WO2011118619A1 - フィルム表面処理装置 - Google Patents
フィルム表面処理装置 Download PDFInfo
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- WO2011118619A1 WO2011118619A1 PCT/JP2011/056950 JP2011056950W WO2011118619A1 WO 2011118619 A1 WO2011118619 A1 WO 2011118619A1 JP 2011056950 W JP2011056950 W JP 2011056950W WO 2011118619 A1 WO2011118619 A1 WO 2011118619A1
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- film
- electrode
- roll electrode
- roll
- discharge space
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
- B29C59/14—Surface shaping of articles, e.g. embossing; Apparatus therefor by plasma treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
Definitions
- the present invention relates to an apparatus for surface treatment of a continuous film, for example, a film surface treatment apparatus suitable for a treatment for improving the adhesion of a protective film of a polarizing plate.
- a polarizing plate is incorporated in a liquid crystal display device.
- the polarizing plate is obtained by bonding a protective film made of a resin film containing triacetate cellulose (TAC) as a main component to a polarizing film made of a resin film containing polyvinyl alcohol (PVA) as a main component using an adhesive.
- TAC triacetate cellulose
- PVA polyvinyl alcohol
- As the adhesive water-based adhesives such as polyvinyl alcohol and polyether are used. PVA films have good adhesion to these adhesives, but TAC films do not have good adhesion.
- a saponification treatment is generally used. In the saponification treatment, the TAC film is immersed in a high-temperature, high-concentration alkaline solution. Therefore, problems of workability and waste liquid treatment have been pointed out.
- Patent Document 1 describes that a polymerizable monomer is coated on the surface of a protective film and irradiated with atmospheric pressure plasma before the bonding step.
- the atmospheric pressure plasma irradiation apparatus one roll electrode is accommodated in a sealed container, and a plurality of plate electrodes are arranged at intervals along the outer periphery of the roll electrode.
- the protective film coated with the polymerizable monomer is wound around the roll electrode.
- discharge gas such as nitrogen
- the plasma processing apparatus of Patent Document 2 has a pair of roll electrodes and a processing gas blowing nozzle.
- the blowing nozzle faces the gap between the roll electrodes.
- a continuous film is wound around a pair of roll electrodes, and plasma treatment is performed in the gap between the roll electrodes.
- a pair of roll electrodes rotate in synchronization with each other to convey a continuous film.
- the roll electrode of the plasma irradiation apparatus is covered with a protective film, but the flat plate electrode is directly exposed to plasma. For this reason, dirt composed of a polymer of a polymerizable monomer or the like tends to adhere to the plate electrode. This dirt component causes particles and causes a decrease in yield.
- the present invention activates a reactive component such as a polymerizable monomer and plasma-treats a film to be treated such as a protective film for a polarizing plate while preventing the contamination of the electrode while reacting the reactive component.
- a reactive component such as a polymerizable monomer
- plasma-treats a film to be treated such as a protective film for a polarizing plate while preventing the contamination of the electrode while reacting the reactive component.
- the purpose is to ensure sufficient and enhance treatment effects such as adhesion.
- the present invention is a film surface treatment apparatus that activates a reaction component to react on the surface of the film to be treated while conveying a continuous film to be treated,
- a main processing unit disposed relatively upstream in the transport direction; and a reactivation unit disposed relatively downstream in the transport direction;
- the main processing part is arranged in parallel so as to form a main discharge space near atmospheric pressure between each other, and the transport direction from the main discharge space in the film to be processed, the first roll electrode and the second roll electrode
- a nozzle that blows out a reaction gas containing the reaction component toward a portion on the upstream side or toward the main discharge space, and the film to be processed is wound around the first roll electrode, and After being passed through the main discharge space, it is folded and wound around the second roll electrode, and the first roll electrode and the second roll electrode are rotated around their own axes and in the same direction.
- the film to be treated is conveyed from the first roll electrode to the second roll electrode,
- the reactivation unit includes a pair of rear electrodes in which a redischarge space near atmospheric pressure is formed between each other, and a gas supply unit that supplies a discharge generation gas that does not contain the reaction component between the rear electrodes.
- the film to be processed is passed through the re-discharge space, and the opposing surfaces of the pair of subsequent electrodes are flat surfaces, a flat surface and a convex cylindrical surface, or a concave cylindrical surface and a convex cylindrical surface, To do.
- reaction components are reacted to some extent by plasma irradiation in the main discharge space.
- it can prevent that a to-be-processed film covers a 1st roll electrode and a 2nd roll electrode, and a dirt adheres to a 1st, 2nd roll electrode.
- production of a particle can be prevented and a yield can be improved.
- the film to be treated is again irradiated with plasma in the re-discharge space between the pair of subsequent electrodes of the reactivation unit.
- the opposing surfaces of the pair of subsequent electrodes are configured by planes, or one opposing surface is configured as a plane and the other opposing surface is configured as a convex cylindrical surface, or one opposing surface is configured as a concave cylindrical surface and the other opposing surface.
- the path length along the transport direction of the re-discharge space can be made longer than the path length along the transport direction of the main discharge space. Therefore, sufficient energy can be imparted to the surface molecules and reaction components of the film to be treated in the reactivation part, and preferably greater energy than in the main treatment part.
- the reaction component is a polymerizable monomer
- a polymerization reaction can be sufficiently caused, and an odor due to an unpolymerized polymerizable monomer can be prevented from being generated from a treated film after treatment.
- the said to-be-processed film is a protective film of a polarizing plate
- an adhesive promotion layer can be reliably formed in this protective film, and adhesiveness with a polarizing film can be improved. Since the reaction product is not included in the discharge product gas of the reactivation part, it is possible to prevent the dirt from adhering to the electrode in the reactivation part and to prevent generation of particles. Therefore, the yield can be improved reliably.
- One of the pair of post-stage electrodes of the reactivation unit has an opposing surface formed of a flat surface or a concave cylindrical surface and is opposed to the second roll electrode, and the second roll electrode is formed of the reactivation unit. It is preferably provided as the other latter-stage electrode.
- the outer peripheral surface of the second roll electrode constitutes an opposing surface composed of the convex cylindrical surface.
- the power supplied to the reactivation unit is larger than the power supplied to the main processing unit. Thereby, the reactivity in the reactivation part can fully be raised.
- the present invention is a film surface treatment apparatus that activates a reaction component to react on the surface of the film to be treated while conveying a continuous film to be treated, A main processing unit disposed relatively upstream in the transport direction; and a reactivation unit disposed relatively downstream in the transport direction;
- the main processing part is arranged in parallel so as to form a main discharge space near atmospheric pressure between each other, and the transport direction from the main discharge space in the film to be processed, the first roll electrode and the second roll electrode
- a nozzle that blows out a reaction gas containing the reaction component toward a portion on the upstream side or toward the main discharge space, and the film to be processed is wound around the first roll electrode, and After being passed through the main discharge space, it is folded and wound around the second roll electrode, and the first roll electrode and the second roll electrode are rotated around their own axes and in the same direction.
- the film to be treated is conveyed from the first roll electrode to the second roll electrode,
- the second feature is that the reactivation unit includes light energy
- reaction components are reacted to some extent by plasma irradiation. At this time, it can prevent that a to-be-processed film covers a 1st roll electrode and a 2nd roll electrode, and a dirt adheres to a 1st, 2nd roll electrode. As a result, generation
- the reaction component is a polymerizable monomer
- a polymerization reaction can be sufficiently caused, and an odor caused by an unpolymerized polymerizable monomer can be prevented from being generated from a treated film after processing.
- the said to-be-processed film is a protective film of a polarizing plate
- an adhesive promotion layer can be reliably formed in this protective film, and adhesiveness with a polarizing film can be improved.
- light energy it is preferable to use ultraviolet light energy or infrared light energy.
- the surface treatment is preferably performed near atmospheric pressure.
- the vicinity of atmospheric pressure refers to a range of 1.013 ⁇ 10 4 to 50.663 ⁇ 10 4 Pa, and considering the ease of pressure adjustment and the simplification of the apparatus configuration, 1.333 ⁇ 10 4 to 10.664 ⁇ 10 4 Pa is preferable, and 9.331 ⁇ 10 4 to 10.9797 ⁇ 10 4 Pa is more preferable.
- the present invention is suitable for processing difficult-to-adhere optical resin films.
- the adhesiveness of the hardly-adhesive optical resin film is improved. It is suitable for improving.
- the main component of the hardly adhesive optical resin film include triacetate cellulose (TAC), polypropylene (PP), polyethylene (PE), cycloolefin polymer (COP), cycloolefin copolymer (COC), and polyethylene terephthalate. (PET), polymethyl methacrylate (PMMA), polyimide (PI) and the like.
- Examples of the main component of the easily adhesive optical resin film include polyvinyl alcohol (PVA) and ethylene vinyl acetate copolymer (EVA).
- PVA polyvinyl alcohol
- EVA ethylene vinyl acetate copolymer
- a polymerizable monomer As the reaction component, it is preferable to use a polymerizable monomer as the reaction component.
- the polymerizable monomer include monomers having an unsaturated bond and a predetermined functional group.
- the predetermined functional group is preferably selected from a hydroxyl group, a carboxyl group, an acetyl group, a glycidyl group, an epoxy group, an ester group having 1 to 10 carbon atoms, a sulfone group, and an aldehyde group.
- a hydrophilic group is preferred.
- Examples of the monomer having an unsaturated bond and a hydroxyl group include ethylene glycol methacrylate, allyl alcohol, and hydroxyethyl methacrylate.
- Examples of the monomer having an unsaturated bond and a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, 2-methacryloylpropionic acid and the like.
- Examples of the monomer having an unsaturated bond and an acetyl group include vinyl acetate.
- Examples of the monomer having an unsaturated bond and a glycidyl group include glycidyl methacrylate.
- Monomers having an unsaturated bond and an ester group include methyl acrylate, ethyl acrylate, butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid
- Examples include butyl, t-butyl methacrylate, isopropyl methacrylate and 2-ethyl methacrylate.
- Examples of the monomer having an unsaturated bond and an aldehyde group include acrylic aldehyde and crotonaldehyde.
- the polymerizable monomer is a monomer having an ethylenically unsaturated double bond and a carboxyl group.
- examples of such monomers include acrylic acid (CH 2 ⁇ CHCOOH) and methacrylic acid (CH 2 ⁇ C (CH 3 ) COOH).
- the polymerizable monomer is preferably acrylic acid or methacrylic acid. Thereby, the adhesiveness of a hardly-adhesive resin film can be improved reliably. More preferably, the polymerizable monomer is acrylic acid.
- the polymerizable monomer may be conveyed by a carrier gas.
- the carrier gas is preferably selected from an inert gas such as nitrogen, argon or helium. From the economical viewpoint, it is preferable to use nitrogen as the carrier gas.
- Many polymerizable monomers such as acrylic acid and methacrylic acid are in a liquid phase at normal temperature and pressure. Such a polymerizable monomer may be vaporized in a carrier gas such as an inert gas.
- a method of vaporizing the polymerizable monomer into the carrier gas a method of extruding a saturated vapor on the surface of the polymerizable monomer solution with the carrier gas, a method of bubbling the carrier gas into the polymerizable monomer solution, a polymerizable monomer solution
- a method of promoting evaporation by heating can be used. Extrusion and heating, or bubbling and heating may be used in combination.
- the reaction of the reactive component can be sufficiently ensured while preventing contamination of the electrode, and the processing effect is improved. Can be increased.
- FIG. 1 shows a first embodiment of the present invention.
- the film 9 to be processed has a continuous sheet shape.
- a protective film for a polarizing plate is applied as the film 9 to be processed.
- the protective film 9 contains triacetate cellulose (TAC) as a main component.
- TAC triacetate cellulose
- the components of the film 9 are not limited to TAC, but polypropylene (PP), polyethylene (PE), cycloolefin polymer (COP), cycloolefin copolymer (COC), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA), polyimide (PI), or the like may be used.
- the thickness of the film 9 is, for example, about 100 ⁇ m.
- a polarizing film made of a PVA film and a protective film are bonded together with an adhesive to constitute a polarizing plate.
- an aqueous adhesive such as an aqueous PVA solution is used.
- the protective film is surface-treated by the film surface treatment apparatus 1 to improve the adhesion of the protective film.
- the film surface treatment apparatus 1 includes a main treatment unit 10 and a reactivation unit 30.
- the protective film 9 to be processed is conveyed in a substantially right direction with the width direction orthogonal to the paper surface in FIG.
- the main processing unit 10 is arranged on the upstream side (left side in FIG. 1) of the film 9 to be processed, and the reactivation unit 30 is arranged on the downstream side (right side in FIG. 1) of the film 9 to be processed. ing.
- the main processing unit 10 includes a pair of electrodes 11 and 12 and gas nozzles 21, 22 and 23.
- the electrodes 11 and 12 have a roll shape (cylindrical shape). Roll electrodes 11 and 12 are arranged in parallel to each other with their respective axes oriented in a horizontal direction perpendicular to the paper surface of FIG.
- a direction along the axis of the electrodes 11 and 12 is appropriately referred to as a “process width direction” (see FIG. 2).
- the left first roll electrode 11 is connected to a power source 18.
- the second roll electrode 12 on the right side is electrically grounded.
- the power source 18 supplies, for example, pulsed high frequency power to the electrode 11.
- a plasma discharge is generated between the electrodes 11 and 12 under a pressure near atmospheric pressure.
- a space between the portions of the roll electrodes 11 and 12 facing each other becomes a main discharge space 19 near atmospheric pressure.
- the narrowest portion between the roll electrodes 11 and 12 and the space in the vicinity thereof become the main discharge space 19.
- the main discharge space 19 is defined by the outer peripheral surfaces formed by the convex cylindrical surfaces of the roll electrodes 11 and 12, the path length in the vertical direction (vertical direction) is short. For example, when the diameter of the roll electrodes 11 and 12 is about 310 mm, the vertical path length of the main discharge space 19 is about 40 mm.
- the film 9 to be treated is wound around the upper peripheral surface of the first roll electrode 11 about a half turn.
- the film to be processed 9 is passed through the main discharge space 19 along the peripheral surface of the first roll electrode 11, is hung below the main discharge space 19, and is folded up by the guide rolls 16 and 16. Further, the film 9 to be processed is passed through the main discharge space 19 along the peripheral surface of the second roll electrode 12, and is wound around the upper peripheral surface of the second roll electrode 12 about a half turn. About half a circumference including a portion defining the main discharge space 19 of both roll electrodes 11 and 12 is covered with the film 9 to be processed.
- the rotation mechanism includes a drive unit such as a motor or an internal combustion engine, and a transmission unit that transmits the driving force of the drive unit to the shafts of the roll electrodes 11 and 12.
- the transmission means is constituted by, for example, a belt / pulley mechanism or a gear train.
- the roll electrodes 11 and 12 are rotated around their own axes and in the same direction (clockwise in FIG. 1) in synchronization with each other by the rotation mechanism. . Thereby, the to-be-processed film 9 is conveyed from the 1st roll electrode 11 to the 2nd roll electrode 12.
- Temperature control means (not shown) is incorporated in each roll electrode 11, 12.
- the temperature adjusting means is constituted by a temperature adjusting path formed in the roll electrodes 11 and 12, for example.
- the temperature of the roll electrodes 11 and 12 can be controlled by flowing a temperature-controlled medium such as water through the temperature control path.
- a temperature-controlled medium such as water
- Discharge generation gas nozzles 21 and 22 are arranged above and below the main discharge space 19 between the roll electrodes 11 and 12, respectively.
- a discharge generated gas supply source 24 is connected to each of the nozzles 21 and 22.
- the upper nozzle 21 extends long in the processing width direction, and a cross section perpendicular to the extending direction tapers downward.
- the outlet at the lower end (tip) of the nozzle 21 faces the main discharge space 19.
- the upper end of the main discharge space 19 is blocked to some extent by the nozzle 21.
- a rectifying unit (not shown) is provided on the upper side of the nozzle 21, and the discharge generating gas is made uniform in the processing width direction by this rectifying unit and introduced into the nozzle 21. This discharge generated gas is blown out from the blowout port at the lower end of the nozzle 21 into the main discharge space 19.
- the discharge flow of the discharge product gas is a uniformly distributed flow in the processing width direction.
- the lower nozzle 22 has a shape obtained by inverting the upper nozzle 21 up and down. That is, the lower nozzle 22 extends long in the processing width direction, and a cross section perpendicular to the extending direction tapers upward. An outlet at the upper end (tip) of the nozzle 22 faces the main discharge space 19. The lower end portion of the main discharge space 19 is blocked to some extent by the nozzle 22.
- a rectification unit (not shown) is provided at the lower end of the nozzle 22, and the rectification unit makes the discharge generated gas uniform in the processing width direction and introduces it into the nozzle 22. This discharge generated gas is blown out from the outlet of the nozzle 22 into the main discharge space 19.
- the discharge flow of the discharge product gas is a uniformly distributed flow in the processing width direction.
- the discharge generated gas may be blown out from the upper and lower nozzles 21 and 22 at the same time.
- the gas is blown out from only one of the upper and lower nozzles 21 and 22, and the other nozzle is used as a closing member for closing the upper end or the lower end of the main discharge space 19. It may be used.
- the discharge generated gas may be blown out only from the lower nozzle 22 and the gas may not be blown out from the upper nozzle 21.
- An inert gas is used as the discharge product gas.
- nitrogen (N 2) can be mentioned as an inert gas for discharge product gas, not limited to this, Ar, may be used a noble gas such as He.
- the reaction gas nozzle 23 is disposed above the first roll electrode 11 so as to face the electrode 11.
- the reactive gas nozzle 23 is separated from the main discharge space 19 along the circumferential direction of the first roll electrode 11 by about a quarter of the turn in the electrode rotation direction and thus upstream in the film transport direction.
- the reactive gas nozzle 23 faces the film 9 to be processed on the electrode 11 on the upstream side in the transport direction from the main discharge space 19.
- the reactive gas nozzle 23 extends long in the processing width direction and has a certain width in the circumferential direction of the first roll electrode 11 (left and right in FIG. 1).
- a rectification unit is incorporated in the reaction gas nozzle 23.
- An outlet is provided on the lower surface of the reactive gas nozzle 23. The outlets are formed so as to be distributed over a wide range (the processing width direction and the electrode circumferential direction) of the lower surface of the nozzle 23.
- the reaction gas supply source 20 is connected to the nozzle 23.
- the reaction gas from the supply source 20 is supplied to the nozzle 23.
- the reaction gas is made uniform by the rectifying unit and blown out from the blowout port on the lower surface of the nozzle 23.
- the blow-out flow of the reaction gas is a flow that is uniformly distributed in the processing width direction.
- the reaction gas contains a polymerizable monomer as a reaction component.
- acrylic acid AA is used as the polymerizable monomer.
- Acrylic acid has an acetic acid-like odor and has explosive properties, and therefore requires appropriate management.
- the polymerizable monomer is not limited to acrylic acid, and may be methacrylic acid, itaconic acid, maleic acid, or the like.
- the reaction gas further includes a carrier gas in addition to the reaction component (polymerizable monomer).
- An inert gas is used as the carrier gas.
- nitrogen (N 2 ) is used as the inert gas for the carrier gas, but the present invention is not limited to this, and a rare gas such as Ar or He may be used.
- the reactive gas supply source 20 is constituted by a vaporizer.
- Acrylic acid AA is stored in the vaporizer as a polymerizable monomer in a liquid state.
- Nitrogen (N 2 ) is introduced into the vaporizer as a carrier gas.
- Acrylic acid is vaporized and mixed with this carrier gas (N 2 ) to generate a reaction gas (acrylic acid AA + N 2 ).
- the carrier gas may be introduced above the liquid acrylic acid level in the vaporizer, or may be introduced into the liquid acrylic acid and bubbled. A part of the carrier gas may be introduced into the vaporizer and the remaining part may not be passed through the vaporizer, and the part of the carrier gas and the remaining part may be merged on the downstream side of the vaporizer.
- the acrylic acid concentration in the reaction gas can be adjusted according to the temperature of the vaporizer and the distribution ratio of the part and the remainder of the carrier gas.
- the reaction gas supply line from the reaction gas supply source 20 to the nozzle 23 is temperature-controlled by a reaction gas temperature adjusting means (not shown) such as a ribbon heater.
- a shielding member 40 is provided at the bottom of the reaction gas nozzle 23.
- the shielding member 40 has a curved plate shape extending in the processing width direction substantially the same length as the electrode 11 and having a cross section orthogonal to the extending direction forming an arc shape along the circumferential direction of the first roll electrode 11.
- the reaction gas nozzle 23 is connected to the central portion of the shielding member 40 in the arc direction (left and right in FIG. 1). Both ends of the shielding member 40 in the arc direction extend from the nozzle 23 in the circumferential direction of the electrode 11.
- the end of the shielding member 40 on the nozzle 21 side (right side in FIG. 1) is abutted against and connected to the side of the nozzle 21.
- the shielding member 40 is placed slightly above the first roll electrode 11.
- the shielding member 40 covers the upper peripheral surface of the first roll electrode 11 to some extent.
- a shielding space 41 is formed between the shielding member 40 and the peripheral surface of the first roll electrode 11.
- the shielding space 41 is along the upper peripheral surface of the first roll electrode 11.
- the outlet on the lower surface of the reactive gas nozzle 23 penetrates the shielding member 40 and communicates with the shielding space 41.
- An end portion of the shielding space 41 on the nozzle 21 side (right side in FIG. 1) is connected to the main discharge space 19 through a space between the nozzle 21 and the peripheral surface of the first roll electrode 11.
- the end of the shielding space 41 opposite to the nozzle 21 (left side in FIG. 1) is open to the outside.
- the film surface treatment apparatus 1 is provided with a reactivation unit 30 in addition to the main treatment unit 10.
- the reactivation unit 30 is disposed downstream of the main discharge space 19 in the transport direction of the film 9 to be processed.
- the reactivation unit 30 includes one or a plurality of (two in the drawing) rear electrodes 31.
- the rear electrode 31 has a flat plate shape extending in the processing width direction.
- Each subsequent-stage electrode 31 is disposed above the second roll electrode 12 and faces the peripheral surface on the upper side of the second roll electrode 12.
- a plurality of subsequent electrodes 31, 31 are arranged at intervals in the circumferential direction of the second roll electrode 12.
- each post-stage electrode 31 in the processing width direction is substantially equal to the axial length of the second roll electrode 12.
- the dimension of each rear electrode 31 along the circumferential direction of the electrode 12 is, for example, about 20 mm to 40 mm.
- the arrangement pitch of the adjacent rear electrodes 31 and 31 is, for example, about 20 mm to 40 mm.
- each rear electrode 31 is a surface 31 a facing the second roll electrode 12.
- the facing surface 31a is a flat surface.
- a solid dielectric 32 is provided on the facing surface 31a.
- the solid dielectric 32 is configured by a flat plate made of ceramic such as alumina, but may be a film coated on the opposing surface 31a by thermal spraying or the like.
- the solid dielectric 32 is not limited to ceramic but may be other dielectrics such as resin.
- a reactivation power supply 38 is connected to each post-stage electrode 31.
- the power supply 38 supplies, for example, pulsed power to each electrode 31.
- an electric field is applied between the grounded second roll electrode 12 and each subsequent electrode 31 to generate a plasma discharge near atmospheric pressure.
- a space between the solid dielectric 32 and the second roll electrode 12 of each rear electrode 31 becomes a re-discharge space 39 near atmospheric pressure.
- the second roll electrode 12 is provided as the other rear electrode that is paired with the rear electrode 31 in the reactivation unit 30.
- one second roll electrode 12 is paired with a plurality of electrodes 31, 31.
- the opposing surface 31a of one rear electrode 31 constituting the reactivation unit 30 is a flat surface, and the opposing surface of the other rear electrode 12 is a convex cylindrical surface. Therefore, the path length along the circumferential direction of the electrode 12 in each redischarge space 39 is larger than the path length of the main discharge space 19. Therefore, the total path length of the plurality of redischarge spaces 39 of the reactivation unit 30 is larger than the path length of the main discharge space 19.
- the power supplied to the reactivation unit 30 is larger than the power supplied to the main processing unit 10.
- the power supplied to the reactivation unit 30 refers to the total power supplied to the plurality of electrodes 31 and 31.
- the power supplied to the reactivation unit 30 is, for example, 1.5 to 2.0 times the power supplied to the main processing unit 10.
- a gas supply unit 33 is connected to each re-discharge space 39.
- the gas supply unit 33 supplies the discharge generated gas to the redischarge space 39.
- the gas supply unit 33 includes a rectification unit and a nozzle.
- the nozzle of the supply unit 33 faces the re-discharge space 39 and extends in the processing width direction.
- the discharge generated gas is made uniform in the processing width direction by the rectifying unit of the supply unit 33 and then blown out from the nozzle to the re-discharge space 39.
- the discharge flow of the discharge product gas is uniformly distributed in the processing width direction.
- Nitrogen (N 2 ) is used as the discharge product gas of the gas supply unit 33.
- An inert gas other than nitrogen for example, a rare gas such as Ar or He
- the discharge generated gas of the gas supply unit 33 does not contain a polymerizable monomer.
- the discharge generated gas supply source of the gas supply unit 33 may be shared with the discharge generated gas supply source of the nozzles 21 and 22.
- a supply path extending from one discharge generation gas supply source may be branched and connected to the nozzles 21 and 22 and the gas supply unit 33.
- a method for surface-treating the film 9 to be processed by the film surface treatment apparatus 1 having the above configuration will be described.
- the film to be treated 9 is wound around the roll electrodes 11 and 12.
- the roll electrodes 11 and 12 are rotated clockwise in FIG. 1, and the film 9 to be processed is conveyed substantially rightward in FIG.
- a reactive gas (acrylic acid + N 2 ) is introduced from the supply source 20 into the nozzle 23 and blown out from the nozzle 23 into the shielding space 41. This reaction gas comes into contact with the film to be processed 9 on the upper peripheral surface of the first roll electrode 11, and acrylic acid (reaction component) in the reaction gas is condensed and adheres to the film to be processed 9.
- the shielding member 40 can confine the reaction gas in the shielding space 41 and can prevent or suppress the leakage of acrylic acid into the external atmosphere. As a result, the opportunity for acrylic acid to contact the film 9 to be processed can be increased, and acrylic acid can be reliably attached to the film 9 to be processed. In addition, atmospheric gas containing oxygen such as external air can be prevented from entering the shielded space 41.
- the portion of the film 9 to which the acrylic acid adheres is introduced into the main discharge space 19 by the conveyance of the film 9 to be processed.
- a discharge generated gas (N 2 ) is supplied to the main discharge space 19 from the nozzle 21 or 22.
- power is supplied to the electrode 11 to generate an atmospheric pressure plasma discharge in the main discharge space 19.
- the nitrogen of the discharge product gas is turned into plasma and nitrogen plasma is generated.
- the nitrogen plasma or plasma light is irradiated to the film 9 to be processed, and the bonds such as CC, C—O, and C—H of the surface molecules of the film 9 are cut.
- the acrylic acid on the surface of the film to be processed 9 is activated by the plasma, the double bond is cleaved, polymerized, etc., and the polymer of acrylic acid is bonded to the bond cutting part of the film to be processed 9 (graft polymerization).
- graft polymerization it is considered that a COOH group decomposed from acrylic acid is bonded.
- an adhesion promoting layer is formed on the surface of the film 9 to be processed. Since the shielding member 40 can prevent the outside atmosphere from entering, the reaction in the main discharge space 19 can be prevented or suppressed by oxygen in the outside atmosphere.
- the film 9 to be processed passes through the main discharge space 19 in contact with the first roll electrode 11, is turned back by the guide roll 16, and passes through the main discharge space 19 again in contact with the second roll electrode 12. Therefore, the film to be processed 9 is processed twice in the main discharge space 19.
- the film 9 to be processed moves in the circumferential direction of the second roll electrode 12 and is introduced into the redischarge space 39 of the reactivation unit 30.
- a discharge generated gas (N 2 ) is supplied from the gas supply unit 33 to the re-discharge space 39.
- power is supplied to the electrode 31 to generate an atmospheric pressure plasma discharge in the redischarge space 39.
- nitrogen in the discharge generated gas is turned into plasma in the redischarge space 39 to generate nitrogen plasma.
- the bond molecules such as C—C—C—O—C—H, etc. of the surface molecules of the film to be processed 9 again occur.
- unpolymerized acrylic acid on the surface of the film 9 to be processed and acrylic acid having a low degree of polymerization are activated, and polymerization proceeds. It is considered that this polymer of acrylic acid is bonded (graft polymerization) to the bond cutting portion of the film 9 to be processed, or a COOH group decomposed from acrylic acid is bonded.
- the film to be processed 9 and the acrylic acid on the surface thereof can be exposed to the plasma for a longer time than the main discharge space 19.
- Sufficient energy can be imparted to the surface molecules and acrylic acid. Thereby, it can fully polymerize without remaining acrylic acid, and can form an adhesion promotion layer on the surface of the to-be-processed film 9 reliably. Accordingly, it is possible to prevent an acetic acid-like odor peculiar to acrylic acid from being processed.
- the film to be processed 9 and the PVA film can be reliably bonded with the water-based adhesive, and an unbonded portion can be prevented from being formed. Therefore, a polarizing plate having good adhesive strength can be manufactured.
- the film 9 to be processed covers the roll electrodes 11 and 12, particularly the portions that define the discharge space 19, it is possible to prevent the electrodes 11 and 12 from being contaminated. Further, since acrylic acid (reaction component) is not supplied to the reactivation unit 30, contamination of the electrode 31 can be prevented or suppressed. Accordingly, generation of particles can be prevented or suppressed, and the yield can be improved.
- the second roll electrode 12 as an electrode element of the reactivation unit 30, the number of parts can be reduced and the device configuration can be simplified.
- one roll electrode 12 is paired with a plurality of subsequent electrodes 31, 31, the number of parts can be further reduced, and the device configuration can be further simplified. Since the number of roll electrodes in the entire film surface treatment apparatus 1 is two and the electrode 31 can be composed of a metal flat plate or the like, an increase in manufacturing cost of the film surface treatment apparatus 1 can be suppressed.
- FIG. 3 shows a film surface treatment apparatus 1A according to the second embodiment of the present invention.
- the film surface treatment apparatus 1A of the second embodiment is different from the film surface treatment apparatus 1 (FIG. 1) of the first embodiment in that the reaction gas nozzle 23 and the shielding member 40 of the main processing unit 10 are omitted.
- a reactive gas supply source 20 is connected to the upper nozzle 21.
- the reactive gas supply source 20 may be connected to the lower nozzle 22 instead of the upper nozzle 21, or may be connected to both the upper nozzle 21 and the lower nozzle 22.
- the reaction gas (acrylic acid AA + N 2 ) is sent from the supply source 20 to the nozzle 21 and blown out from the nozzle 21 into the main discharge space 19. Therefore, the acrylic acid is sprayed onto the film 9 to be treated and the polymerization reaction is performed almost simultaneously, and an adhesion promoting layer is formed.
- the carrier gas (N 2 ) in the reaction gas also serves as a discharge product gas and is converted into plasma in the main discharge space 19, thereby contributing to the formation of the adhesion promoting layer.
- FIG. 4 shows a film surface treatment apparatus 1B according to the third embodiment of the present invention.
- the film surface treatment apparatus 1B includes three roll electrodes 11, 12, and 34 as a whole. Three roll electrodes 11, 12, and 34 are arranged in a line in this order. A film to be processed 9 is wound around these roll electrodes 11, 12 and 34.
- the electrode rotation mechanism is connected to the third roll electrode 34 in addition to the first and second roll electrodes 11 and 12.
- the three roll electrodes 11, 12, and 34 rotate in synchronization with each other, and the film 9 to be processed is conveyed rightward in FIG. 4 in the order of the first roll electrode 11, the second roll electrode 12, and the third roll electrode 34.
- the power source 18 is connected not to the first roll electrode 11 but to the central second roll electrode 12.
- the first roll electrode 11 and the third roll electrode 34 are electrically grounded. Therefore, the ground electrode 11, the hot electrode 12, and the ground electrode 34 are arranged in this order along the transport direction of the film 9 to be processed.
- a main discharge space 19 is formed between the first and second roll electrodes 11 and 12. Furthermore, a discharge space is also formed between the second roll electrode 12 and the third roll electrode 34.
- a discharge generated gas such as nitrogen may be supplied also to the discharge space between the electrodes 12 and 34.
- the third roll electrode 34 constitutes the other rear electrode paired with the rear electrode 31 in the reactivation unit 30.
- One or a plurality of (two in the figure) rear electrodes 31 are disposed above the roll electrode 34 instead of the second roll electrode 12.
- a facing surface 31 a forming a flat surface of each electrode 31 faces a circumferential surface forming a convex cylindrical surface of the roll electrode 34.
- a redischarge space 39 is formed between each electrode 31 and the roll electrode 34.
- the discharge between the second and third roll electrodes 12 and 34 is performed.
- Plasma treatment can be performed again in the space.
- the to-be-processed film 9 can be introduce
- acrylic acid can be more fully polymerized and an adhesion promoting layer can be reliably formed. Since the to-be-processed film 9 has covered all (three) roll electrodes 11, 12, and 34, it can prevent that these electrodes 11, 12, and 34 become dirty.
- FIG. 5 shows a film surface treatment apparatus 1C according to the fourth embodiment of the present invention.
- a light energy irradiation unit 50 is provided as a reactivation unit subsequent to the main processing unit 10 in place of the plasma processing unit 30.
- the light energy irradiation means 50 is constituted by an infrared lamp or an ultraviolet lamp.
- the light energy irradiation means 50 is arranged to face the film 9 to be processed on the downstream side in the transport direction from the second roll electrode 12.
- the light emitting part of the light energy irradiation means 50 extends in the processing width direction (direction orthogonal to the paper surface of FIG. 5) for substantially the same length as the film 9.
- the light energy irradiation means 50 may be disposed so as to face the peripheral surface of the second roll electrode 12.
- the infrared light or ultraviolet light 51 (light energy) from the light energy irradiation means 50 is irradiated almost uniformly in the processing width direction on the film 9 after passing through the main processing portion 10. Thereby, energy can be provided again to the surface molecules of the film to be processed 9 and acrylic acid, and the polymerization reaction of acrylic acid can be caused again.
- acrylic acid can be sufficiently polymerized to reliably form the adhesion promoting layer on the surface of the film 9 to be processed, and the adhesion can be improved.
- the number of the rear electrodes 31 of the reactivation unit 30 may be one or may be three or more.
- the electrode structure of the reactivation unit 30 may be such that the path length of the redischarge space 39 is longer than the path length of the discharge space 19 of the electrodes 11 and 12 with the convex cylindrical surfaces of the main processing unit 10 facing each other. It is not limited to the combination of the electrode 31 and the electrodes 12 and 34 in which the plane and the convex cylindrical surface are opposed to each other.
- the reactivation part 30 may be comprised with the parallel plate electrode with which both electrodes 35 and 35 made plane 35a, 35a and each face each other.
- the film to be processed 9 is passed between the electrodes 35 and 35.
- the opposing surface of one electrode 36 of the reactivation unit 30 may be a concave cylindrical surface 36a, and the opposing surface of the other electrode 37 may be a convex cylindrical surface 37a.
- the electrode 37 is preferably composed of a roll electrode.
- the film to be processed 9 is wound around the electrode 37.
- a concave cylindrical surface electrode 36 may be used instead of the flat plate electrode 31.
- the reactivation unit may include a plasma processing unit 30 including a pair of electrodes and a light energy irradiation unit 50.
- the present invention is not limited to the surface treatment of the protective film for a polarizing plate, but can be applied to the surface treatment of various resin films. Furthermore, the present invention is not limited to the plasma polymerization treatment of polymerizable monomers, but can be applied to various plasma surface treatments such as plasma CVD, plasma cleaning, and plasma surface modification. In these various plasma surface treatments, a sufficient degree of treatment can be obtained, dirt can be prevented from adhering to the roll electrodes 11 and 12 of the main treatment unit 10, and the electrode 31 of the reactivation unit 30 and the like. Can be suppressed or prevented from being contaminated by the reaction component, and as a result, generation of particles can be prevented and yield can be improved.
- the reaction component of the reaction gas is appropriately selected according to the processing content. For example, as a reaction component used in plasma CVD, TMOS (tetramethoxysilane), TEOS (tetraethoxysilane), and the like can be given.
- Example 1 using the film surface treatment apparatus 1 shown in FIG. 1, following the plasma treatment by the main treatment unit 10, re-plasma treatment by the reactivation unit 30 was performed.
- a TAC film was used as the film 9 to be processed.
- the width of the TAC film 9 was 330 mm.
- the conveyance speed of the TAC film 9 was 15 m / min.
- the temperature of the electrodes 11 and 12, and thus the temperature of the TAC film 9, was set to 25 ° C.
- Acrylic acid was used as the polymerizable monomer for the reaction gas, and nitrogen was used as the carrier gas.
- the temperature of the liquid acrylic acid in the vaporizer 20 was set to 70 ° C.
- the discharge generated gas (N 2 ) was blown out only from the lower nozzle 22 among the upper and lower nozzles 21, 22 and supplied to the main discharge space 19.
- the gas blowing width of the nozzle 22 was 325 mm.
- the N 2 supply flow rate from the nozzle 22 was 20 slm.
- the diameter of each roll electrode 11 and 12 was 320 mm.
- the axial length of each roll electrode 11 and 12 was 340 mm.
- the gap (the thickness of the main discharge space 19) at the narrowest portion between the roll electrodes 11 and 12 was 1 mm.
- the power supplied to the electrode 11 was 1100W.
- each post-stage electrode 31 in the processing width direction was 340 mm.
- latter stage electrode 31 was 20 mm.
- the distance between the lower surface 31a of each electrode 31 and the outer peripheral surface of the second roll electrode 12 was 1 mm.
- the thickness of the solid dielectric 32 was 1 mm.
- the power supplied to each electrode 31 was 600W. Therefore, the total supply power of the two electrodes 31 was 1200 W.
- the supply flow rate of the discharge generated gas (N 2 ) to each redischarge space 39 was 20.0 L / min.
- the TAC film after the surface treatment did not have an acetic acid odor peculiar to acrylic acid.
- pH 7.
- a pH meter manufactured by Testo Co., Ltd., model number TETO230 was used for pH measurement. The above pH measurement results indicate that almost no acrylic acid remains as a monomer on the surface of the TAC film, and the polymerization reaction has been sufficiently performed.
- the to-be-treated TAC film 9 after the surface treatment was bonded to one side of the PVA film.
- an aqueous solution obtained by mixing (A) a 5 wt% PVA aqueous solution with a polymerization degree of 500 and (B) a 2 wt% aqueous sodium carboxymethylcellulose solution was used.
- the adhesive was dried at 80 ° C. for 5 minutes.
- a saponified TAC film was bonded to the opposite surface of the PVA film with the same adhesive as described above. Thereby, a polarizing plate sample having a three-layer structure was produced.
- the width of the polarizing plate sample was 25 mm.
- the adhesive strength between the treated TAC film 9 and the PVA film was measured by the floating roller method (JIS K6854). As a result of the measurement, the adhesive strength was 9.8 N / 25 mm.
- Example 1 a polarizing plate sample was produced and the adhesive strength was measured. As a result of the measurement, the adhesive strength was 8.5 N / 25 mm. According to the present invention, by providing the reactivation part 30 and performing the replasma treatment, it was possible to increase the adhesive strength by 1 N / 25 mm or more compared to the case where the replasma treatment was not performed (Comparative Example 1).
- Example 2 the film surface treatment apparatus 1 ⁇ / b> C shown in FIG. 5 was used, and light irradiation by the light energy irradiation means 50 was performed following the plasma processing by the main processing unit 10.
- the plasma processing conditions in the main processing unit 10 are the same as those in the first embodiment.
- an infrared lamp manufactured by Hybek, model number HYP45
- the distance between the light exit surface of the light energy irradiation means 50 and the TAC film 9 was 10 mm.
- the wavelength of the irradiation light from the light energy irradiation means 50 was 0.8 ⁇ m, and the illuminance was 15 W / cm 2 .
- the TAC film after the surface treatment did not give an acetic acid odor peculiar to acrylic acid.
- a sample was prepared and the adhesive strength was measured. As a result of the measurement, the adhesive strength was 9.5 N / 25 mm.
- the present invention is applicable, for example, to the manufacture of flat panel display (FPD) polarizing plates and various semiconductor devices.
- FPD flat panel display
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Abstract
Description
本発明は、上記事情に鑑み、重合性モノマー等の反応成分を活性化させて偏光板用保護フィルム等の被処理フィルムをプラズマ処理する際、電極の汚れを防止しつつ、反応成分の反応を十分に確保し、接着性等の処理効果を高めることを目的とする。
前記搬送方向の相対的に上流側に配置された主処理部と、前記搬送方向の相対的に下流側に配置された再活性化部とを備え、
前記主処理部が、互いの間に大気圧近傍の主放電空間を形成するよう平行に配置された第1ロール電極及び第2ロール電極と、前記被処理フィルムにおける前記主放電空間より前記搬送方向の上流側の部分に向けて又は前記主放電空間に向けて前記反応成分を含有する反応ガスを吹き出すノズルと、を含み、前記被処理フィルムが、前記第1ロール電極に掛け回され、かつ前記主放電空間に通された後に折り返されて前記第2ロール電極に掛け回され、前記第1ロール電極及び第2ロール電極が、それぞれ自らの軸線まわりに、かつ互いに同方向に回転されることにより、前記被処理フィルムが前記第1ロール電極から前記第2ロール電極へ搬送され、
前記再活性化部が、互いの間に大気圧近傍の再放電空間が形成される一対の後段電極と、これら後段電極間に前記反応成分を含まない放電生成ガスを供給するガス供給部とを含み、前記再放電空間に前記被処理フィルムが通され、前記一対の後段電極の対向面が、平面どうし、平面と凸円筒面、又は凹円筒面と凸円筒面であることを第1特徴とする。
その後、再活性化部の一対の後段電極間の再放電空間において、被処理フィルムに再度プラズマ照射を行なう。一対の後段電極の対向面を平面どうしにて構成し、又は一方の対向面を平面、他方の対向面を凸円筒面にて構成し、又は一方の対向面を凹円筒面、他方の対向面を凸円筒面にて構成することによって、再放電空間の前記搬送方向に沿う路長を、前記主放電空間の前記搬送方向に沿う路長より長くできる。したがって、再活性化部において被処理フィルムの表面分子及び反応成分に十分なエネルギーを付与でき、好ましくは主処理部よりも大きなエネルギーを付与できる。これにより、主処理部における処理だけでは反応が不十分であっても、更に再活性化部を経ることによって十分な反応度を得ることができ、ひいては処理効果を高めることができる。
前記反応成分が重合性モノマーである場合、十分に重合反応を起こすことができ、処理後の被処理フィルムから未重合の重合性モノマーに起因する臭気が発生するのを防止できる。前記被処理フィルムが偏光板の保護フィルムである場合、該保護フィルムに接着性促進層を確実に形成でき、偏光フィルムとの接着性を高めることができる。
再活性化部の放電生成ガスには反応成分が含まれないため、再活性化部において電極に汚れが付着するのを防止でき、パーティクルの発生を防止できる。よって、歩留まりを確実に向上できる。
第2ロール電極の外周面が、前記凸円筒面からなる対向面を構成する。主処理部の第2ロール電極を再活性化部の電極要素として兼用することで、装置構造を簡素化でき、製造コストを低廉化できる。
これにより、再活性化部における反応度を十分に高めることができる。
前記搬送方向の相対的に上流側に配置された主処理部と、前記搬送方向の相対的に下流側に配置された再活性化部とを備え、
前記主処理部が、互いの間に大気圧近傍の主放電空間を形成するよう平行に配置された第1ロール電極及び第2ロール電極と、前記被処理フィルムにおける前記主放電空間より前記搬送方向の上流側の部分に向けて又は前記主放電空間に向けて前記反応成分を含有する反応ガスを吹き出すノズルと、を含み、前記被処理フィルムが、前記第1ロール電極に掛け回され、かつ前記主放電空間に通された後に折り返されて前記第2ロール電極に掛け回され、前記第1ロール電極及び第2ロール電極が、それぞれ自らの軸線まわりに、かつ互いに同方向に回転されることにより、前記被処理フィルムが前記第1ロール電極から前記第2ロール電極へ搬送され、
前記再活性化部が、前記被処理フィルムに光エネルギーを照射する光エネルギー照射手段を含むことを第2特徴とする。
その後、光エネルギー照射手段から光エネルギーを被処理フィルムに照射する。これにより、主処理部における処理だけでは反応が不十分であっても、更に光エネルギー照射手段を経ることによって十分な反応度を得ることができ、ひいては処理効果を高めることができる。
前記反応成分が重合性モノマーである場合、十分に重合反応を起こすことができ、処理後の被処理フィルムから未重合の重合性モノマーに起因する臭気が発生するのを防止できる。前記被処理フィルムが偏光板の保護フィルムである場合、該保護フィルムに接着性促進層を確実に形成でき、偏光フィルムとの接着性を高めることができる。 光エネルギーとしては、紫外光エネルギー又は赤外光エネルギーを用いるのが好ましい。
前記難接着性の光学樹脂フィルムの主成分としては、例えばトリアセテートセルロース(TAC)、ポリプロピレン(PP)、ポリエチレン(PE)、シクロオレフィン重合体(COP)、シクロオレフィン共重合体(COC)、ポリエチレンテレフタレート(PET)、ポリメタクリル酸メチル(PMMA)、ポリイミド(PI)等が挙げられる。
前記重合性モノマーとしては、不飽和結合及び所定の官能基を有するモノマーが挙げられる。所定の官能基は、水酸基、カルボキシル基、アセチル基、グリシジル基、エポキシ基、炭素数1~10のエステル基、スルホン基、アルデヒド基から選択されることが好ましく、特に、カルボキシル基や水酸基等の親水基が好ましい。
不飽和結合及びカルボキシル基を有するモノマーとしては、アクリル酸、メタクリル酸、イタコン酸、マイレン酸、2-メタクリロイルプロピオン酸等が挙げられる。
不飽和結合及びアセチル基を有するモノマーとしては、酢酸ビニル等が挙げられる。
不飽和結合及びグリシジル基を有するモノマーとしては、メタクリル酸グリシジル等が挙げられる。
不飽和結合及びエステル基を有するモノマーとしては、アクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸t-ブチル、アクリル酸2-エチルヘキシル、アクリル酸オクチル、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸t-ブチル、メタクリル酸イソプロピル、メタクリル酸2-エチル等が挙げられる。
不飽和結合及びアルデヒド基を有するモノマーとしては、アクリルアルデヒド、クロトンアルデヒド等が挙げられる。
アクリル酸やメタクリル酸等の重合性モノマーの多くは、常温常圧で液相である。そのような重合性モノマーは、不活性ガス等のキャリアガス中に気化させるとよい。重合性モノマーをキャリアガス中に気化させる方法としては、重合性モノマー液の液面上の飽和蒸気をキャリアガスで押し出す方法、重合性モノマー液中にキャリアガスをバブリングする方法、重合性モノマー液を加熱して蒸発を促進させる方法等が挙げられる。押し出しと加熱、又はバブリングと加熱を併用してもよい。
図1は、本発明の第1実施形態を示したものである。被処理フィルム9は、連続シート状になっている。ここでは、被処理フィルム9として、偏光板の保護フィルムが適用されている。保護フィルム9は、トリアセテートセルロース(TAC)を主成分として含む。なお、フィルム9の成分は、TACに限られず、ポリプロピレン(PP)、ポリエチレン(PE)、シクロオレフィン重合体(COP)、シクロオレフィン共重合体(COC)、ポリエチレンテレフタレート(PET)、ポリメタクリル酸メチル(PMMA)、ポリイミド(PI)等であってもよい。フィルム9の厚さは、例えば100μm程度である。
反応ガス供給源20からノズル23に至る反応ガス供給ラインは、リボンヒータ等の反応ガス温度調節手段(図示省略)にて温調されている。
ガス供給部33の放電生成ガス供給源を、ノズル21,22の放電生成ガス供給源と共有化してもよい。1つの放電生成ガス供給源から延びる供給路が分岐して、ノズル21,22とガス供給部33に連なっていてもよい。
ロール電極11,12に被処理フィルム9を掛け回す。
ロール電極11,12を図1において時計周りに回転させ、被処理フィルム9を図1において概略右方向に搬送する。
反応ガス(アクリル酸+N2)を供給源20からノズル23に導入し、ノズル23から遮蔽空間41に吹き出す。この反応ガスが、第1ロール電極11の上側の周面上の被処理フィルム9に接触し、反応ガス中のアクリル酸(反応成分)が凝縮して、被処理フィルム9に付着する。
遮蔽部材40によって、反応ガスを遮蔽空間41内に閉じ込めることができ、アクリル酸が外部雰囲気中に漏れるのを防止又は抑制できる。ひいては、アクリル酸が被処理フィルム9に接触する機会を増やし、アクリル酸を被処理フィルム9に確実に付着させることができる。また、外部の空気等の酸素を含む雰囲気ガスが遮蔽空間41に侵入するのを防止できる。
主放電空間19にノズル21又は22から放電生成ガス(N2)を供給する。併行して、電極11に電力を供給し、主放電空間19内に大気圧プラズマ放電を生成する。これにより、主放電空間19内において放電生成ガスの窒素がプラズマ化されて窒素プラズマが生成される。この窒素プラズマやプラズマ光が被処理フィルム9に照射され、被処理フィルム9の表面分子のC-C、C-O、C-H等の結合を切断する。更に、プラズマによって被処理フィルム9の表面のアクリル酸が活性化され、二重結合の開裂、重合等が起き、上記被処理フィルム9の結合切断部にアクリル酸の重合物が結合(グラフト重合)し、或いはアクリル酸から分解したCOOH基等が結合すると考えられる。これにより、被処理フィルム9の表面に接着性促進層が形成される。
遮蔽部材40にて外部雰囲気の進入を防止できるため、外部雰囲気中の酸素によって主放電空間19内での反応が阻害されるのを防止又は抑制できる。
再放電空間39にガス供給部33から放電生成ガス(N2)を供給する。併行して、電極31に電力を供給し、再放電空間39内に大気圧プラズマ放電を生成する、これにより、再放電空間39内において放電生成ガスの窒素がプラズマ化されて窒素プラズマが生成される。この窒素プラズマやプラズマ光が被処理フィルム9に照射されることにより、再び被処理フィルム9の表面分子のC-C、C-O、C-H等の結合切断が起きる。更に、被処理フィルム9の表面の未重合のアクリル酸や重合度が低いアクリル酸が活性化されて重合が進む。このアクリル酸の重合物が上記被処理フィルム9の結合切断部に結合(グラフト重合)し、或いはアクリル酸から分解したCOOH基等が結合すると考えられる。
フィルム表面処理装置1全体でロール電極の数は2つであり、かつ電極31は金属平板等にて構成できるから、フィルム表面処理装置1の製造コストの上昇を抑えることができる。
図3は、本発明の第2実施形態に係るフィルム表面処理装置1Aを示したものである。第2実施形態のフィルム表面処理装置1Aは、主処理部10の反応ガスノズル23及び遮蔽部材40が省略されている点で第1実施形態のフィルム表面処理装置1(図1)と異なる。反応ガス供給源20が上ノズル21に接続されている。反応ガス供給源20を、上ノズル21に代えて下ノズル22に接続してもよく、上ノズル21及び下ノズル22の両方に接続してもよい。
被処理フィルム9が、全て(3つ)のロール電極11,12,34を覆っているため、これら電極11,12,34が汚れるのを防止できる。
光エネルギー照射手段50を第2ロール電極12の周面と対面するよう配置してもよい。
例えば、第1~第3実施形態において、再活性化部30の後段電極31の数は、1つでもよく、3つ以上でもよい。
再活性化部30の電極構造は、再放電空間39の路長が、主処理部10の凸円筒面どうしを対向させた電極11,12の放電空間19の路長より長いものであればよく、平面と凸円筒面とを対向させた電極31と電極12,34との組み合わせに限られない。例えば、図6(a)に示すように、再活性化部30は、両方の電極35,35が平面35a,35a,どうしを対向させた平行平板電極にて構成されていてもよい。これら電極35,35間に被処理フィルム9が通される。或いは、図6(b)に示すように、再活性化部30の一方の電極36の対向面が凹円筒面36aであり、他方の電極37の対向面が凸円筒面37aであってもよい。電極37は、ロール電極にて構成されているのが好ましい。電極37に被処理フィルム9が巻き付けられる。第1~第3実施形態において、平板電極31に代えて、凹円筒面電極36を用いてもよい。
第1、第3、第4実施形態において、遮蔽部材40を省略してもよい。
複数の実施形態を互いに組み合わせてもよい。例えば、第2実施形態の主処理部10の構造を第3~第4実施形態に適用してもよい。
再活性化部が、一対の電極を含むプラズマ処理部30と、光エネルギー照射手段50とを含んでいてもよい。
反応ガスの反応成分は、処理内容に応じて適宜選択される。例えば、プラズマCVDで用いる反応成分としては、TMOS(テトラメトキシシラン)、TEOS(テトラエトキシシラン)等が挙げられる。
実施例1では、図1に示すフィルム表面処理装置1を用い、主処理部10によるプラズマ処理に引き続いて、再活性化部30による再プラズマ処理を行なった。
被処理フィルム9として、TACフィルムを用いた。TACフィルム9の幅は、330mmであった。
TACフィルム9の搬送速度は、15m/minとした。
電極11,12の温度、ひいてはTACフィルム9の温度は、25℃に設定した。
反応ガスの重合性モノマーとしてアクリル酸を用い、キャリアガスとして窒素を用いた。
気化器20内の液体アクリル酸の温度は70℃とした。
キャリアガス(N2)の流量、ひいては反応ガス(アクリル酸+N2)の流量は、40slmとした。
上下のノズル21,22のうち下ノズル22からのみ放電生成ガス(N2)を吹き出し、主放電空間19に供給した。ノズル22のガス吹き出し幅は、325mmであった。ノズル22からのN2供給流量は、20slmとした。
各ロール電極11,12の直径は、320mmであった。各ロール電極11,12の軸長は、340mmであった。
ロール電極11,12間の最も狭くなった箇所のギャップ(主放電空間19の厚さ)は、1mmであった。
電極11への供給電力は、1100Wとした。
電極11,12間の印加電圧は、Vpp=18.0kVであった。
各電極31の下面31aと第2ロール電極12の外周面との間隔は、1mmであった。
固体誘電体32の厚さは、1mmであった。
各電極31への供給電力は、600Wとした。したがって、2つの電極31の合計の供給電力は、1200Wであった。
電極31,12間の印加電圧は、Vpp=18.0kVであった。
各再放電空間39への放電生成ガス(N2)の供給流量は、20.0L/minとした。
PVAフィルムの反対側の面には、鹸化処理したTACフィルムを上記と同じ接着剤にて貼り合わせた。これにより、3層構造の偏光板サンプルを作製した。偏光板サンプルの幅は、25mmとした。
測定の結果、接着強度は9.8N/25mmであった。
比較例として、再活性化部30(電極31)を省いた点を除き、図1のフィルム表面処理装置1と同一構造の装置を用い、TACフィルム9のプラズマ処理を行なった。処理条件は、実施例1の主処理部10での処理条件と同一とした。
表面処理後のTACフィルムからはアクリル酸特有の酢酸臭がした。上記処理後のTACフィルムの表面を実施例1と同じ測定手段にてpH測定したところ、pH=4であった。上記のpH測定結果は、TACフィルムの表面にアクリル酸モノマーが未だ残っており、重合が不十分であることを示す。
測定の結果、接着強度は、8.5N/25mmであった。
本発明によれば、再活性化部30を設けて再プラズマ処理することによって、再プラズマ処理しない場合(比較例1)よりも接着強度を1N/25mm以上高めることができた。
主処理部10におけるプラズマ処理の処理条件は、実施例1と同一とした。
光エネルギー照射手段50として赤外ランプ(ハイベック社製、型番HYP45)を用いた。光エネルギー照射手段50の光出射面とTACフィルム9との距離は、10mmとした。光エネルギー照射手段50からの照射光の波長は、0.8μmであり、照度は、15W/cm2であった。
表面処理後のTACフィルムからはアクリル酸特有の酢酸臭がしなかった。上記処理後のTACフィルムの表面を実施例1と同じ測定手段にてpH測定したところ、pH=7であった。この結果は、モノマーのままのアクリル酸がほぼ存在しなくなり、重合反応が十分になされたことを示す。
更に実施例1と同様にして、サンプルを作製し、かつ接着強度を測定した。
測定の結果、接着強度は、9.5N/25mmであった。
9 被処理フィルム
10 主処理部
11 第1ロール電極
12 第2ロール電極
16 ガイドロール
18 電源
19 主放電空間
20 反応ガス供給源(気化器)
21 上側放電生成ガスノズル
22 下側放電生成ガスノズル
23 反応ガスノズル
24 放電生成ガス源
30 再活性化部
31 後段電極
31a 対向面
32 固体誘電体
33 ガス供給部
34 再活性化用ロール電極
35 平行平板電極
36 凹円筒面電極
37 ロール(凸円筒面)電極
38 再活性化用電源
39 再放電空間
40 遮蔽部材
41 遮蔽空間
50 光エネルギー照射手段
51 照射光
Claims (5)
- 連続する被処理フィルムを搬送しながら、反応成分を活性化させて前記被処理フィルムの表面上で反応させるフィルム表面処理装置であって、
前記搬送方向の相対的に上流側に配置された主処理部と、前記搬送方向の相対的に下流側に配置された再活性化部とを備え、
前記主処理部が、互いの間に大気圧近傍の主放電空間を形成するよう平行に配置された第1ロール電極及び第2ロール電極と、前記被処理フィルムにおける前記主放電空間より前記搬送方向の上流側の部分に向けて又は前記主放電空間に向けて前記反応成分を含有する反応ガスを吹き出すノズルと、を含み、前記被処理フィルムが、前記第1ロール電極に掛け回され、かつ前記主放電空間に通された後に折り返されて前記第2ロール電極に掛け回され、前記第1ロール電極及び第2ロール電極が、それぞれ自らの軸線まわりに、かつ互いに同方向に回転されることにより、前記被処理フィルムが前記第1ロール電極から前記第2ロール電極へ搬送され、
前記再活性化部が、互いの間に大気圧近傍の再放電空間が形成される一対の後段電極と、これら後段電極間に前記反応成分を含まない放電生成ガスを供給するガス供給部とを含み、前記再放電空間に前記被処理フィルムが通され、前記一対の後段電極の対向面が、平面どうし、平面と凸円筒面、又は凹円筒面と凸円筒面であることを特徴とするフィルム表面処理装置。 - 前記再活性化部の一対の後段電極のうち一方が、平面又は凹円筒面からなる対向面を有して前記第2ロール電極と対向し、前記第2ロール電極が、前記再活性化部の他方の後段電極として提供されていることを特徴とする請求項1に記載のフィルム表面処理装置。
- 前記再活性化部に供給される電力が、前記主処理部に供給される電力より大きいことを特徴とする請求項1又は2に記載のフィルム表面処理装置。
- 連続する被処理フィルムを搬送しながら、反応成分を活性化させて前記被処理フィルムの表面上で反応させるフィルム表面処理装置であって、
前記搬送方向の相対的に上流側に配置された主処理部と、前記搬送方向の相対的に下流側に配置された再活性化部とを備え、
前記主処理部が、互いの間に大気圧近傍の主放電空間を形成するよう平行に配置された第1ロール電極及び第2ロール電極と、前記被処理フィルムにおける前記主放電空間より前記搬送方向の上流側の部分に向けて又は前記主放電空間に向けて前記反応成分を含有する反応ガスを吹き出すノズルと、を含み、前記被処理フィルムが、前記第1ロール電極に掛け回され、かつ前記主放電空間に通された後に折り返されて前記第2ロール電極に掛け回され、前記第1ロール電極及び第2ロール電極が、それぞれ自らの軸線まわりに、かつ互いに同方向に回転されることにより、前記被処理フィルムが前記第1ロール電極から前記第2ロール電極へ搬送され、
前記再活性化部が、前記被処理フィルムに光エネルギーを照射する光エネルギー照射手段を含むことを特徴とするフィルム表面処理装置。 - 前記反応成分が、重合性モノマーであることを特徴とする請求項1~4の何れか1項に記載のフィルム表面処理装置。
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| JP6183870B1 (ja) * | 2016-05-31 | 2017-08-23 | 春日電機株式会社 | 表面改質装置 |
| JP6403227B2 (ja) * | 2016-11-18 | 2018-10-10 | 日東電工株式会社 | 光学フィルムの活性化処理方法および製造方法、光学フィルムならびに画像表示装置 |
| JP6581269B2 (ja) * | 2018-09-25 | 2019-09-25 | 日東電工株式会社 | 光学フィルムの活性化処理方法および製造方法、光学フィルムならびに画像表示装置 |
| CN109967019A (zh) * | 2019-04-19 | 2019-07-05 | 华东理工大学 | 一种颗粒干法连续表面改性反应器 |
| JP2019215574A (ja) * | 2019-08-29 | 2019-12-19 | 日東電工株式会社 | 光学フィルムの活性化処理方法および製造方法、光学フィルムならびに画像表示装置 |
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