WO2011111558A1 - フィルム表面処理装置 - Google Patents

フィルム表面処理装置 Download PDF

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Publication number
WO2011111558A1
WO2011111558A1 PCT/JP2011/054497 JP2011054497W WO2011111558A1 WO 2011111558 A1 WO2011111558 A1 WO 2011111558A1 JP 2011054497 W JP2011054497 W JP 2011054497W WO 2011111558 A1 WO2011111558 A1 WO 2011111558A1
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WO
WIPO (PCT)
Prior art keywords
film
discharge
roll electrode
discharge space
nozzle
Prior art date
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PCT/JP2011/054497
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English (en)
French (fr)
Japanese (ja)
Inventor
良憲 中野
光秀 野上
真一 川崎
崇 佐藤
純一 松崎
Original Assignee
積水化学工業株式会社
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Publication date
Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to JP2012504409A priority Critical patent/JP5167431B2/ja
Priority to KR1020127026204A priority patent/KR101316963B1/ko
Priority to CN201180012728.0A priority patent/CN102791777B/zh
Publication of WO2011111558A1 publication Critical patent/WO2011111558A1/ja

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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
    • C08J7/12—Chemical modification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00634—Production of filters
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H05H1/48—Generating plasma using an arc
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/12—Optical coatings produced by application to, or surface treatment of, optical elements by surface treatment, e.g. by irradiation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05H—PLASMA TECHNIQUE; PRODUCTION OF ACCELERATED ELECTRICALLY-CHARGED PARTICLES OR OF NEUTRONS; PRODUCTION OR ACCELERATION OF NEUTRAL MOLECULAR OR ATOMIC BEAMS
    • H05H1/00—Generating plasma; Handling plasma
    • H05H1/24—Generating plasma
    • H05H1/47—Generating plasma using corona discharges
    • H05H1/473—Cylindrical electrodes, e.g. rotary drums
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid

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 to a polarizing film with an adhesive.
  • the polarizing film is comprised with the resin film (henceforth a "PVA film") which contains polyvinyl alcohol (PVA) as a main component.
  • the protective film is composed of a resin film (hereinafter referred to as “TAC film”) containing triacetate cellulose (TAC) as a main component.
  • TAC film resin film
  • TAC film triacetate cellulose
  • 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.
  • 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
  • Patent Documents 2 and 3 have 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.
  • JP 2009-25604 A International Publication WO 2009/008284 (Fig. 5) JP 2009-035724 A
  • the roll electrode of the plasma irradiation apparatus is covered with a protective film, but the plate electrode and the gas nozzle are directly exposed to the plasma. For this reason, dirt composed of a polymer of a polymerizable monomer or the like tends to adhere to the flat electrode or the gas nozzle. This dirt component causes particles and causes a decrease in yield. Therefore, it is difficult to operate stably for a long time.
  • the film to be processed covers both roll electrodes, so that there is little contamination of the electrodes.
  • a polymerizable monomer can be plasma-polymerized by blowing out the polymerizable monomer containing gas from the blowing nozzle which faces discharge space.
  • the polymerizable monomer is directly blown out from the blow nozzle into the discharge space, a polymerization reaction occurs simultaneously with the blowout, and it is easy to be discharged through the discharge space without adhering to the surface of the film to be treated.
  • the present invention enhances treatment effects such as adhesion while preventing contamination of electrodes and the like when plasma-treating a film to be treated such as a protective film for a polarizing plate using a polymerizable monomer as a reaction component. With the goal.
  • the present invention is an apparatus for contacting a polymerizable monomer with a continuous film to be processed, and surface-treating the film to be processed through a discharge space near atmospheric pressure,
  • the discharge space is formed between the first roll electrode and the first roll electrode, and a portion of the film to be processed on the downstream side in the transport direction from the first roll electrode defines the discharge space.
  • a second roll electrode that is folded after being passed through and is rotated in the same direction as the first roll electrode around its own axis to convey the film to be treated; Along the circumferential direction of the first roll electrode, it is disposed away from the discharge space to the upstream side in the rotation direction of the first roll electrode so as to face a portion of the first roll electrode around which the film to be treated is wound.
  • a reaction gas nozzle for blowing out a reaction gas containing the polymerizable monomer A discharge generation gas nozzle that is disposed inside the folded portion of the film to be processed between the first and second roll electrodes and blows out the discharge generation gas not containing the polymerizable monomer toward the discharge space; It is provided with.
  • the apparatus can be stably operated over a long period.
  • the film to be processed is conveyed from the first roll electrode to the second roll electrode by the rotation of the first roll electrode and the second roll electrode.
  • the reaction gas is blown out from the reaction gas nozzle.
  • the reactive gas is sprayed onto the film to be processed on the peripheral surface of the first roll electrode upstream of the discharge space in the transport direction.
  • At least a part of the reaction gas flows on the surface of the film to be processed along the transport direction of the film to be discharged.
  • the polymerizable monomer in the reaction gas can contact the film to be treated. Therefore, the polymerizable monomer can be condensed on the film to be treated in an unpolymerized state and attached to the film to be treated.
  • the discharge product gas is blown out from the discharge product gas nozzle on the side opposite to the side where the reaction gas flows through the discharge space.
  • the discharge generated gas flows in a direction opposite to the flow of the reaction gas, passes through the discharge space, is turned into plasma (including excitation, activation, radicalization, ionization, etc.) and collides with the reaction gas.
  • the reaction gas can be retained, the opportunity for the unpolymerized polymerizable monomer to come into contact with the film to be processed can be increased, and the adhesion amount of the polymerizable monomer to the film to be processed can be increased.
  • the part to which the polymerizable monomer in the to-be-treated film adheres is eventually introduced into the discharge space.
  • the attached polymerizable monomer undergoes a polymerization reaction to become a polymer and binds to the surface molecules of the film to be treated (graft polymerization). Therefore, a polymerized monomer film can be reliably formed on the surface of the film to be treated. As a result, the processing effect of the film to be processed can be enhanced.
  • a shielding member extending from the reaction gas nozzle toward the discharge space so as to cover the circumferential surface of the first roll electrode; and between the circumferential surface of the first roll electrode and the shielding member, It is preferable that a continuous shielding space is formed.
  • the reaction gas can be confined in the shielding space by the shielding member, and the reaction gas can be prevented from diffusing into the external atmosphere. After the reaction gas collides with the discharge generated gas flowing in the opposite direction, the reaction gas can be reliably retained on the surface of the film to be processed. Therefore, the opportunity for the polymerizable monomer in the reaction gas to come into contact with the film to be processed can be surely increased, and the amount of the polymerizable monomer attached to the film to be processed can be further reliably increased.
  • the reaction gas can be reliably guided to the discharge space.
  • the shielding member can prevent or suppress a reaction inhibiting component such as oxygen in the external atmosphere from entering the shielding space and thus the discharge space. Therefore, the processing effect can be improved with certainty. Furthermore, the shielding member can ensure the uniformity of the gas flow, and thus improve the uniformity of processing.
  • the reactive gas nozzle is preferably disposed about 45 ° to 180 ° away from the discharge space along the circumferential direction of the first roll electrode, and more preferably about 90 ° or about 4 °. They are placed one minute apart. Thereby, it can prevent reliably that a dirt adheres to a reactive gas nozzle. In addition, the reaction gas can surely flow into the discharge space along the circumferential direction of the first roll electrode. The adhesion amount of the polymerizable monomer to the film to be treated can be ensured by increasing the distance from spraying to the discharge space.
  • a closing member disposed to face the discharge-generating gas nozzle with the discharge space interposed therebetween, wherein the shielding space is formed between a peripheral surface of the first roll electrode and the closing member; It is preferable that a second gap is formed between the discharge member and the peripheral surface of the second roll electrode.
  • the end of the discharge space opposite to the discharge generated gas nozzle side can be blocked to some extent by the closing member. Both ends of the discharge space in the direction perpendicular to the electrode axial direction and the electrode facing direction can be blocked to some extent by the discharge generated gas nozzle and the closing member. Part of the discharge generated gas can be reliably guided to the shielded space through the first gap.
  • the discharge generated gas and the reactive gas can be surely collided in the shielded space, and the amount of the polymerizable monomer attached to the film to be treated can be reliably increased.
  • Another part of the discharge generated gas is discharged to the outside through the second gap. This reliably prevents the reaction-inhibiting component such as oxygen in the external atmosphere from entering the discharge space.
  • the discharge product gas is preferably at a lower temperature than the reaction gas. Specifically, it is preferable that the temperature at which the discharge gas is blown from the discharge gas nozzle is lower than the temperature at which the reaction gas is blown from the reaction gas nozzle.
  • the discharge temperature of the discharge product gas is 20 ° C. to 70 ° C. lower than the discharge temperature of the reaction gas. More preferably, the discharge temperature of the discharge product gas is lower than the condensation temperature of the polymerizable monomer vapor in the reaction gas.
  • 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 treatment effect can be enhanced while preventing contamination of electrodes and the like.
  • the to-be-processed film 9 is a continuous sheet form.
  • a protective film for a polarizing plate is applied as the film 9 to be processed.
  • the protective film 9 is composed of a TAC film containing 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.
  • the protective film is bonded to the polarizing film with an adhesive, thereby forming a polarizing plate.
  • a polarizing film consists of a PVA film.
  • 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 treatment unit 10.
  • the processing unit 10 includes a pair of electrodes 11, 12, a discharge generation gas nozzle 21, and a reaction gas nozzle 31.
  • the electrodes 11 and 12 are in 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.
  • process width direction the direction along the axis of the electrodes 11 and 12 (the direction orthogonal to the plane of FIG. 1) is appropriately referred to as “process width direction” (see FIG. 2).
  • the left first roll electrode 11 is connected to the power source 2.
  • the second roll electrode 12 on the right side is electrically grounded.
  • the power source 2 supplies, for example, pulsed high frequency power to the electrode 11. As a result, 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 discharge space 14 near atmospheric pressure. Specifically, the narrowest portion between the roll electrodes 11 and 12 and the space near the upper and lower sides thereof become the discharge space 14.
  • the power source 2 may be connected to the second roll electrode 12 and the first electrode 11 may be electrically grounded.
  • the film to be treated 9 is incorporated in the film surface treatment apparatus 1 with the width direction directed in the treatment width direction (direction perpendicular to the plane of FIG. 1).
  • a film 9 to be processed is wound around the upper peripheral surface of the first roll electrode 11 about a half turn.
  • the film 9 to be processed is passed through the discharge space 14 along the peripheral surface of the first roll electrode 11, and is hung below the discharge space 14. Further, the film to be processed 9 is folded upward by the guide rolls 16 and 16 and passed through the discharge space 14 along the peripheral surface of the second roll electrode 12. Thereby, the part between the roll electrodes 11 and 12 in the to-be-processed film 9 and the lower side from the discharge space 14 forms the folding
  • the folded portion 9a has a triangular shape when viewed from the processing width direction. Furthermore, the to-be-processed film 9 is wound around the upper peripheral surface of the second roll electrode 12 by about a half turn. About half a circumference including a portion defining the discharge space 14 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 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
  • the discharge generated gas nozzle 21 is disposed between the roll electrodes 11 and 12 below the discharge space 14.
  • a discharge generated gas supply source 20 is connected to the nozzle 21 via a gas supply path 22.
  • the nozzle 21 is disposed inside the triangular folded portion 9a of the film 9 to be processed.
  • the nozzle 21 extends long in the processing width direction, and a cross section perpendicular to the extending direction is tapered upward.
  • An outlet at the upper end (tip) of the nozzle 21 faces the discharge space 14.
  • the lower end of the discharge space 14 is blocked to some extent by the nozzle 21.
  • a rectifying unit (not shown) is provided at the lower end of the nozzle 21, and discharge generated gas is made uniform in the processing width direction and introduced into the nozzle 21. This discharge generated gas is blown out from the outlet of the nozzle 21 toward the discharge space 14.
  • the discharge flow of the discharge product gas is a uniformly distributed flow in the processing width direction.
  • 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.
  • discharge generated gas temperature adjusting means is incorporated in the nozzle 21.
  • the temperature adjusting means is constituted by a temperature adjusting path formed in the nozzle 21, for example. By flowing a temperature-controlled medium such as water through the temperature adjustment path, the temperature of the nozzle 21 can be adjusted, and thus the discharge temperature of the discharge generated gas can be adjusted.
  • the discharge temperature of the discharge product gas is lower than that of the reaction gas, and preferably lower than the condensation temperature of acrylic acid (polymerizable monomer) in the reaction gas.
  • the discharge temperature of the discharge product gas is 10 ° C. to 50 ° C.
  • a closing member 50 is disposed between the roll electrodes 11 and 12 above the discharge space 14.
  • the closing member 50 faces the discharge generated gas nozzle 21 with the discharge space 14 in between.
  • the closing member 50 extends long in the processing width direction, and a cross section perpendicular to the extending direction tapers downward.
  • the lower end (tip) of the closing member 50 faces the discharge space 14.
  • a first gap 51 is formed between the closing member 50 and the peripheral surface of the first roll electrode 11.
  • a second gap 52 is formed between the closing member 50 and the peripheral surface of the second roll electrode 12.
  • the discharge space 14 is connected to the outside through the second gap 52.
  • As the closing member 50 a nozzle having the same structure as the discharge generation gas nozzle 21 may be used, and this may be installed upside down with respect to the discharge generation gas nozzle 21.
  • the reaction gas nozzle 31 is disposed above the first roll electrode 11 so as to face the electrode 11.
  • the reactive gas nozzle 31 is separated from the discharge space 14 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 31 faces the film 9 to be processed on the electrode 11 on the upstream side in the transport direction from the discharge space 14.
  • the reactive gas nozzle 31 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). Although detailed illustration is omitted, a rectification unit is incorporated in the reaction gas nozzle 31.
  • An outlet is provided on the lower surface of the reaction gas nozzle 31. The outlets are formed so as to be distributed over a wide range (processing width direction and electrode circumferential direction) of the lower surface of the nozzle 31.
  • a reactive gas supply source 30 is connected to a nozzle 31 via a supply line 32.
  • the reaction gas from the supply source 30 is supplied to the nozzle 31.
  • the reaction gas is made uniform by the rectifying unit and blown out from the blowout port on the lower surface of the nozzle 31.
  • 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 30 includes 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 32 and the nozzle 31 are temperature-controlled by reaction gas temperature adjusting means (not shown).
  • the temperature adjusting means of the reaction gas supply line 32 is constituted by, for example, a ribbon heater.
  • the temperature adjusting means in the nozzle 31 is constituted by a temperature adjustment path through which a medium such as temperature-controlled water passes, for example.
  • the temperature of the reaction gas is adjusted to be higher than the condensation temperature of acrylic acid. For example, the temperature of the reaction gas is adjusted to 30 ° C. to 80 ° C.
  • a shielding member 40 is provided at the bottom of the reaction gas nozzle 31.
  • the shielding member 40 has a curved plate shape that extends in the processing width direction substantially the same length as the electrode 11, and a cross section orthogonal to the extending direction forms an arc shape along the circumferential direction of the upper surface of the first roll electrode 11. .
  • the shielding member 40 covers the upper peripheral surface of the first roll electrode 11 to some extent.
  • the reaction gas nozzle 31 is connected to the central portion of the shielding member 40 in the arc direction (left and right in FIG. 1). Both end portions of the shielding member 40 in the arc direction (left and right in FIG. 1) extend in the circumferential direction of the electrode 11 from the nozzle 31. In FIG. 1, the right end of the shielding member 40 is abutted against and connected to the side of the closing member 50.
  • 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 a space having an arcuate cross section along the upper peripheral surface of the first roll electrode 11.
  • the shielding space 41 is narrow at the center in the arc direction (left and right in FIG. 1), and is slightly wider toward both ends in the arc direction.
  • the outlet on the lower surface of the reactive gas nozzle 31 passes through the shielding member 40 and communicates with the shielding space 41.
  • the right end of the shielding space 41 is connected to the discharge space 14 via a first gap 51.
  • the end portion on the left side (the side opposite to the closing member 50) of the shielding space 41 is open to the outside.
  • the circumferential length of the shielding member 40 in the arc direction is, for example, about 240 to 300 mm.
  • the thickness of the shielding space 41 is preferably about 1 mm to 10 mm.
  • the thickness of the narrowest part of the shielding space 41 is preferably about 1 mm, for example.
  • the thickness of the widest part of the shielding space 41 is preferably about 10 mm, for example.
  • the thickness of the shielding space 41 may be constant throughout the area.
  • the shielding member 40 may be separated into an upstream portion and a downstream portion in the rotation direction of the roll electrode 11 with the nozzle 31 interposed therebetween, and the bottom surface of the nozzle 31 faces the shielding space 41 directly. Also good.
  • a method for surface-treating the film 9 to be treated by the film surface treatment apparatus 1 having the above-described configuration, and a method for producing a polarizing plate will be described.
  • a film to be processed 9 made of a TAC film 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 from the first roll electrode 11 to the second roll electrode 12 in a substantially right direction in FIG. 1.
  • an electric field is applied between the roll electrodes 11 and 12, and atmospheric pressure plasma discharge is generated in the interelectrode space 14.
  • a reactive gas (acrylic acid + N 2 ) is introduced from the supply source 30 to the nozzle 31 and blown out from the nozzle 31 to the shielding space 41.
  • the reactive gas is sprayed onto the film 9 to be processed on the upstream side of the first roll electrode 11, that is, on the upstream side in the transport direction from the discharge space 14.
  • Acrylic acid (reaction component) in the reaction gas condenses and adheres to the film 9 to be processed.
  • the majority of the reaction gas flows along the transport direction of the film to be processed 9 on the surface of the film to be processed 9.
  • the reaction gas can be confined in the shielding space 41 by the shielding member 40, and the reaction gas can be prevented or suppressed from leaking into the external atmosphere. Therefore, the opportunity for the acrylic acid in the reaction gas to contact the film to be processed 9 can be increased, and the amount of acrylic acid attached to the film to be processed 9 can be secured. Further, the shielding member 40 can ensure the uniformity of the gas flow in the processing width direction.
  • the reactive gas flows from the shielding space 41 toward the discharge space 14 through the first gap 51.
  • the shielding member 40 can prevent atmospheric gas containing oxygen such as external air from entering the shielding space 41 and can prevent oxygen from being mixed into the reaction gas.
  • the discharge product gas (N 2 ) is blown out from the discharge product gas nozzle 21 on the side (lower side) opposite to the side from which the reaction gas flows with the discharge space 14 in between.
  • the discharge temperature of the discharge product gas is lower than the discharge temperature of the reaction gas.
  • This discharge product gas flows in a direction (upward) opposite to the flow of the reaction gas, and is introduced into the discharge space 14.
  • the discharge generated gas that has passed through the discharge space 14 is shunted into the first gap 51 and the second gap 52 by the closing member 50.
  • the discharge generated gas that has entered the first gap 51 is further guided to the shielding space 41. Therefore, in the shielding space 41 and the first gap 51, the reaction gas and the discharge generated gas collide and mix.
  • reaction gas can be retained and the opportunity for acrylic acid to contact the to-be-processed film 9 can be increased further.
  • the reaction gas is cooled by the low-temperature discharge product gas. Therefore, condensation of acrylic acid in the reaction gas can be promoted and can be reliably attached to the film 9 to be processed. Therefore, the adhesion amount of acrylic acid to the film to be processed 9 can be reliably increased.
  • the discharge generated gas that has flowed into the second gap 52 is discharged to the outside through the second gap 52. This exhaust flow can prevent the external atmosphere from entering the second gap 52.
  • the portion of the film 9 to which the acrylic acid is attached is introduced into the discharge space 14.
  • the plasma in the discharge space 14 activates acrylic acid on the surface of the film 9 to be processed, causing double bond cleavage, polymerization, and the like.
  • nitrogen in the discharge product gas and the reaction gas is turned into plasma to generate nitrogen plasma.
  • the nitrogen plasma or plasma light is irradiated to the film 9 to be processed, and the bonds such as C—C, C—O, C—H, etc. of the surface molecules of the film 9 are cut. It is considered that a polymer of acrylic acid is bonded (graft polymerization) to this bond cutting part, or 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 acrylic acid is sufficiently adhered to the film to be treated 9 prior to introduction into the discharge space 14, an adhesion promoting layer can be reliably formed in the discharge space 14. Since the shielding member 41 can ensure the uniformity of the gas flow in the treatment width direction, the uniformity of treatment in the discharge space 14 can be ensured, and a uniform adhesion promoting layer can be obtained. Further, the shielding member 40 can prevent or suppress the external atmospheric gas from entering the discharge space 14. Furthermore, the discharge of the discharge product gas from the second gap 52 can also prevent or suppress the entry of the external atmospheric gas into the discharge space 14. Therefore, it is possible to sufficiently prevent or suppress the reaction in the discharge space 14 from being inhibited by a reaction inhibiting component such as oxygen in the external atmosphere. Therefore, the processing effect can be improved with certainty.
  • the film 9 to be processed passes through the discharge space 14 while being in contact with the first roll electrode 11, is turned back by the guide roll 16, and passes through the discharge space 14 again while being in contact with the second roll electrode 12. Therefore, the processed film 9 is processed twice in the discharge space 14.
  • the film 9 to be treated covers at least a portion of the first roll electrode 11 and the second roll electrode 12 that defines the discharge space 14, thereby preventing or suppressing contamination of the electrodes 11 and 12.
  • the reactive gas nozzle 31 is disposed away from the discharge space 14, and the acrylic acid in the shielded space 41 is almost unpolymerized. Therefore, it is possible to prevent or suppress the adhesion of dirt such as a polymer of acrylic acid to the outlet of the nozzle 31 and the shielding member 40. Therefore, the generation of particles can be prevented or suppressed, and the yield can be improved. Therefore, the surface treatment apparatus 1 can be stably operated over a long period.
  • the surface-treated TAC film 9 is adhered to a PVA polarizing film via an aqueous adhesive such as a PVA aqueous solution to produce a polarizing plate. Since the adhesion promoting layer is sufficiently and uniformly formed on the TAC film 9, a polarizing plate having good adhesive strength can be obtained.
  • the film surface treatment apparatus 1A includes three roll electrodes 11, 12, and 13. These three roll electrodes 11 to 13 constitute a two-stage processing unit 10A, 10B.
  • the upstream processing unit 10A includes roll electrodes 11 and 12 and nozzles 21 and 31 as components, and corresponds to the processing unit 10 of the first embodiment.
  • the post-stage processing unit 10B includes roll electrodes 12 and 13 and nozzles 23 and 33 as components.
  • the left roll electrode 11 constitutes the first roll electrode of the pre-treatment unit 10A.
  • the center roll electrode 12 serves as both the second roll electrode of the pre-processing unit 10A and the first roll electrode of the post-processing unit 10B.
  • the right roll electrode 13 constitutes a second roll electrode of the post-processing unit 10B.
  • the power source 2 (see FIG. 1) is connected to the central roll electrode 12, and the left and right roll electrodes 11 and 13 are electrically grounded.
  • a power source may be connected to the left and right roll electrodes 11 and 13 and the central roll electrode 12 may be electrically grounded. Due to the power supply from the power source, a discharge space 14 of the upstream processing unit 10A is formed between the left roll electrode 11 and the center roll electrode 12. Between the central roll electrode 12 and the right roll electrode 13, a discharge space 15 of the post-processing unit 10 ⁇ / b> B is formed.
  • the film 9 to be processed is wound around the upper peripheral surfaces of the three roll electrodes 11, 12, and 13.
  • the point that the folded portion 9a of the film 9 to be processed is formed below the roll electrodes 11 and 12 is the same as in the first embodiment.
  • a folded portion 9b of the film 9 to be processed is formed below the roll electrodes 12 and 13.
  • the folded portion 9b is wound around the guide rolls 17 and 17, and has a triangular shape when viewed from the processing width direction orthogonal to FIG.
  • the three roll electrodes 11, 12, 13 are rotated clockwise in the figure in synchronization with each other. Thereby, the to-be-processed film 9 is conveyed in the substantially right direction.
  • the closing member 50 is arranged on the upper portion of the same as the processing unit 10 of the first embodiment.
  • the discharge generation gas nozzle 23 of the rear stage processing unit 10B is disposed inside the folded portion 9b.
  • the discharge generated gas nozzle 23 has the same structure as that of the discharge generated gas nozzle 21, and its tip end faces upward and faces the discharge space 15.
  • the discharge generation gas supply path 22 is branched and connected to the discharge generation gas nozzle 21 at the front stage and the discharge generation gas nozzle 23 at the rear stage.
  • the reaction gas nozzle 33 of the post-processing unit 10B is disposed on the upper side of the roll electrode 12.
  • the reactive gas nozzle 33 has the same structure as the reactive gas nozzle 31 and faces the upper peripheral surface of the roll electrode 12.
  • a reaction gas supply line 32 is branched and connected to a front reaction gas nozzle 31 and a rear reaction gas nozzle 33.
  • the bottom of the reaction gas nozzle 33 is provided with a shield member 43 having an arc-shaped cross section having substantially the same structure as the shield member 40.
  • the circumferential length of the shielding member 43 in the arc direction is, for example, about 240 to 300 mm.
  • a shielding space 44 is formed between the shielding member 43 and the upper peripheral surface of the roll electrode 12.
  • the outlet of the reactive gas nozzle 33 passes through the shielding member 43 and communicates with the shielding space 44.
  • the shielding space 44 is a space having an arcuate cross section along the upper peripheral surface of the roll electrode 12.
  • the shielding space 44 is narrow at the central portion in the arc direction (left and right in FIG. 3), and is slightly wider toward both ends in the arc direction.
  • the thickness of the shielding space 44 is preferably about 1 mm to 10 mm.
  • the thickness of the narrowest part of the shielding space 44 is preferably about 1 mm, for example.
  • the thickness of the widest part of the shielding space 44 is preferably about 10 mm, for example.
  • the thickness of the shielding space 44 may be constant over the entire area.
  • the shielding member 44 may be separated into an upstream portion and a downstream portion in the rotation direction of the roll electrode 12 with the nozzle 33 interposed therebetween, and the bottom surface of the nozzle 33 faces the shielding space 44 directly. Also good.
  • a closing member 53 having substantially the same structure as the closing member 50 is disposed on the upper portion between the roll electrodes 12 and 13.
  • a first gap 54 of the second processing unit 10B is formed between the closing member 53 and the roll electrode 12.
  • a second gap 55 of the second processing unit 10B is formed between the closing member 53 and the roll electrode 13.
  • the left end portion of the shielding member 43 is in contact with or close to the closing member 50.
  • the left end portion of the shielding space 44 is continuous with the upper end portion of the second gap 52 of the first processing unit 10A.
  • the right end portion of the shielding member 43 is in contact with or close to the closing member 53.
  • the right end portion of the shielding space 44 is continuous with the first gap 54 of the second processing unit 10 ⁇ / b> B, and thus is connected with the discharge space 15 via the first gap 54.
  • the second gap 55 of the second processing unit 10 ⁇ / b> B is continuous with the external space above the roll electrode 13.
  • acrylic acid is sprayed onto the film 9 to be treated from the reaction gas nozzle 31 of the pretreatment unit 10A. Subsequently, the plasma to be processed 9 is irradiated with nitrogen plasma in the discharge space 14. Thereafter, acrylic acid is sprayed onto the film 9 to be processed by the reaction gas nozzle 33 of the post-processing unit 10B. Subsequently, the plasma to be processed 9 is irradiated with nitrogen plasma in the discharge space 15. Therefore, the formation process of the plasma polymerization film of acrylic acid can be performed twice. Therefore, the degree of polymerization of acrylic acid can be increased and the thickness of the polymer film can be increased. As a result, the adhesiveness of the film 9 to be processed can be reliably improved.
  • the acrylic acid-containing gas from the reaction gas nozzle 31 collides with the nitrogen gas that has entered the first gap 51 from the discharge generation gas nozzle 21 and stays, and adhesion of acrylic acid to the film 9 to be processed is promoted.
  • the point is the same as in the first embodiment.
  • the acrylic acid-containing gas from the reaction gas nozzle 33 is guided by the shielding member 43 and is divided into the left side and the right side of the shielding space 44 in FIG.
  • the acrylic acid-containing gas that has flowed to the left side collides with the nitrogen gas that has entered the second gap 52 from the discharge generation gas nozzle 21 of the pre-treatment unit 10A and stays there.
  • the acrylic acid-containing gas that has flowed to the right side collides with the nitrogen gas that has entered the first gap 54 from the discharge generation gas nozzle 23 of the post-stage processing unit 10B and stays there. Thereby, it is possible to promote the adhesion of acrylic acid to the surface of the film 9 to be processed in the post-processing unit 10B.
  • the nitrogen gas that has flowed into the second gap 55 from the discharge generation gas nozzle 23 of the post-processing unit 10B is discharged to the external atmosphere. This exhaust flow can prevent external atmospheric gas (air) from entering the discharge space 15 from the second gap 55.
  • the reactive gas nozzle 31 is a portion of the first roll electrode 11 around which the film 9 to be processed is wound. What is necessary is just to leave
  • the reactive gas nozzle 31 may be disposed obliquely so as to face the peripheral surface on the discharge space 14 side from the upper end portion of the electrode 11, and face the peripheral surface on the side opposite to the discharge space 14 from the upper end portion of the electrode 11. It may be arranged diagonally.
  • the shielding member 40 only needs to extend from the reaction gas nozzle 31 toward the discharge space 14 at least. It does not need to extend from the gas nozzle 31 to the side opposite to the discharge space 14 side. You may narrow opening of the edge part on the opposite side to the discharge space 14 side of the shielding space 41.
  • FIG. The above point is the same also about the shielding member 43 of the back
  • the shielding members 40 and 43 may be omitted.
  • the closing members 50 and 53 are constituted by nozzles having a structure in which the discharge generation gas nozzles 21 and 23 are turned upside down, and the discharge generation gas is blown out toward the discharge spaces 14 and 15 also from the closing member / nozzles 50 and 53. You may decide.
  • the blocking members 50 and 53 may be omitted.
  • the number of roll electrodes in the film surface treatment apparatus is not limited to two or three, and may be four or more.
  • the number of stages of the processing unit of the film surface treatment apparatus is not limited to one (FIG. 1) or two (FIG. 3), and may be three or more.
  • the present invention is not limited to the surface treatment of a protective film for a polarizing plate, but can be applied to a treatment for forming a polymer film of a polymerizable monomer on various resin films.
  • the film 9 was subjected to a surface treatment using the film surface treatment apparatus 1 shown in FIGS.
  • the dimensional configuration of the apparatus 1 was as follows. Axial length of roll electrodes 11 and 12 in the processing width direction: 390 mm Diameter of roll electrodes 11 and 12: 320 mm External dimension of reaction gas nozzle 31 in the processing width direction: 390 mm Blowing width of reaction gas nozzle 31: 300 mm Circumferential length of shielding member 40 in the arc direction: 275 mm Thickness of shielding space 41: 5 mm (constant) throughout Gap between roll electrodes 11 and 12: 1 mm
  • a TAC film was used as the film 9 to be processed.
  • the width of the TAC film 9 was 325 mm.
  • the conveyance speed of the TAC film 9 was 15 m / min.
  • Acrylic acid was used as the polymerizable monomer for the reaction gas, and nitrogen (N 2 ) was used as the carrier gas.
  • the temperature of the liquid acrylic acid in the vaporizer 30 was 120 ° C.
  • the acrylic acid concentration in the reaction gas was 4.5 g / min.
  • the temperature of the reaction gas nozzle 31 (reaction gas blowing temperature) was set to 55 ° C.
  • Nitrogen (N 2 ) was used as the discharge product gas.
  • the discharge flow rate of the discharge generated gas (N 2 ) from the lower nozzle 21 was 10 slm.
  • the temperature of the lower nozzle 21 (discharge temperature of discharge generated gas) was set to 15 ° C.
  • the closing member 50 of the apparatus 1 used in Example 1 was a gas nozzle having a structure in which the lower nozzle 21 was inverted up and down.
  • the gas supply pipe from the discharge generated gas supply source 20 was branched and connected to the lower nozzle 21 and the upper nozzle 50, respectively.
  • the discharge flow rate of the discharge generated gas (N 2 ) from the upper nozzle 50 was 0 slm.
  • the power source 2 270V, 6.1A direct current was converted into alternating current.
  • the power supplied to the electrodes 11 and 12 was 1647 W, and the applied voltage between the electrodes 11 and 12 was 17.3 kV.
  • 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. Sample pieces were cut out from five places in the width direction of the film 9 to be processed, and five polarizing plate samples were prepared.
  • Example 2 in the apparatus 1, the flow rate of the discharge generated gas (N 2 ) was set to 20 slm. The supplied power was 1809 W (270 V, 6.7 A), and the applied voltage was 17.6 kV. Other processing conditions were the same as those in Example 1. Deposits were not confirmed at the nozzles 21 and 31 after the surface treatment. After the surface treatment, a polarizing plate sample was prepared in the same procedure as in Example 1, and the adhesive strength was measured. As a result of the measurement, the average adhesive strength was 9.9 N / 25 mm. The degree of variation was 4.2%.
  • Example 3 in the apparatus 1, the flow rate of the discharge product gas (N 2 ) was set to 30 slm. The supplied power was 1944 W (270 V, 7.2 A), and the applied voltage was 17.8 kV. Other processing conditions were the same as those in Example 1. Deposits were not confirmed at the nozzles 21 and 31 after the surface treatment. After the surface treatment, a polarizing plate sample was prepared in the same procedure as in Example 1, and the adhesive strength was measured. As a result of the measurement, the average adhesive strength was 9.3 N / 25 mm. The degree of variation was 6.5%.
  • Comparative Example 1 In Comparative Example 1, a nozzle having the same structure as the lower nozzle 21 and having the lower nozzle 21 turned upside down is used as the member 50, and the reactive gas supply line 32 from the vaporizer 30 is replaced with the nozzle 31. Connected to the nozzle 50.
  • the vaporization conditions of the vaporizer 30 were the same as in Example 1, and a reaction gas having the same composition and flow rate as in Example 1 was blown out from the lower end of the upper nozzle 50 into the discharge space 14.
  • the temperature of the upper nozzle 50 was adjusted to 55 ° C.
  • the gas blowing flow rate from the lower nozzle 21 was 0 slm.
  • the supplied power was 1080 W (270 V, 4 A), and the applied voltage was 15.7 kV.
  • Other processing conditions were the same as those in Example 1.
  • Comparative Example 1 deposits were confirmed at the outlet of the nozzle 50 after the surface treatment.
  • a polarizing plate sample was prepared in the same procedure as in Example 1 and the adhesive strength was measured. As a result, the average adhesive strength was 4.9 N / 25 mm, and the degree of variation was 60%.
  • Comparative Example 2 In Comparative Example 2, in the same apparatus 1 as in Example 1, a member 50 having the same structure as that of the lower nozzle 21 and a nozzle in which the lower nozzle 21 is inverted up and down is used. Was connected to the upper nozzle 50. The discharge flow rate of the discharge generated gas (N 2 ) from the upper nozzle 50 was set to 10 slm. The blowing flow rate from the lower nozzle 21 was set to 0 slm. The supplied power was 1377 W (270 V, 5.1 A), and the applied voltage was 16.7 kV. Other processing conditions were the same as those in Example 1. Deposits were not confirmed at the outlet of the nozzle 31 after the surface treatment. After the surface treatment, a polarizing plate sample was prepared in the same procedure as in Example 1, and the adhesive strength was measured. The average adhesive strength was 3.9 N / 25 mm, and the variation was 3.7%.
  • the present invention is applicable to the manufacture of a polarizing plate for a flat panel display (FPD), for example.
  • FPD flat panel display

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TWI554655B (zh) * 2015-08-06 2016-10-21 財團法人工業技術研究院 電極防汙裝置與鍍膜系統

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KR102360735B1 (ko) * 2016-08-10 2022-02-08 에이지씨 엔지니아링 가부시키가이샤 기재 시트의 처리 방법, 개질 기재 시트의 제조 방법, 그래프트 중합 사슬이 형성된 기재, 및 이온 교환막
JP7019576B2 (ja) 2016-08-10 2022-02-15 Ａｇｃエンジニアリング株式会社 基材シートの処理方法、および改質基材シートの製造方法
US11517894B2 (en) 2016-08-10 2022-12-06 Agc Engineering Co., Ltd. Processing method of base material sheet, manufacturing method of modified base material sheet, base material with grafted polymer chain, and ion exchange membrane
KR102577832B1 (ko) * 2016-08-10 2023-09-12 에이지씨 엔지니아링 가부시키가이샤 기재 시트의 처리 방법, 개질 기재 시트의 제조 방법, 그래프트 중합 사슬이 형성된 기재, 및 이온 교환막

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