95200917A EP95200917A EP0678398B1 EP 0678398 B1 EP0678398 B1 EP 0678398B1 EP 95200917 A EP95200917 A EP 95200917A EP 95200917 A EP95200917 A EP 95200917A EP 0678398 B1 EP0678398 B1 EP 0678398B1
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EP
European Patent Office
Prior art keywords
pvc
fluorine
oxygen
treatment
ink
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Expired - Lifetime
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EP95200917A
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English (en)
French (fr)
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EP0678398A1 (de
Inventor
Claude Dehennau
Zdenek Hruska
Frédéric Menu
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.)
SIFMAR SA
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Solvay SA
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Publication of EP0678398A1 publication Critical patent/EP0678398A1/de
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M1/00—Inking and printing with a printer's forme
    • B41M1/26—Printing on other surfaces than ordinary paper
    • B41M1/30—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials
    • B41M1/305—Printing on other surfaces than ordinary paper on organic plastics, horn or similar materials using mechanical, physical or chemical means, e.g. corona discharge, etching or organic solvents, to improve ink retention

Definitions

  • the invention relates to articles based on polyolefins printed with inks for poly (vinyl chloride) (PVC) and a process for their production.
  • PVC poly (vinyl chloride)
  • articles made of plastic, and in particular films, sheets and hollow bodies are printed using conventional printing techniques such as screen printing, rotogravure or flexography.
  • Inks have been developed specifically for printing on articles made of certain polymers having very specific surface polarity characteristics, such as a high surface tension, for example on articles based on polymethyl methacrylate (PMMA) or polyvinyl chloride (PVC); they are generally called "PVC inks".
  • PMMA polymethyl methacrylate
  • PVC polyvinyl chloride
  • PVC inks are very popular with printers because they give printed designs a higher print quality than is generally obtained with other types of plastic inks. As explained above, these inks can be used on PVC articles, for example on PVC films. However, more and more attempts are currently being made by plastic processors to substitute polyolefins (PO) for PVC. To meet this demand, new surface treatment techniques had to be developed by the plastics and paints industry, in order to allow the printing of PO articles on conventional printing lines. Indeed, due to their apolarity, certain plastics such as polyolefins require, prior to their printing, an appropriate surface treatment such as corona discharge, flame treatment, plasma treatment, fluorination or oxyfluorination, and the use ink suitable for these materials.
  • PO polyolefins
  • the first object of the invention is therefore an article, at least one surface area of which comprises at least one polyolefin, treated surface with oxygen and fluorine and printed with PVC ink.
  • the invention relates to an article printed using an ink for PVC, at least one surface area of which comprises at least one polyolefin and has been treated with oxygen and fluorine, characterized by the presence on the surface of fluorine and oxygen in concentrations such as the oxygen / carbon atomic ratio (O / C), measured by ESCA spectroscopy at a depth of 1.5 nm, or at least 0.08, and that the fluorine / carbon atomic ratio (F / C), measured in the same way, has a value of at least 90% of that of the O / C ratio, and of at most 290% of this ratio.
  • O / C oxygen / carbon atomic ratio
  • F / C fluorine / carbon atomic ratio
  • the articles referred to in the context of the present invention can be of any type, in particular films, sheets or plates, or even hollow bodies such as bottles, barrels, tanks, flasks, pipes, etc.
  • the invention is particularly advantageous in the case of flat articles, especially in the case of films.
  • These flat articles can be produced by any means, in particular by calendering, by extrusion or by coextrusion, for example by extrusion-blowing, extrusion-coating, extrusion in a flat die as well as by related coextrusion techniques.
  • at least one surface area of the article must comprise at least one polyolefin.
  • this zone essentially consists of at least one polyolefin.
  • One or more other parts of the article may consist essentially of one or more other materials such as a metal or a cellulosic material.
  • the invention applies to monolayer and multilayer articles.
  • the invention applies inter alia to multilayer articles in which at least the printed surface layer is based on polyolefin, one or more other layers which may essentially consist of one or more other materials.
  • the above definition of the surface area relates to the surface of the article before it is printed, and not to the ink which may possibly cover it.
  • the articles are printed using PVC ink.
  • PVC ink is meant an ink which, applied to a PVC substrate, adheres well to the latter, that is to say obtains a classification of "1" or "2" in the test defined by the ASTM D-3359 standard ("scotch tape test").
  • ASTM D-3359 standard scotch tape test
  • polyolefins is intended to denote both homopolymers of olefins and copolymers comprising at least 70% of units derived from olefins, any copolymer consisting of at least two different types of olefins, as well as mixtures of these homo - And / or copolymers.
  • olefins is intended to denote both mono-olefins such as ethylene, propylene or butene as well as olefins comprising more than one double bond, for example diolefins such as butadiene.
  • polystyrene foams can also optionally be added one or more conventional mineral fillers, such as calcium carbonate, titanium dioxide, mica, etc., reinforcing fibers such as for example glass fibers or carbon, as well as one or more conventional additives such as stabilizers, lubricants, antioxidants, etc.
  • mineral fillers such as calcium carbonate, titanium dioxide, mica, etc.
  • reinforcing fibers such as for example glass fibers or carbon
  • additives such as stabilizers, lubricants, antioxidants, etc.
  • the articles in question may optionally include one or more other polymers intended to give them specific properties, for example in order to improve their impact resistance.
  • the O / C atomic ratio is greater than 0.1.
  • the O / C ratio is moreover generally less than 0.40, and preferably less than 0.30.
  • the F / C atomic ratio is greater than 95% of the O / C ratio. Preferably, it is less than 200% of this ratio.
  • a second object of the present invention relates to a method making it possible to manufacturing these articles, and more precisely a method of surface treatment of an article intended to be printed, at least one surface area of which comprises at least one polyolefin, comprising at least one oxidation step and one fluorination step, under such conditions that said zone contains fluorine and oxygen on the surface in concentrations such as the oxygen / carbon atomic ratio (O / C), measured by ESCA spectroscopy at a depth of 1.5 nm, or at least 0.08, and that the fluorine / carbon atomic ratio (F / C), measured in the same way, has a value of at least 90% of that of the O / C ratio, and at most 290% of this ratio.
  • O / C oxygen / carbon atomic ratio
  • F / C fluorine / carbon atomic ratio
  • this article is intended to be printed using PVC ink.
  • the article concerned can be treated both over its entire surface and over one or more zones of its surface, meeting the above definitions.
  • the article concerned can be treated both over its entire surface and over one or more zones of its surface, meeting the above definitions.
  • the article concerned can be treated both over its entire surface and over one or more zones of its surface, meeting the above definitions.
  • the abovementioned values concerning the oxygen and fluorine concentrations obviously only apply to areas comprising at least one polyolefin which have been effectively surface treated.
  • the surface treatment by means of oxygen and fluorine can be carried out by any known method, continuously or batchwise, provided that it leads to the above-mentioned F / C and O / C ratios.
  • the O / C atomic ratio is greater than 0.1.
  • the O / C ratio is moreover generally less than 0.40, and preferably less than 0.30.
  • the F / C atomic ratio is greater than 95% of the O / C ratio. Preferably, it is less than 200% of this ratio. Concrete examples of surface treatment are given in documents US 4,296,151 and WO 93/24559 cited above.
  • This surface treatment method applies to any type of article, as defined above. It works very well when applied to films.
  • fluorination is intended to denote any known treatment carried out by means of a gaseous mixture containing fluorine and making it possible to chemically bond the latter to a plastic material; examples are given in documents US 4,296,151 and WO 93/24559 cited above.
  • a mixture of nitrogen and 1 to 10% by volume of fluorine is preferably used. Good results have been obtained by heating the enclosure and / or the gas mixture during the fluorination step.
  • the duration of treatment is obviously linked to all of the operating conditions. Fluoridation is generally short-lived.
  • the duration of fluorination is advantageously at most 12 seconds. Preferably, it does not exceed 4 seconds and more preferably still it does not exceed 2 seconds.
  • oxidation is intended to denote any known treatment carried out which makes it possible to chemically bond oxygen to a plastic material.
  • a well-known example of such treatment consists in using a gaseous mixture containing oxygen.
  • Other examples of oxidation steps will be given below ("energetic surface oxidation steps").
  • the oxidation step and the fluorination step can take place in any order.
  • the fluorination and oxidation steps can optionally be combined. In practice, it is moreover very difficult, especially in continuously operating installations, to prevent the presence of traces of oxygen during fluorination.
  • the surface treatment method comprises an oxyfluorination step, that is to say a treatment using a gaseous mixture comprising oxygen and fluorine.
  • an oxyfluorination step that is to say a treatment using a gaseous mixture comprising oxygen and fluorine. This allows the simple and simultaneous incorporation of oxygen and fluorine on the surface of the treated articles.
  • the method consists solely of an oxyfluorination step.
  • the oxidation comprises a step of energetic surface oxidation. This variant leads to excellent results.
  • energetic surface oxidation is meant any high-energy oxidative treatment such as flame treatment, corona discharge, plasma treatment in presence of oxygen, ozone treatment, or an oxygen oxidation step with heating to a temperature below the melting temperature of the material in the zone, as well as combinations of several of these treatments.
  • the zone is preferably brought to a temperature 20 to 90 ° C lower than the melting temperature of its constituent material.
  • This heating can be achieved by any known means, for example by infrared radiation or by blowing hot air.
  • the energetic surface oxidation comprises a corona treatment.
  • An oxidation with heating and a corona treatment are advantageously combined.
  • Vigorous surface oxidation and fluorination can take place in any order. They can also be simultaneous, for example by a cold plasma treatment, as described in particular in J. Appl. Polym. Sc., Appl. Polym. Symp., Vol. 46, 61 (1990) and in J. Appl. Polym. Sc., Vol. 50, 585 (1993) or by oxyfluorination with heating. It is generally preferred that these treatments are separated over time. In this case, it is particularly preferred that at least one fluorination step is preceded by at least one energetic surface oxidation step. The time periods separating the different stages may be arbitrary, provided that the activation effect of a given stage always remains at the time of the next.
  • the surface treatment process can include a vigorous surface oxidation step, followed by a fluorination step a few days later.
  • the energetic surface oxidation comprises an oxidation with heating
  • the oxidation with heating is most often quickly followed by the fluorination step and even preferably these two treatments are simultaneous.
  • the treatment superficial is carried out in line with the manufacturing stages of the articles (extrusion, etc.).
  • the surface treatment method thus defined makes it possible to obtain articles of which at least one surface zone comprises at least one polyolefin on which the PVC inks adhere well, even when the printing takes place several months after their manufacture.
  • a final object of the present invention relates to a method of manufacturing a printed article of which at least one surface area comprises at least one polyolefin, comprising a specific surface treatment as defined above and at least one step of printing this area using PVC ink.
  • Printing can be done by any known method, for example by screen printing, rotogravure printing, flexography or by means of a wire scraper.
  • Figures 1 and 2 show the evolution over time of the pressure prevailing in the treatment chamber during the surface treatment cycles 1 and 2 used in some of the examples.
  • the abscissa axis corresponds to time, and that of the ordinate to pressure (expressed in mbar).
  • the films are printed by coating using a wire scraper, which allows the deposition of a 6 ⁇ m layer; the ink drying time (at room temperature) is fixed at 3 hours for all the inks used.
  • a 100 ⁇ m thick transparent homopolymer polypropylene (PP) film was used, extruded from MOPLEN® F30S resin (HIMONT).
  • This film was treated by corona discharge using an AHLBRANDT® brand installation at a speed of 12 m / min.
  • the system uses a generator of type 5402 (frequency 30 kHz; voltage 14 kV).
  • the two electrodes, coated with ceramic, are 3 mm apart from the counter electrode.
  • the output current is 5.6 A.
  • a film identical to that used in Example 1R was treated by flame treatment using an AEROGEN® brand installation at a speed of 30 m / min.
  • the unit uses an AEROGEN AT533 type burner.
  • the gas used is propane.
  • the oxygen content of the gas mixture is maintained at 20.00 ⁇ 0.02% by volume (measured using a paramagnetic cell of the SERVOMEX® 1420 type).
  • the distance between the burner and the film surface is 30 mm.
  • Example 1R A film identical to that of Example 1R was treated by plasma discharge using a HITACHI® brand installation using radio frequency mode (13.56 MHz), at a speed of 12 m / min.
  • the voltage coupled to the plasma is 6.8 kV.
  • the installation is equipped with electrodes and treats only one side of the film.
  • the pressure in the chamber is maintained at 1.33 Pa.
  • the gas used is nitrogen, the flow rate of which is 100 ml / min.
  • the fluorination was carried out discontinuously, and according to one of the following two cycles: a fluorination cycle (cycle 1 - FIG. 1), and an oxyfluorination cycle (cycle 2 - FIG. 2) ).
  • the total pressure was slightly less than 400 mbar at the start and end of the treatment period, due to the gradual filling and emptying of the treatment chamber.
  • a transparent film 100 ⁇ m thick was used, extruded from a polypropylene-polyethylene copolymer (PP-PE) (MOPLEN EP2C 30F resin from HIMONT).
  • PP-PE polypropylene-polyethylene copolymer
  • MOPLEN EP2C 30F resin from HIMONT The film was fluorinated according to the surface treatment cycle 1 (fluorination).
  • a 100 ⁇ m thick film was used, consisting of the same copolymer as in Example 4R but also loaded with TiO 2 (17.5% by weight per compared to the polymer).
  • the film was fluorinated according to the surface treatment cycle 1 (fluorination).
  • a 100 ⁇ m thick transparent homopolymer PP film was used, extruded from MOPLEN F30S resin and fluorinated according to surface treatment cycle 1 (fluorination).
  • a high density PE film (HDPE) ELTEX® XF714 (SOLVAY) extruded 150 ⁇ m thick was fluorinated according to the surface treatment cycle 2 (oxyfluorination).
  • the films passed through a chamber supplied continuously, under a total pressure of 1 bar, by a treatment gas mixture containing, an inert gas (nitrogen) and fluorine, also in the presence of oxygen. .
  • Example 12 in accordance with the invention, a film identical to that of Example 1R was fluorinated online at the speed of 5 m / min, in an installation such that the duration of the treatment is 12 s.
  • the treatment gas contained by volume 5% fluorine and 95% nitrogen.
  • Example 13 also in accordance with the invention, a film identical to that of Example 5R was fluorinated online under the same conditions as in Example 12.
  • Table 1 shows the values of the total surface tension ⁇ T and its dispersive and polar components ⁇ d and ⁇ p for examples 4R to 11, as well as the total surface tension for examples 12 and 13.
  • the films of Examples 9 to 11, in accordance with the invention, on the other hand remain perfectly printable, both by inks for PO and by inks for PVC, after storage for 12 months at room temperature.
  • the films of Examples 12 and 13, in accordance with the invention, also remain perfectly printable, both by inks for PO and by inks for PVC, after storage for 100 hours in an oven ventilated at 70 ° C.
  • An extruded film consisting of a mixture of PP (ELTEX P HL001) and PE (ELTEX B 4020) (80:20 by weight) was processed continuously, at a speed of 5 m / min (corresponding to a time of treatment of 12 s), using a gas mixture comprising (by volume) 10% fluorine and 90% nitrogen.
  • Example 17R Before being fluorinated, the same film as in Example 17R underwent a corona treatment, under the same conditions as in Example 1R but at the speed of 5 m / min.
  • a calendered film consisting of a PP-PE ELTEX P KL 177 copolymer comprising 11 phr of TiO 2 was treated continuously, at a speed of 5 m / min, by means of a gas mixture comprising (by volume) 5 % fluorine and 95% nitrogen.
  • Example 19R Before being fluorinated, the same film as in Example 19R underwent a corona treatment under the conditions mentioned in Example 18.
  • Examples 18 and 20 show that the films having undergone a corona treatment before their fluorination have a surface tension which is more stable over time and higher. In addition, their printability is excellent, both with inks for PVC and for PO, unlike the films of Examples 17R and 19R.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Printing Methods (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Claims (7)

  1. Mittels einer Tinte für PVC bedruckter Gegenstand, wovon mindestens ein Oberflächenbereich mindestens ein Polyolefin umfaßt und mittels Sauerstoff und Fluor behandelt worden ist, gekennzeichnet durch die Gegenwart von Fluor und Sauerstoff an der Oberflache in Konzentrationen, so daß das Atomverhältnis von Sauerstoff/Kohlenstoff (O/C), durch ESCA-Spektroskopie bis auf eine Tiefe von 1,5 nm gemessen, mindestens 0,08 ist und daß das Atomverhältnis von Fluor/Kohlenstoff (F/C), in gleicher Art und Weise gemessen, einen Wert von mindestens 90% desjenigen des Verhältnisses von O/C hat und höchstens 290% dieses Verhältnisses.
  2. Gegenstand nach Anspruch 1, in Form eines Films.
  3. Gegenstand nach einem der vorhergehenden Ansprüche, worin der behandelte Oberflächenbereich im wesentlichen aus einem Propylenpolymer besteht oder aus einer Mischung aus 50 bis 99% (bezogen auf das Gesamtgewicht der Polymere) mindestens eines Propylenpolymers und von 50 bis 1% mindestens eines Ethylenpolymers.
  4. Verfahren zur Oberflächenbehandlung eines Gegenstands, wovon mindestens ein Oberflächenbereich mindestens ein Polyolefin umfaßt, umfassend mindestens einen Oxidationsschritt und einen Fluorierungsschritt unter Bedingungen, so daß der Bereich eine Oberfläche aus Fluor und Sauerstoff umfaßt, in Konzentrationen, so daß das Atomverhältnis von Sauerstoff/Kohlenstoff (O/C), durch ESCA-Spektroskopie bis auf eine Tiefe von 1,5 nm gemessen, mindestens 0,08 ist und daß das Atomverhältnis von Fluor/Kohlenstoff (F/C), in der gleichen Art und Weise gemessen, einen Wert von mindestens 90% desjenigen des Verhältnisses von O/C hat und von höchstens 290% dieses Verhältnisses.
  5. Verfahren zur Oberflächenbehandlung nach Anspruch 4, worin die Oxidation eine kräftige Oberflächenoxidation umfaßt.
  6. Verfahren nach Anspruch 5, worin die kräftige Oberflächenoxidation eine Coronabehandlung umfaßt.
  7. Verfahren zur Herstellung eines bedruckten Gegenstands, wovon mindestens ein Oberflächenbereich mindestens ein Polyolefin umfaßt, umfassend eine Oberflächenbehandlung nach einem der Ansprüche 4 bis 6 und mindestens einen Schritt des Bedruckens dieses Bereichs mittels einer Tinte für PVC.
EP95200917A 1994-04-19 1995-04-11 Mit Tinte für PVC gedrückte Gegenstände aus Polyolefnien und Verfahren zur Herstellung Expired - Lifetime EP0678398B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BE9400403 1994-04-19
BE9400403A BE1008319A3 (fr) 1994-04-19 1994-04-19 Articles a base de polyolefines imprimes au moyen d'encres pour pvc et procedes pour leur fabrication.

Publications (2)

Publication Number Publication Date
EP0678398A1 EP0678398A1 (de) 1995-10-25
EP0678398B1 true EP0678398B1 (de) 1997-12-17

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EP95200917A Expired - Lifetime EP0678398B1 (de) 1994-04-19 1995-04-11 Mit Tinte für PVC gedrückte Gegenstände aus Polyolefnien und Verfahren zur Herstellung

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US (1) US5654378A (de)
EP (1) EP0678398B1 (de)
JP (1) JPH07292131A (de)
AT (1) ATE161229T1 (de)
BE (1) BE1008319A3 (de)
DE (1) DE69501226T2 (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE1008320A3 (fr) * 1994-04-19 1996-04-02 Solvay Procede pour le traitement superficiel d'articles comprenant au moins une matiere plastique.
BE1012312A3 (fr) * 1998-11-25 2000-09-05 Solvay Articles imprimes par electrophotographie.
BE1012796A3 (fr) 1999-07-26 2001-03-06 Solvay Article imprimable a base de polyolefine.
US6462142B1 (en) 1999-11-03 2002-10-08 Air Products And Chemicals, Inc. Processes for improved surface properties incorporating compressive heating of reactive gases
US20030052033A1 (en) * 2001-09-14 2003-03-20 Schwester Charles P. Retail sales package
US20040241335A1 (en) * 2003-05-08 2004-12-02 Honda Motor Co., Ltd. Process for applying a camouflage pattern to a vehicle
DE102004058209A1 (de) * 2004-12-02 2006-06-08 Printed Systems Gmbh Verfahren und Vorrichtung zur Erzeugung von Strukturen aus Funktionsmaterialien
DE102006012366A1 (de) * 2006-03-17 2007-09-20 Air Liquide Deutschland Gmbh Verfahren zur Modifizierung der Oberfläche von Kunststoff-Formteilen durch fluorinitiierte Oxidation

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4296151A (en) * 1978-12-12 1981-10-20 Phillips Petroleum Company Fluorinated polymeric surfaces
JPH0717759B2 (ja) * 1986-07-28 1995-03-01 旭電化工業株式会社 プロピレン系樹脂成形品
JPH05329342A (ja) * 1992-05-29 1993-12-14 Dainippon Ink & Chem Inc 高分子分離膜の製法
JPH07507582A (ja) * 1992-06-04 1995-08-24 エクソン・ケミカル・パテンツ・インク ポリオレフィンフイルムのフッ素化処理

Also Published As

Publication number Publication date
ATE161229T1 (de) 1998-01-15
EP0678398A1 (de) 1995-10-25
DE69501226T2 (de) 1998-06-25
JPH07292131A (ja) 1995-11-07
DE69501226D1 (de) 1998-01-29
BE1008319A3 (fr) 1996-04-02
US5654378A (en) 1997-08-05

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