WO2012133154A1 - フィルム表面処理方法及び装置 - Google Patents

フィルム表面処理方法及び装置 Download PDF

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Publication number
WO2012133154A1
WO2012133154A1 PCT/JP2012/057466 JP2012057466W WO2012133154A1 WO 2012133154 A1 WO2012133154 A1 WO 2012133154A1 JP 2012057466 W JP2012057466 W JP 2012057466W WO 2012133154 A1 WO2012133154 A1 WO 2012133154A1
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WIPO (PCT)
Prior art keywords
film
roll electrode
gas
roll
pmma film
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PCT/JP2012/057466
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English (en)
French (fr)
Japanese (ja)
Inventor
平 長谷川
純一 松崎
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積水化学工業株式会社
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Priority to CN201280015839.1A priority Critical patent/CN103459476B/zh
Priority to KR1020137022592A priority patent/KR101899177B1/ko
Publication of WO2012133154A1 publication Critical patent/WO2012133154A1/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
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • 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
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical

Definitions

  • the present invention relates to a method and an apparatus for treating the surface of an optical resin film, and in particular, a resin film (hereinafter referred to as “PMMA film”) containing polymethylmethacrylate (hereinafter referred to as “PMMA”) as a main component.
  • PMMA film a resin film
  • PMMA polymethylmethacrylate
  • the present invention relates to a surface treatment method and apparatus suitable for improving adhesiveness.
  • the protective monomer-containing gas is brought into contact with the protective film and plasma is irradiated.
  • acrylic acid is used as the polymerizable monomer.
  • a PMMA film is mentioned as an example of the protective film.
  • Argon is mentioned as an example of the plasma generating gas.
  • a polarizing plate is comprised by bonding the processed protective film with a polarizing film through an adhesive.
  • the adhesive water-based adhesives such as polyvinyl alcohol (hereinafter referred to as “PVA”) and polyether are used.
  • PVA film a resin film containing PVA as a main component
  • JP 2010-150372 A (0013, 0017) JP 2010-150373 A (0011, 0018)
  • the method of the present invention is a film surface treatment method for treating the surface of a PMMA film, A first contact step of contacting a PMMA film with a first reaction gas obtained by vaporizing acrylic acid into a carrier gas; A first irradiation step of irradiating the PMMA film with argon plasma generated near atmospheric pressure after the first contact step or in parallel with the first contact step; A second contact step in which a second reactive gas obtained by vaporizing acrylic acid into a carrier gas after the first irradiation step is brought into contact with the PMMA film; A second irradiation step of irradiating the PMMA film with argon plasma generated under atmospheric pressure after the second contact step or in parallel with the second contact step; It is characterized by including.
  • a first condensed layer of acrylic acid can be formed on the surface of the PMMA film by the first contact step.
  • the first condensed layer can be plasma polymerized in the first irradiation step to form a first plasma polymerized film of polyacrylic acid.
  • a second condensed layer of acrylic acid can be formed on the first plasma polymerization film by the second contact step.
  • the second condensation layer may be plasma-polymerized in a second irradiation step, and a second plasma polymerization film of polyacrylic acid may be laminated on the first plasma polymerization film.
  • the adhesive strength of the hard-to-adhere PMMA film can be improved, and furthermore, the adhesive durability can be sufficiently improved.
  • the adhesion durability refers to the degree to which the adhesion strength does not decrease after the object after bonding is exposed to a high humidity and high temperature wet heat environment.
  • the apparatus of the present invention is a film surface treatment apparatus for treating the surface of a PMMA film, First, second, and third roll electrodes that are arranged in parallel with each other and generate a discharge in the gap between adjacent ones near atmospheric pressure; A first reactive gas nozzle that faces the peripheral surface of the first roll electrode and blows out a first reactive gas containing acrylic acid; A first discharge gas nozzle that blows out argon into a gap between the first roll electrode and the second roll electrode; A second reaction gas nozzle that blows out a second reaction gas containing acrylic acid, facing the peripheral surface of the second roll electrode; A second discharge gas nozzle that blows out argon into the gap between the second roll electrode and the third roll electrode;
  • the PMMA film is wound around the first, second, and third roll electrodes, and the PMMA film is turned into the first roll electrode and the second roll electrode by the rotation of the first, second, and third roll electrodes.
  • the third roll electrode is conveyed in this order.
  • the first reactive gas is sprayed from the first reactive gas nozzle onto the PMMA film on the peripheral surface of the first roll electrode.
  • a first condensed layer of acrylic acid can be formed on the surface of the PMMA film.
  • argon plasma is irradiated to the PMMA film at the gap between the first and second roll electrodes. Accordingly, the first condensed layer can be plasma polymerized to form a first plasma polymerized film of polyacrylic acid.
  • the second reaction gas is sprayed onto the PMMA film from the second reaction gas nozzle on the peripheral surface of the second roll electrode.
  • a second condensed layer of acrylic acid can be formed on the first plasma polymerization film.
  • the PMMA film is irradiated with argon plasma at the gap between the second and third roll electrodes.
  • the second condensed layer can be plasma polymerized to form a second plasma polymerized film of polyacrylic acid on the first plasma polymerized film.
  • the first, second, and third roll electrodes also serve as a PMMA film supporting unit and a conveying unit.
  • the carrier gas of the first and second reaction gases is argon. Thereby, even if the carrier gas flows into the space (for example, the gap between the roll electrodes) in which the first and second irradiation processes are performed, it is possible to prevent the discharge state from changing.
  • the carrier gas may be nitrogen in order to reduce running costs.
  • 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 it is possible to improve the adhesive strength of the difficult-to-adhere PMMA film and to sufficiently improve the adhesion durability.
  • FIG. 1 shows a first embodiment of the present invention.
  • a to-be-processed object is the PMMA film 9 for the protective film of a polarizing plate.
  • the PMMA film 9 contains PMMA as a main component and is extremely difficult to adhere.
  • “containing PMMA as a main component” means that the proportion of PMMA in the film 9 is 60 wt% to 100 wt%.
  • the proportion of methyl methacrylate (MMA) in the film raw material is 60 wt% to 100 wt%.
  • components other than PMMA in the film 9 include ultraviolet absorbers, stabilizers, lubricants, processing aids, plasticizers, impact resistance aids, foaming agents, fillers, colorants, matting agents, and the like.
  • the film surface treatment apparatus 1 includes an electrode structure 10 and gas supply means 20-50.
  • the electrode structure 10 includes a first roll electrode 11, a second roll electrode 12, and a third roll electrode 13.
  • These roll electrodes 11 to 13 are cylindrical bodies having the same diameter and the same axial length. At least the outer periphery of each of the roll electrodes 11 to 13 is made of metal, and a solid dielectric layer is coated on the outer periphery of the metal outer periphery.
  • the axis of each roll electrode 11, 12, 13 is oriented in the horizontal direction (hereinafter referred to as “processing width direction”) orthogonal to the paper surface of FIG. 1.
  • processing width direction orthogonal to the paper surface of FIG.
  • Dimensional shapes such as thickness 15 are equal to each other.
  • the thickness of the narrowest part of the gaps 14 and 15 is preferably about 0.5 mm to 1.0 mm.
  • a power source is connected to the central roll electrode 12, and the left and right roll electrodes 11, 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.
  • the power source outputs, for example, pulsed high frequency power.
  • plasma discharge is generated between the left roll electrode 11 and the central roll electrode 12 under a pressure near atmospheric pressure, and the gap 14 becomes a first discharge space near atmospheric pressure.
  • plasma discharge is generated between the central roll electrode 12 and the right roll electrode 13 under a pressure near atmospheric pressure, and the gap 15 becomes a second discharge space near atmospheric pressure.
  • the frequency of the high frequency power is preferably about 50 kHz to 70 kHz.
  • the rise time and fall time of the pulse are preferably 10 ⁇ sec or less.
  • the pulse duration is preferably 1 to 1000 ⁇ sec.
  • the high frequency is not limited to a pulse wave, and may be a continuous wave.
  • a plurality (two in the figure) of front guide rolls 16 and 16 are arranged below the roll electrodes 11 and 12.
  • a plurality (two in the figure) of rear guide rolls 17 and 17 are arranged below the roll electrodes 12 and 13.
  • a continuous sheet-like PMMA film 9 is wound around the upper peripheral surfaces of the three roll electrodes 11, 12, and 13 by about a half turn, with the width direction directed in the processing width direction (the direction orthogonal to the plane of FIG. Yes.
  • the upper peripheral surface of each roll electrode 11, 12, 13 and the approximately half-periphery portion including the portion defining the gaps 14, 15 are covered with the PMMA film 9.
  • the PMMA film 9 between the roll electrodes 11 and 12 is hung down from the gap 14 and is wound around the guide rolls 16 and 16.
  • the PMMA film 9 between the gap 14 and the guide rolls 16 and 16 forms a folded portion 9a.
  • the PMMA film 9 between the roll electrodes 12 and 13 is hung downward from the gap 15 and is wound around the guide rolls 17 and 17.
  • the PMMA film 9 between the gap 15 and the guide rolls 17 and 17 forms a folded portion 9b.
  • a rotation mechanism is connected to each roll electrode 11, 12, 13.
  • 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, 12, and 13.
  • the transmission means is constituted by, for example, a belt / pulley mechanism or a gear train.
  • the roll electrodes 11, 12, and 13 are rotated around their own axes and in the same direction (clockwise in FIG. 1) in synchronism with each other by the rotation mechanism. Is done.
  • the electrode structure 10 also functions as a support unit that supports the PMMA film 9 and a transport unit that transports the PMMA film 9.
  • Each roll electrode 11, 12, 13 is provided with temperature control means (not shown).
  • the temperature adjustment means is constituted by a temperature adjustment path formed in the roll electrodes 11, 12, and 13, for example.
  • the temperature of the roll electrodes 11, 12, and 13 can be controlled by flowing a temperature-controlled medium such as water through the temperature control path.
  • the set temperature of the roll electrodes 11, 12, 13 is preferably lower than the condensation temperature of the polymerizable monomer (acrylic acid).
  • the set temperature of the PMMA film 9 is preferably about 25 ° C. to 45 ° C.
  • the first reactive gas supply means 20 includes a first reactive gas supply source 21 and a first reactive gas nozzle 23.
  • the first reaction gas contains a polymerizable monomer and a carrier gas.
  • Acrylic acid (AA) is used as the polymerizable monomer.
  • Nitrogen (N 2 ) is used as the carrier gas.
  • the first reaction gas is composed of a mixed gas of acrylic acid and nitrogen.
  • the first reactive gas supply source 21 includes a vaporizer.
  • liquid acrylic acid is vaporized into the carrier gas.
  • the vaporization may be a bubbling method or an extrusion method.
  • the first reaction gas is generated by mixing the vaporized acrylic acid and the carrier gas.
  • the bubbling method refers to a method in which a carrier gas is injected into the liquid acrylic acid solution in the vaporizer and the acrylic acid is vaporized into the bubbles of the carrier gas.
  • the extrusion method refers to a method in which a carrier gas is introduced into a space portion above the liquid acrylic acid level in the vaporizer, and the saturated acrylic acid vapor in the space portion is mixed with the carrier gas and extruded.
  • a first reactive gas supply source 21 is connected to a first reactive gas nozzle 23 via a gas path 22.
  • the first reactive gas nozzle 23 is disposed above the first roll electrode 11.
  • the first 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).
  • An outlet is provided on the lower surface of the first reactive gas nozzle 23.
  • the outlets are formed so as to be distributed over a wide range (the processing width direction and the roll circumferential direction) of the lower surface of the first reactive gas nozzle 23.
  • the blowing surface (lower surface) of the first reactive gas nozzle 23 faces the PMMA film 9 on the first roll electrode 11.
  • the first reactive gas from the first reactive gas supply source 21 is supplied to the first reactive gas nozzle 23 and is made uniform by a rectification unit (not shown) in the first reactive gas nozzle 23, and then the first reactive gas nozzle. It blows out from 23 outlets.
  • the blowout flow of the first reactive gas is a flow that is uniformly distributed in the processing width direction.
  • the gas path 22 and the first reactive gas nozzle 23 are provided with temperature control means (not shown).
  • the temperature adjusting means of the gas path 22 is constituted by a ribbon heater or the like.
  • the temperature control means of the first reactive gas nozzle 23 is configured by a temperature control path through which temperature control water passes.
  • the set temperatures of the gas path 22 and the first reaction gas nozzle 23 are higher than the condensation temperature of acrylic acid. This can prevent the acrylic acid from condensing before blowing out.
  • the set temperatures of the gas path 22 and the first reaction gas nozzle 23 are preferably about 60 ° C. to 80 ° C.
  • Shield members 24 are provided on both sides of the bottom of the first reactive gas nozzle 23.
  • the shielding member 24 has an arcuate cross section along the circumferential direction of the first roll electrode 11 and has a curved plate shape extending substantially the same length as the roll electrode 11 in the processing width direction.
  • the shielding member 24 extends from the first reactive gas nozzle 23 in the circumferential direction of the first roll electrode 11. In FIG. 1, the left end of the left shielding member 24 is released. In FIG. 1, the right end portion of the right shielding member 24 is in contact with or close to the nozzle 34 described later.
  • a first spraying space 25 is defined between the first reactive gas nozzle 23 and the first roll electrode 11.
  • the first blowing space 25 is a space having an arcuate cross section along the upper peripheral surface of the first roll electrode 11.
  • the first blowing space 25 is extended by the shielding member 24 to both sides in the circumferential direction of the first roll electrode 11 rather than the first reactive gas nozzle 23.
  • the left end portion of the first blowing space 25 is connected to the external space on the left side of the roll electrode 11 (the side opposite to the roll electrode 12 side).
  • the right end of the first blowing space 25 is connected to the gap 14 through a gap between a nozzle 34 and a roll electrode 11 described later.
  • the first discharge gas supply means 30 includes a first discharge gas supply source 31 and first discharge gas nozzles 33 and 34.
  • the gas supply source 31 stores argon (Ar) as the first discharge product gas.
  • the gas path 32 from the gas supply source 31 is connected to the first discharge gas nozzles 33 and 34.
  • the first discharge gas nozzles 33 and 34 are paired up and down across the gap 14.
  • the lower first discharge gas nozzle 33 is disposed inside the folded portion 9 a of the PMMA film 9.
  • the upper first discharge gas nozzle 34 is disposed between the roll electrodes 11 and 12 above the gap 14.
  • the first discharge gas nozzles 33 and 34 extend long in the processing width direction, and the cross sections perpendicular to the extending direction are tapered toward the opposing sides. The outlets at the tips of the first discharge gas nozzles 33 and 34 face the gap 14.
  • the argon gas from the gas supply source 31 is made uniform in the processing width direction by a rectification unit (not shown) in the first discharge gas nozzles 33 and 34, and then the gap from the outlet of the first discharge gas nozzles 33 and 34 It blows out toward 14.
  • This blowing flow is a flow that is uniformly distributed in the processing width direction.
  • a temperature control path (not shown) is provided in the first discharge gas nozzles 33 and 34.
  • a temperature control medium such as water is passed through the temperature control path in the first discharge gas nozzles 33 and 34.
  • the set temperature of the first discharge gas nozzles 33 and 34 is preferably about 25 ° C. to 45 ° C.
  • the second reactive gas supply means 40 includes a second reactive gas supply source 41 and a second reactive gas nozzle 43.
  • the second reaction gas is composed of the same gas as the first reaction gas. That is, the second reaction gas contains a polymerizable monomer and a carrier gas. Acrylic acid (AA) is used as the polymerizable monomer. Nitrogen (N 2 ) is used as the carrier gas.
  • the second reaction gas is composed of a mixed gas of acrylic acid and nitrogen.
  • the second reactive gas supply source 41 includes a vaporizer.
  • liquid acrylic acid is vaporized into the carrier gas.
  • the vaporization may be a bubbling method or an extrusion method.
  • a second reaction gas is generated.
  • the first reactive gas supply source 21 and the second reactive gas supply source 41 may be configured by a common acrylic acid supply source.
  • the second reactive gas supply source 41 is connected to the second reactive gas nozzle 43 via the gas path 42.
  • the second reactive gas nozzle 43 is disposed above the second roll electrode 12.
  • the second reactive gas nozzle 43 extends long in the processing width direction and has a certain width in the circumferential direction of the second roll electrode 12 (left and right in FIG. 1).
  • An outlet is provided on the lower surface of the second reactive gas nozzle 43.
  • the outlets are formed so as to be distributed over a wide range (the processing width direction and the roll circumferential direction) of the lower surface of the second reactive gas nozzle 43.
  • the blowing surface (lower surface) of the second reactive gas nozzle 43 faces the PMMA film 9 on the second roll electrode 12.
  • the second reaction gas from the second reaction gas supply source 41 is supplied to the second reaction gas nozzle 43 and is uniformized by a rectification unit (not shown) in the second reaction gas nozzle 43, and then the second reaction gas nozzle. It blows out from 43 outlets.
  • the flow of the second reactive gas is a flow that is uniformly distributed in the processing width direction.
  • the gas passage 42 and the second reactive gas nozzle 43 are provided with temperature control means (not shown).
  • the temperature adjusting means of the gas passage 42 is constituted by a ribbon heater or the like.
  • the temperature control means of the second reactive gas nozzle 43 is configured by a temperature control path through which temperature control water passes.
  • the set temperatures of the gas passage 42 and the second reaction gas nozzle 43 are higher than the condensation temperature of acrylic acid. This can prevent the acrylic acid from condensing before blowing out.
  • the set temperatures of the gas passage 42 and the second reaction gas nozzle 43 are preferably about 60 ° C. to 80 ° C.
  • a shielding member 44 is provided at the bottom of the second reactive gas nozzle 43.
  • the shielding member 44 has an arcuate cross section along the circumferential direction of the second roll electrode 12 and has a curved plate shape extending in the processing width direction substantially the same length as the roll electrode 12.
  • the shielding member 44 extends from the second reactive gas nozzle 43 in the circumferential direction of the second roll electrode 12. In FIG. 1, the left end portion of the left shielding member 44 is in contact with or close to the side portion of the first discharge gas nozzle 34. In FIG. 1, the right end portion of the right shielding member 44 is in contact with or close to the nozzle 54 described later.
  • a second spray space 45 is defined between the shielding member 44 and the second roll electrode 12.
  • the second spray space 45 is a space having an arcuate cross section along the upper peripheral surface of the second roll electrode 12.
  • the shielding member 44 extends the second blowing space 45 to both sides of the second roll electrode 12 in the circumferential direction from the second reactive gas nozzle 43.
  • the left end portion of the second spray space 45 is connected to the first discharge space 14 through a gap between the first discharge gas nozzle 34 and the roll electrode 12.
  • the right end of the second blowing space 45 is connected to the gap 15 through a gap between the nozzle 54 and the roll electrode 12 described later.
  • the second discharge gas supply means 50 includes a second discharge gas supply source 51 and second discharge gas nozzles 53 and 54.
  • Argon (Ar) is stored in the second discharge gas supply source 51 as the second discharge product gas.
  • the first discharge gas supply source 31 and the second discharge gas supply source 51 may be configured by a common argon gas supply source.
  • a gas path 52 from the gas supply source 51 is connected to the second discharge gas nozzles 53 and 54.
  • the second discharge gas nozzles 53 and 54 are paired up and down across the gap 15.
  • the lower second discharge gas nozzle 53 is disposed inside the folded portion 9 b of the PMMA film 9.
  • the upper second discharge gas nozzle 54 is disposed between the roll electrodes 11 and 12 above the gap 15.
  • the argon gas from the gas supply source 51 is made uniform in the processing width direction by a rectification unit (not shown) in the second discharge gas nozzles 53 and 54, and then the gap from the outlet of the second discharge gas nozzles 53 and 54 It blows out toward 15.
  • This blowing flow is a flow that is uniformly distributed in the processing width direction.
  • a temperature control path (not shown) is provided in the second discharge gas nozzles 53 and 54.
  • a temperature control medium such as water is passed through the temperature control path in the second discharge gas nozzles 53 and 54.
  • the set temperature of the second discharge gas nozzles 53 and 54 is preferably about 25 ° C. to 45 ° C.
  • a method for surface-treating the PMMA film 9 by the film surface treatment apparatus 1 having the above-described configuration, and a method for manufacturing a polarizing plate will be described.
  • [Support process, transport process] A continuous sheet-like PMMA film 9 is wound around the roll electrodes 11 to 13 and the guide rolls 16 and 17. The roll electrodes 11 to 13 are rotated clockwise in FIG. 1, and the PMMA film 9 is conveyed in the order of the first roll electrode 11, the second roll electrode 12, and the third roll electrode 13 in a substantially right direction in FIG.
  • the conveyance speed is preferably about 1 m / min to 30 m / min.
  • the first reaction gas supplying means 20 for generating a carrier gas (N 2) the first reaction gas is vaporized acrylic acid (AA) in (AA + N 2).
  • the volume concentration of acrylic acid in the first reaction gas is preferably 2% to 8%.
  • This first reactive gas is blown out from the reactive gas nozzle 23 into the first blowing space 25.
  • the first reactive gas contacts the surface of the PMMA film 9 in the first blowing space 25.
  • the acrylic acid monomer in the first reaction gas is condensed and attached to the PMMA film 9, and a first condensed layer made of the acrylic acid monomer is formed on the surface of the PMMA film 9.
  • argon is blown out from the first discharge gas nozzles 33 and 34 into the first discharge space 14 as the first discharge gas.
  • Argon may be blown out from both the upper and lower first discharge gas nozzles 33 and 34, or argon may be blown out only from one of the first discharge gas nozzles 33 or 34.
  • argon is blown out from the lower first discharge gas nozzle 33.
  • the portion of the PMMA film 9 that has undergone the first irradiation step is conveyed along the second roll electrode 12 to the second spraying space 45.
  • the second reaction gas supplying means 40 for generating a carrier gas (N 2) to vaporize acrylic acid (AA) in a second reaction gas (AA + N 2).
  • the volume concentration of acrylic acid in the second reaction gas is preferably 2% to 8%.
  • the acrylic acid concentration of the second reaction gas may be the same as the acrylic acid concentration of the first reaction gas, may be higher than the acrylic acid concentration of the first reaction gas, or may be lower than the acrylic acid concentration of the first reaction gas. .
  • This second reactive gas is blown out from the second reactive gas nozzle 43 into the second blowing space 45.
  • the second reactive gas contacts the surface of the PMMA film 9 in the second spray space 45.
  • the acrylic monomer in the second reaction gas condenses and adheres to the PMMA film 9, and a second condensed layer made of acrylic acid monomer is further formed on the first plasma polymerization film.
  • argon is blown out from the second discharge gas nozzles 53 and 54 into the second discharge space 15 as the second discharge gas.
  • Argon may be blown out from both the upper and lower second discharge gas nozzles 53, 54, or argon may be blown out only from one of the second discharge gas nozzles 53 or 54.
  • argon is blown out from the lower second discharge gas nozzle 53.
  • the second discharge space 15 discharge near atmospheric pressure is generated by supplying power to the roll electrode 12, and argon (second discharge gas) is turned into plasma.
  • This argon plasma comes into contact with the surface of the PMMA film 9 in the second discharge space 15.
  • the degree of polymerization of the first plasma polymerized film is further increased, and the acrylic acid monomer of the second condensing layer is plasma polymerized, and the second plasma polymerized further comprising polyacrylic acid on the first plasma polymerized film.
  • a film is laminated.
  • the first and second plasma polymerized films constitute an adhesion promoting layer.
  • the first plasma polymerized film has a higher degree of polymerization than the second plasma polymerized film because the polymerization proceeds not only in the first irradiation process but also in the second irradiation process. It is considered that the plasma density in the second discharge space 15 can be increased by using argon as the discharge gas in the second irradiation step, and the degree of polymerization of the first and second plasma polymer films can be increased.
  • the PMMA film 9 is folded back by the guide roll 16 to reciprocate in the second discharge space 15 and is processed twice by the second discharge gas supply means 50. The PMMA film 9 after reciprocating in the second discharge space is sent along the third roll electrode 13 and is unloaded from the apparatus 1.
  • the PMMA film 9 after the surface treatment is bonded to a PVA film through a PVA adhesive to produce a polarizing plate.
  • the adhesive strength between the difficult-to-adhere PMMA film 9 and the PVA adhesive can be improved.
  • the adhesion durability can be sufficiently increased.
  • acrylic acid as the polymerizable monomer of the reaction component and using argon as the discharge gas, it is possible to reliably increase the above-described adhesive strength and thus the adhesive durability.
  • Concerning the adhesive durability when the PMMA film is exposed to a high temperature and high humidity environment, the adhesive strength can be made higher than before the exposure (see Examples 1 to 4 below). Thereby, peeling of a polarizing plate can be prevented and quality can be improved.
  • the carrier gas of the first and second reaction gases is not limited to nitrogen (N 2 ), and may be argon (Ar).
  • the carrier gas may be the same component as the first and second discharge generation gases. Then, even if the carrier gas (Ar) flows into the discharge spaces 14 and 15, it is possible to prevent the discharge state from changing, and to maintain a stable discharge.
  • the carrier gas may be other rare gas such as helium or neon. The first contact step and the first irradiation step may be performed concurrently.
  • the gas nozzle 23 may be omitted, and the first reactive gas containing acrylic acid and argon may be blown out from the gas nozzles 33 and 34 into the first discharge space 14. This argon serves as both the carrier gas for the first reaction gas and the first discharge product gas.
  • the second contact step and the second irradiation step may be performed simultaneously.
  • the gas nozzle 43 may be omitted, and the second reactive gas containing acrylic acid and argon may be blown out from the gas nozzles 53 and 54 into the second discharge space 15. This argon serves as both the carrier gas for the second reaction gas and the second discharge product gas.
  • the PMMA film may be exposed to a high temperature and high humidity environment.
  • the adhesion durability of the PMMA film can be increased.
  • Four or more roll electrodes may be arranged, and acrylic acid-containing reactive gas spraying and argon plasma irradiation may be performed three or more times.
  • the preceding acrylic acid-containing reactive gas spraying is the “first contact process”
  • the preceding argon plasma irradiation is the “first irradiation process”.
  • the subsequent acrylic acid-containing reactive gas spraying becomes the “second contact step”
  • the subsequent argon plasma irradiation becomes the “second irradiation step”.
  • the present invention is not limited to the following examples.
  • an optical film O-PMMA
  • the width of the film 9 was 320 mm.
  • a mixed gas of N 2 and O 2 was converted into plasma and irradiated onto the PMMA film 9 to clean the surface of the film 9 (removal of organic impurities).
  • a first contact process, a first irradiation process, a second contact process, and a second irradiation process are sequentially performed on the PMMA film 9 using an apparatus having substantially the same structure as the surface treatment apparatus 1 of FIG. It was.
  • the dimensional configuration and processing conditions of the surface treatment apparatus 1 were as follows.
  • Axial length in roll width direction of roll electrodes 11, 12, 13: 390mm Diameter of roll electrodes 11, 12, 13: 310mm Power supplied to roll electrode 12: 250 W (DC voltage 120 V x DC current 2.1 A is converted to high frequency) Supply frequency: 50 kHz Applied voltage between roll electrodes 11 and 12 and between roll electrodes 12 and 13: Vpp 6.5 kV Conveying speed of PMMA film 9: 20 m / min Setting temperature of PMMA film 9: 40 ° C First reaction gas (AA + N 2 ) blowing temperature: 75 ° C.
  • a PVA adhesive was applied to the surface to be treated of the PMMA film 9 after the surface treatment, and was bonded to the PVA film.
  • the adhesive was dried at 80 ° C. for 5 minutes. Separately, acrylic acid was sprayed on the TAC film, and N 2 plasma was irradiated. This TAC film was bonded to the opposite surface of the PVA film with the same PVA adhesive as described above. Thus, a plurality of polarizing plate samples having a three-layer structure were produced. The width of the polarizing plate sample was 25 mm.
  • the adhesive strength between the PMMA film 9 and the PVA film was measured for a polarizing plate sample that was not subjected to the wet heat treatment described below.
  • the measuring method was based on the floating roller method (JIS K6854). The result was an average of 2.9 N / inch.
  • the remaining polarizing plate sample was subjected to wet heat treatment after the PVA adhesive was cured.
  • the inside of the wet heat treatment tank was set to a high temperature and high humidity environment of 60 ° C. and 95% RH, and the polarizing plate sample was left in this wet heat treatment tank for 1 hour. Thereafter, the polarizing plate sample was taken out of the wet heat treatment tank and cooled at room temperature for 3 minutes.
  • the adhesive strength (referred to as "durable adhesive strength") between the PMMA film 9 and the PVA film was measured by the same floating roller method (JIS K6854) as the initial adhesive strength. The result was broken at 8.4 N / inch.
  • Example 1 the surface treatment of the PMMA film 9, the preparation of the polarizing plate sample, and the evaluation (initial adhesive strength measurement / durable adhesive strength measurement) were all performed on the same day.
  • Example 2 the acrylic acid concentration in the first reaction gas was 5.8%, and the acrylic acid concentration in the second reaction gas was 5.8%.
  • the other conditions were the same as in Example 1.
  • the procedure for preparing the polarizing plate sample after the surface treatment and the procedure for measuring the initial adhesive strength and the durable adhesive strength were also the same as in Example 1.
  • the initial adhesive strength was 1.8 N / inch on average. In the measurement of the durable adhesive strength, the material was broken at 8.4 N / inch.
  • Example 3 the conveyance speed of the PMMA film 9 was 10 m / min.
  • the other conditions were the same as in Example 2.
  • the procedure for preparing the polarizing plate sample after the surface treatment and the procedure for measuring the initial adhesive strength and the durable adhesive strength were the same as those in Examples 1 and 2.
  • the initial adhesive strength was 2.9 N / inch on average. In the measurement of the durable adhesive strength, the material was broken at 8.7 N / inch.
  • the initial adhesive strength can be adjusted by setting the acrylic acid concentrations in the first and second reaction gases or by setting the conveying speed. That is, the initial adhesive strength could be increased by increasing the acrylic acid concentration or decreasing the transport speed. In addition, the durable adhesive strength could be sufficiently increased regardless of the acrylic acid concentration and the conveyance speed.
  • Example 4 the surface treatment of PMMA film 9 (OP-PMMA) was performed under the same conditions as in Example 1.
  • the PMMA film 9 after the surface treatment was wound into a roll, and this was left at room temperature for 38 days.
  • the polarizing plate sample was produced in the same procedure as Example 1, and the initial stage adhesive strength and durable adhesive strength were measured.
  • the initial adhesive strength was 2.8 N / inch on average.
  • the durable adhesive strength the material was broken at 9.9 N / inch. It was confirmed that almost no change with time after the surface treatment occurred.
  • Table 1 summarizes the main processing conditions and evaluations of Examples 1 to 4.
  • Comparative Example 1 As Comparative Example 1, a polarizing plate sample was prepared for the PMMA film 9 (OP-PMMA) not subjected to the surface treatment, and the initial adhesive strength and the durable adhesive strength were measured. The procedure for preparing the polarizing plate sample and the measurement procedure for the initial adhesive strength and the durable adhesive strength were the same as in Example 1. The initial adhesive strength was 0.4 N / inch on average. The average durable adhesive strength was 0.5 N / inch.
  • Comparative Example 2 As Comparative Example 2, the second contact step and the second irradiation step were omitted in the surface treatment of the PMMA film 9 (OP-PMMA), and only the first contact step and the first irradiation step were performed.
  • the other surface treatment conditions, the preparation procedure of the polarizing plate sample, and the measurement procedure of the initial adhesive strength and the durable adhesive strength were the same as in Example 1.
  • the initial adhesive strength was 1.2 N / inch on average.
  • the average durable adhesive strength was 2.7 N / inch. From the results of Examples and Comparative Example 2 above, it was confirmed that the initial adhesive strength and the durable adhesive strength can be improved by repeating the acrylic acid spraying and the argon plasma irradiation.
  • Comparative Example 3 In Comparative Example 3, nitrogen (N 2 ) was used as the first and second discharge generation gases. The other surface treatment conditions were the same as in Example 1, including the flow rates of the first and second discharge product gases. The production procedure of the polarizing plate sample and the measurement procedure of the initial adhesive strength and the durable adhesive strength were also the same as in Example 1. The initial adhesive strength was 1.3 N / inch on average. The average durable adhesive strength was 6.3 N / inch. From the results of Examples and Comparative Example 3 above, it was confirmed that the initial adhesive strength and the durable adhesive strength can be improved by using argon as the discharge generation gas.
  • Comparative Example 4 In Comparative Example 4, the second contact step and the second irradiation step were omitted in Comparative Example 3, and only the first contact step and the first irradiation step were performed.
  • the other surface treatment conditions, the preparation procedure of the polarizing plate sample, and the measurement procedure of the initial adhesive strength and the durable adhesive strength were the same as those in Comparative Example 3.
  • the initial adhesive strength was 1.2 N / inch on average.
  • the durable adhesive strength was 1.6 N / inch on average.
  • Comparative Example 6 In Comparative Example 6, the second contact step and the second irradiation step were omitted in the surface treatment for the PMMA film (OS-PMMA manufactured by Sekisui Chemical Co., Ltd.), and only the first contact step and the first irradiation step were performed.
  • the other surface treatment conditions, the preparation procedure of the polarizing plate sample, and the measurement procedure of the initial adhesive strength and the durable adhesive strength were the same as in Example 1.
  • the initial adhesive strength was 2.7 N / inch on average.
  • the average durable adhesive strength was 4.8 N / inch.
  • Comparative Example 7 nitrogen (N 2 ) was used as the first discharge product gas in Comparative Example 6.
  • the other processing conditions were the same as those in Comparative Example 6 including the flow rate of the first discharge product gas.
  • the procedure for producing the polarizing plate sample and the measurement procedure for the initial adhesive strength and the durable adhesive strength were the same as those in Example 1.
  • the initial adhesive strength was 2.7 N / inch on average.
  • the average durable adhesive strength was 4.8 N / inch.
  • Table 2 summarizes the main processing conditions and evaluations of Comparative Examples 1-7.
  • “single” in the “number of treatments” column indicates that only the first contact process and the first irradiation process were performed as the surface treatment process, and “twin” represents the first contact process as the surface treatment process. And the first irradiation step, the second contact step, and the second irradiation step.
  • the present invention can be applied to a polarizing plate of a flat panel display (FPD), for example.
  • FPD flat panel display
  • 1 Film surface treatment device 9 Film to be treated (PMMA film) DESCRIPTION OF SYMBOLS 10 Electrode structure 11 1st roll electrode 12 2nd roll electrode 13 3rd roll electrode 14 Gap, 1st discharge space 15 Gap, 2nd discharge space 16 Guide roll 17 Guide roll 20 1st reaction gas supply means 21 1st reaction gas Supply source 22 Gas path 23 First reaction gas nozzle 24 Shield member 25 First blowing space 30 First discharge gas supply means 31 First discharge gas supply source 32 Gas path 33 Lower first discharge gas nozzle 34 Upper first discharge gas nozzle 40 second reaction gas supply means 41 second reaction gas supply source 42 gas path 43 second reaction gas nozzle 44 shielding member 45 second blowing space 50 second discharge gas supply means 51 second discharge gas supply source 52 gas path 53 lower side Second discharge gas nozzle 54 of the second upper discharge gas nozzle

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EP3320986A1 (en) 2016-11-09 2018-05-16 Europlasma NV Hydrophilic, multifunctional ultra-thin coatings with excellent stability and durability

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KR101930972B1 (ko) * 2011-08-30 2018-12-19 세키스이가가쿠 고교가부시키가이샤 필름 표면 처리 방법 및 장치
JP6319000B2 (ja) * 2014-09-05 2018-05-09 日産自動車株式会社 強化基材の表面改質方法及び表面改質装置
JP6421962B1 (ja) * 2017-08-09 2018-11-14 春日電機株式会社 表面改質装置

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JP2010150372A (ja) * 2008-12-25 2010-07-08 Sekisui Chem Co Ltd フィルムの表面処理方法及び装置並びに偏光板の製造方法
JP2010150373A (ja) * 2008-12-25 2010-07-08 Sekisui Chem Co Ltd フィルムの表面処理方法及び接着方法並びに偏光板の製造方法

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JPH11241165A (ja) * 1998-02-26 1999-09-07 Sekisui Chem Co Ltd 表面処理品の製造方法
JP2009025604A (ja) * 2007-07-20 2009-02-05 Konica Minolta Opto Inc 偏光板保護フィルム、その製造方法及び製造装置、並びに偏光板、その製造方法及び表示装置
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Publication number Priority date Publication date Assignee Title
EP3320986A1 (en) 2016-11-09 2018-05-16 Europlasma NV Hydrophilic, multifunctional ultra-thin coatings with excellent stability and durability
WO2018087192A1 (en) 2016-11-09 2018-05-17 Europlasma Nv Hydrophilic, multifunctional ultra-thin coatings with excellent stability and durability
US11167311B2 (en) 2016-11-09 2021-11-09 Europlasma Nv Hydrophilic, multifunctional ultra-thin coatings with excellent stability and durability

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