EP0949013B1 - Verfahren zur Herstellung von Haftvermittlerschichten - Google Patents
Verfahren zur Herstellung von Haftvermittlerschichten Download PDFInfo
- Publication number
- EP0949013B1 EP0949013B1 EP99106117A EP99106117A EP0949013B1 EP 0949013 B1 EP0949013 B1 EP 0949013B1 EP 99106117 A EP99106117 A EP 99106117A EP 99106117 A EP99106117 A EP 99106117A EP 0949013 B1 EP0949013 B1 EP 0949013B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- adhesive
- process according
- adhesion
- plasma
- backing
- 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 - Lifetime
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/62—Plasma-deposition of organic layers
Definitions
- the invention relates to a method for producing at least one-sided Adhesive tapes, wherein between the carrier and adhesive for adhesion promotion Adhesive layers are applied to the carrier.
- primer layers on sheet-like materials for a variety different applications are used.
- Examples are packaging materials, Adhesive tapes or protective films in which adhesion promoter layers in each case are provided in order to achieve sufficient strength of the composite layer.
- Adhesive tapes this is often particularly problematic because generally high Requirements for the adhesion between adhesive and carrier material are made. A detachment of the adhesive from the carrier should neither during the removal of the adhesive tape of the role (before use) still when removing the tape of any Substrate (after use) take place.
- Adhesive layers also called primers can, for example, as a wet chemical coating from solution (Solvent or water) are applied, with subsequent drying and / or networking is necessary.
- Another disadvantage of the flame pretreatment is the high thermal load of the treating materials, so that in particular temperature-sensitive materials can not or only partially be treated.
- the low-pressure plasma polymerization is not yet for the industrial production of Adhesive layers applied to web-like materials, although for dormant substrates already processes for a variety of different applications exist. Examples are the coating of plastic bottles with permeation barrier layers or the scratch-resistant coating of plastic surfaces.
- web-shaped Materials is the use of low pressure plasma polymerization so far in general not useful, since the deposition rates are too low, so that coating time of Minutes or hours. For this is the production of coatings by low-pressure plasma polymerization in sheet-like materials, in particular the production of adhesive layers, uneconomical.
- primers which are applied wet-chemically, usually brings high costs associated with the equipment of the sheet material with a primer a complete additional coating process means. There are also some Primer under environmental and health aspects classified as questionable, in particular because for wet chemical coating of the primer solvents are necessary.
- wet chemical primer is also problematic in rough web-shaped Materials, since it is difficult in these cases, a constant, even Layer thickness to achieve.
- temperature-sensitive materials can only conditionally coated with wet chemical primers, as an economical primer drying when processing web-shaped materials normally drying temperatures of at least 80 ° C is required.
- the object of the invention is to avoid the disadvantages of the prior art, at least diminish.
- it is the object of the invention in adhesive layers on carriers to achieve a significant liability increase, the Liability increase must be long-term stable, no solvents are used should and the procedure and the adhesive layers health and under Environmental aspects should be safe.
- the object is achieved by a method for producing at least one-sided Adhesive tapes, wherein between the carrier and the adhesive for adhesion promotion adhesion promoter layers be applied to the carrier, as characterized in detail in the main claim is.
- the subject of the dependent claims are particularly advantageous embodiments of the procedure.
- the invention relates to a method for producing at least one-sided Adhesive tapes, wherein between the carrier and the adhesive for adhesion promotion adhesion promoter layers be applied to the carrier by means of low-pressure plasma polymerization, by passing the carrier continuously through a plasma zone in which a low-pressure plasma is present, by electrical discharge, in particular kHz, MHz or GHz discharge is generated.
- the process of deposition of the adhesion-promoting Layers and thus control the layer properties are the monomers used or carrier or additional gases, the gas or gas mixture pressure during the coating and the electrical discharge used for plasma excitation.
- the variation of Process parameters serve to optimize and adapt the adhesive layers to the technical boundary conditions in the respective application. Especially can by way of appropriate choice of process parameters, as in the examples by way of example explains, a significant increase in the deposition rate compared to the state of Technique can be achieved so that coating times of less than 1 second result.
- it is coated at a gas pressure or mixed gas pressure of 10 -3 to 20 mbar.
- the carrier is at a speed of more than 0.1 m / min, in particular greater than 50 m / min, through the coating zone emotional.
- the coating times are shorter than one minute, in particular less than a second.
- saturated hydrocarbons having chain lengths of C 1 to C 6 in particular methane, ethane or propane, and / or mono- or polyunsaturated hydrocarbons having chain lengths of C 1 to C 6 , preferably acetylene or ethylene, and / or or oxygen or hetero element substituted compounds of the saturated or unsaturated hydrocarbons, such as ethylene oxide used.
- a carrier or additional gases are preferably non-polymerizable gases such Noble gases, oxygen, hydrogen, nitrogen or compounds respectively Gas mixtures used.
- Additional and carrier gases are used to control the layer deposition and in particular, to increase the uniformity and the stability of the plasma.
- the carriers are preferably Kunststoffoffolien, foam carrier, fabric carrier, non-woven carrier or paper carrier used.
- adhesion promoter layers produced by means of the process according to the invention has proved to be particularly advantageous in at least one-sided adhesive tapes for bonding adhesion between the support and the adhesive.
- a strong improvement in adhesion is particularly typical for the combination of acrylate-based vehicles and adhesives.
- various forms of electrical discharge can be used become. This is preferably done by kHz, MHz or GHz discharge.
- critical for selection of the excitation form are the procedural constraints, for example, necessary coating speed or gas mixture pressure, during the coating.
- a particular advantage of the method compared to the prior art is the possibility the process of layer deposition and thus the adhesion-promoting effect of To be able to control coatings by varying the process parameters. This makes possible an optimal adaptation of the coating properties to the respective application.
- Another advantage of the novel process is the absence of solvents and the Possibility of using substances that are considered health or environmental aspects are to be avoided.
- An additional advantage of the method is the ability to evenly with rough carriers Coating adhesive layers to coat.
- thermo load of the carrier due to the low pressure plasma used low so that in particular temperature-sensitive materials such Polyethylene, polypropylene or foams can be coated without damage.
- Another advantage is the high long-term stability of the novel adhesive layers, since these are highly cross-linked and thermally stable due to the novel process.
- these are insoluble in common solvents, so that their use, in particular for adhesion between carrier and wet-chemical applied Coatings, leads to very good results.
- the carrier 1 is moved from an unwinding station 2 through the plasma coating zone 3 moves.
- the plasma coating zone 3 which is bounded by boundaries 8 from Remains of the vacuum chamber 7 is separated, monomers via a monomer 4 initiated.
- the plasma excitation and thus the fragmentation of the monomers takes place via a high-frequency alternating field which is applied between the electrodes 5 and 6.
- Electrode 5 is designed as a grounded cooling roller and thus serves the same time Transport of the carrier 1.
- the carrier 1 after coating a Winding station 9 fed.
- Electrodes 10, 11 formed flat and the carrier 1 is non-contact by the Leaded electrode gap.
- the electrodes are by appropriate Replace GHz couplings.
- a primer layer is applied by means of low-pressure plasma polymerization.
- the coating takes place in a plant according to FIG. 1 with an acetylene flow of 500 sccm and an oxygen flow of 50 sccm at a process pressure of 0.5 mbar.
- the film is passed at a speed of 100 m / min through the plasma zone (length 200 mm), so that a coating time of 0.12 sec results with a layer thickness of 130 nm.
- the plasma excitation takes place by means of kHz discharge.
- a transparent acrylate adhesive (self-polymer of 48% butyl acrylate, 48% ethylhexyl acrylate, 4% acrylic acid) is applied from solution to the adhesion-promoting layer (solvent acetone / gasoline, adhesive application after drying: 40 g / m 2 ).
- the adhesion between adhesive and carrier film is checked by an anchoring test.
- an adhesive tape with the bonding agent layer according to the invention and a width of 20 mm is glued and rolled onto a PVC sheet (steel roll, 80 mm diameter, 2 kg weight, is pushed over the adhesive tape at about 10 m / min five times). and rolled over).
- a primer layer is applied by means of low-pressure plasma polymerization.
- the coating takes place in a plant according to FIG. 1 with an acetylene flow of 500 sccm at a process pressure of 3 mbar.
- the film is passed at a speed of 50 m / min through the plasma zone (length 200 mm), so that there is a coating time of 0.24 sec with a layer thickness of 180 nm.
- the plasma excitation takes place by means of MHz discharge.
- a transparent acrylate adhesive self-polymer of 47% butyl acrylate, 47% ethylhexyl acrylate, 6% acrylic acid
- the adhesion-promoting layer solvent acetone / gasoline, adhesive application after drying: 40 g / m 2 .
- the adhesion between adhesive and carrier film is checked by an anchoring test.
- adhesive tape with the bonding agent layer according to the invention and a width of 20 mm are glued and rolled on PVC sheets (steel roll, 80 mm diameter, 2 kg weight, is rolled back and forth five times over the adhesive strip at about 10 m / min ).
- the adhesion between backing film and adhesive is tested after storage by subtracting the test strips at a speed of 2400 mm / min at an angle of 180 ° or 90 °. Due to the adhesion-promoting layer according to the invention, the adhesion between the carrier film and the adhesive is increased substantially and surprisingly strongly and permanently, so that cohesive splitting of the adhesive occurs during the test.
- the adhesion between adhesive and carrier film is thus significantly better than comparative adhesive films in which instead of the primer layer according to the invention wet-chemical primer or a corona or flame pretreatment were used.
- the comparative adhesive tapes an adhesive failure between the carrier foil and the adhesive was observed in all cases and thus a significantly poorer adhesion between the adhesive and the carrier foil.
- a primer layer is applied by means of low-pressure plasma polymerization.
- the coating takes place in a plant according to FIG. 1 with an ethylene flow of 1000 sccm at a process pressure of 0.5 mbar.
- the film is passed through the plasma zone (length 200 mm) at a speed of 20 m / min.
- the plasma excitation takes place by means of kHz discharge.
- a transparent acrylate adhesive self-polymer of 47% butyl acrylate, 47% ethylhexyl acrylate, 6% acrylic acid
- the adhesion-promoting layer solvent acetone / gasoline, adhesive application after drying: 20 g / m 2 .
- the adhesion between adhesive and carrier film is checked by an anchoring test.
- Kfir strip with the bonding agent layer according to the invention and a width of 20 mm are glued and rolled on PVC plates (steel roll, 80 mm diameter, 2 kg weight, is rolled back and forth five times over the adhesive strip at about 10 m / min ).
- the adhesion between backing film and adhesive is tested after storage by subtracting the test strips at a speed of 2400 mm / min at an angle of 180 ° or 90 °. Due to the adhesion-promoting layer according to the invention, the adhesion between the carrier film and the adhesive is increased substantially and surprisingly strongly and permanently, so that cohesive splitting of the adhesive occurs during the test.
- the adhesion between adhesive and carrier film is thus significantly better than in comparison adhesive films in which wet-chemical primer or a corona or flame pretreatment were used instead of the adhesion promoter layer according to the invention.
- the comparative adhesive tapes an adhesive failure between the carrier foil and the adhesive was observed in all cases and thus a significantly poorer adhesion between the adhesive and the carrier foil.
- a primer layer is applied by means of low-pressure plasma polymerization.
- the coating takes place in a plant according to FIG. 1 with an acetylene flow of 500 sccm at a process pressure of 3 mbar.
- the film is passed through the plasma zone (length 200 mm) at a speed of 25 m / min to give a coating time of 0.48 sec with a layer thickness of 750 nm.
- the plasma excitation is carried out by pulsed MHz discharge at a pulse frequency of 10 3 Hz and a duty cycle of 0.3.
- a transparent acrylate adhesive (Primal PS 83 D, Rohm and Haas GmbH, Frankfurt) is applied from solution to the adhesion-promoting layer (solvent water, adhesive application after drying: 20 g / m 2 ).
- the adhesion between adhesive and carrier film is checked by an anchoring test.
- adhesive tape with the bonding agent layer according to the invention and a width of 20 mm are glued and rolled on PVC sheets (steel roll, 80 mm diameter, 2 kg weight, is rolled back and forth five times over the adhesive strip at about 10 m / min ).
- the adhesion between backing film and adhesive is tested after storage by subtracting the test strips at a speed of 2400 mm / min at an angle of 180 ° or 90 °. Due to the adhesion-promoting layer according to the invention, the adhesion between the carrier film and the adhesive is increased substantially and surprisingly strongly and permanently, so that cohesive splitting of the adhesive occurs during the test. The adhesion between adhesive and carrier film is thus significantly better than comparative adhesive films in which instead of the primer layer according to the invention wet-chemical primer or a corona or flame pretreatment were used. In the case of the comparative adhesive tapes, an adhesive failure between the carrier foil and the adhesive was observed in all cases and thus a significantly poorer adhesion between the adhesive and the carrier foil.
- a primer layer is applied by means of low-pressure plasma polymerization.
- the coating takes place in a plant according to FIG. 1 with an acetylene flow of 500 sccm and an argon flow of 50 sccm at a process pressure of 0.5 mbar.
- the film is passed at a speed of 20 m / min through the plasma zone (length 200 mm), so that a coating time of 0.6 sec results.
- the plasma excitation is done by means of kHz-discharge.
- a transparent acrylate adhesive self-polymer of 47% butyl acrylate, 47% ethylhexyl acrylate, 6% acrylic acid
- the adhesion-promoting layer solvent acetone / gasoline, adhesive application after drying: 50 g / m 2 .
- the adhesion between adhesive and carrier film is checked by an anchoring test.
- an adhesive strip with the adhesion promoter layer according to the invention width 20 mm
- the entire composite is stored at 40 ° C and a humidity of 50% for 3 days in a drying oven.
- the adhesion between foam carrier and adhesive is tested after storage by deduction of the test strip. Due to the adhesion-promoting layer according to the invention, the adhesion between the carrier film and the adhesive is increased substantially and surprisingly strongly and permanently, so that cohesive splitting of the foam or detachment of the test strip occurs.
- the adhesion between adhesive and foam carrier is thus significantly better than in comparison samples in which a corona or flame pretreatment was used instead of the adhesion promoter layer according to the invention. In the case of the comparative samples, an adhesive failure between the foam carrier and the adhesive and thus a clearly poor adhesion was observed in all cases.
- a primer layer is applied by means of low-pressure plasma polymerization.
- the coating takes place in a plant according to FIG. 1 with an acetylene flow of 500 sccm at a process pressure of 3 mbar.
- the film is passed through the plasma zone (length 200 mm) at a speed of 100 m / min.
- the plasma excitation is carried out by pulsed MHz discharge at a pulse frequency of 10 3 Hz and a duty cycle of 0.3.
- a rubber adhesive self-polymer of 43% natural rubber, 3% Sillithin Z 86 white, 12% zinc oxide, 21% Escorez® 1202 (exon), 20% Escorez® 365 (exon), 0.4% AS MBI 2 PLV® (Bayer), 0.6% Sontal® (Bayer)
- the adhesion between adhesive and carrier film is checked by an anchoring test.
- adhesive tape with the bonding agent layer according to the invention and a width of 20 mm are glued and rolled on PVC sheets (steel roll, 80 mm diameter, 2 kg weight, is rolled back and forth five times over the adhesive strip at about 10 m / min ).
- PVC sheets steel roll, 80 mm diameter, 2 kg weight, is rolled back and forth five times over the adhesive strip at about 10 m / min ).
- the adhesion between backing film and adhesive is tested after storage by subtracting the test strips at a speed of 2400 mm / min at an angle of 180 ° or 90 °.
- the adhesion between the carrier film and the adhesive is increased substantially and surprisingly strongly and permanently, so that the test strips can be completely removed again.
- the adhesion between adhesive and carrier film is thus significantly better than comparative adhesive films in which instead of the primer layer according to the invention wet-chemical primer or a corona or flame pretreatment were used.
- the comparative adhesive tapes an adhesive failure between the carrier foil and the adhesive was observed in all cases and thus a significantly poorer adhesion between the adhesive and the carrier foil.
Landscapes
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Adhesive Tapes (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Description
Eine starke Verbesserung der Haftung ist besonders typisch für die Verbindung von Trägem und Klebmassen auf Acrylatbasis.
- Figur 1
- den Aufbau einer erfindungsgemäßen Vakuumbeschichtungsanlage und
- Figur 2
- eine alternative Anordnung der Elektroden aus Figur 1.
Claims (11)
- Verfahren zur Herstellung von zumindest einseitigen Klebebändern, wobei zwischen Träger und Klebmasse zur Haftvermittlung Haftvermittlerschichten mittels Niederdruckplasmapolymerisation auf den Träger aufgebracht werden, indem der Träger kontinuierlich durch eine Plasmazone geführt wird, in der ein Niederdruckplasma vorhanden ist, das durch elektrische Entladung, insbesondere kHz-, MHz- oder GHz-Entladung, erzeugt wird.
- Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass
bei einem Gasdruck oder Gasgemischdruck von 10-3 bis 20 mbar beschichtet wird. - Verfahren nach den Ansprüchen 1 oder 2, dadurch gekennzeichnet, dass
gepulste elektrische Entladungen zur Erzeugung des Plasmas eingesetzt werden. - Verfahren nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, dass
der Träger mit einer Geschwindigkeit von über 0,1 m/min, insbesondere größer 50 m/min, durch die Beschichtungszone bewegt wird. - Verfahren nach Anspruch 1 bis 4, dadurch gekennzeichnet, dass
die Beschichtungszeiten kürzer als eine Minute, insbesondere kleiner als eine Sekunde, sind. - Verfahren nach Anspruch 1 bis 5, dadurch gekennzeichnet, dass
sich die Abwickelstation des Trägers, die Aufwickelstation und die Plasmazone in einer Vakuumkammer befinden. - Verfahren nach Anspruch 1 bis 5, dadurch gekennzeichnet, dass
der Träger mittels Vakuumschleusen durch die Plasmazone geführt wird. - Verfahren nach Anspruch 1 bis 7 dadurch gekennzeichnet, dass
zur Bildung des Niederdruckplasmas als Monomere gesättigte Kohlenwasserstoffe mit Kettenlängen von C1 bis C6, insbesondere Methan, Ethan oder Propan, und/oder einfach beziehungsweise mehrfach ungesättigte Kohlenwasserstoffe mit Kettenlängen von C1 bis C6, vorzugsweise Acetylen oder Ethylen, und/oder sauerstoff- oder heteroelementsubstituierte Verbindungen der gesättigten oder ungesättigten Kohlenwasserstoffe eingesetzt werden. - Verfahren nach Anspruch 1 bis 8 dadurch gekennzeichnet, dass
als Träger- oder Zusatzgase nicht-polymerisierbare Gase wie Edelgase, Sauerstoff, Wasserstoff, Stickstoff oder Verbindungen beziehungsweise Gasgemische eingesetzt werden. - Verfahren nach Anspruch 1 bis 9 dadurch gekennzeichnet, dass
die Haftvermittlerschichten nahezu oder völlig transparent sind. - Verfahren nach Anspruch 1 bis 10, dadurch gekennzeichnet, dass
als Träger Kunstofffolien, Schaumträger, Gewebeträger, Vliesträger oder Papierträger eingesetzt werden.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19815182 | 1998-04-04 | ||
DE19815182A DE19815182A1 (de) | 1998-04-04 | 1998-04-04 | Verfahren zur Herstellung von Haftvermittlerschichten |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0949013A2 EP0949013A2 (de) | 1999-10-13 |
EP0949013A3 EP0949013A3 (de) | 2003-04-16 |
EP0949013B1 true EP0949013B1 (de) | 2005-06-08 |
Family
ID=7863624
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99106117A Expired - Lifetime EP0949013B1 (de) | 1998-04-04 | 1999-04-01 | Verfahren zur Herstellung von Haftvermittlerschichten |
Country Status (4)
Country | Link |
---|---|
US (1) | US6106904A (de) |
EP (1) | EP0949013B1 (de) |
DE (2) | DE19815182A1 (de) |
ES (1) | ES2243021T3 (de) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3345545B2 (ja) * | 1996-02-21 | 2002-11-18 | アルケア株式会社 | 成形材 |
KR100320197B1 (ko) * | 1999-08-21 | 2002-01-10 | 구자홍 | 직류전원 플라즈마중합 연속처리장치 |
DE10009856A1 (de) * | 2000-03-01 | 2001-09-06 | Beiersdorf Ag | Verfahren zur Herstellung von antiadhäsiven Beschichtungen |
JP4746738B2 (ja) * | 2000-10-10 | 2011-08-10 | リンテック株式会社 | 耐放射線性粘着剤及びこれを用いた粘着製品 |
US10934617B2 (en) * | 2010-11-16 | 2021-03-02 | Cuptronic Technology Ltd. | Metal coating of objects using plasma polymerisation pretreatment |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3814983A (en) * | 1972-02-07 | 1974-06-04 | C Weissfloch | Apparatus and method for plasma generation and material treatment with electromagnetic radiation |
DE3147986C2 (de) * | 1981-12-04 | 1992-02-27 | Leybold-Heraeus GmbH, 5000 Köln | Vorrichtung zur Erzeugung eines Mikrowellenplasmas für die Behandlung von Substraten, insbesondere zur Plasmapolymerisation von Monomeren |
US4563388A (en) * | 1983-03-28 | 1986-01-07 | Minnesota Mining And Manufacturing Company | Polyolefin substrate coated with acrylic-type normally tacky and pressure-sensitive adhesive and a method of making same |
DE3521625A1 (de) * | 1985-06-15 | 1986-12-18 | Leybold-Heraeus GmbH, 5000 Köln | Verfahren zum beschichten von substraten durch niederdruck-plasmapolymerisation von monomeren |
CN1074006C (zh) * | 1995-10-13 | 2001-10-31 | 陶氏化学公司 | 涂覆的塑料基材 |
-
1998
- 1998-04-04 DE DE19815182A patent/DE19815182A1/de not_active Withdrawn
-
1999
- 1999-03-25 US US09/276,341 patent/US6106904A/en not_active Expired - Lifetime
- 1999-04-01 DE DE59912131T patent/DE59912131D1/de not_active Expired - Lifetime
- 1999-04-01 EP EP99106117A patent/EP0949013B1/de not_active Expired - Lifetime
- 1999-04-01 ES ES99106117T patent/ES2243021T3/es not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
US6106904A (en) | 2000-08-22 |
ES2243021T3 (es) | 2005-11-16 |
DE59912131D1 (de) | 2005-07-14 |
EP0949013A2 (de) | 1999-10-13 |
EP0949013A3 (de) | 2003-04-16 |
DE19815182A1 (de) | 1999-10-14 |
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