WO2011118408A1 - Dispositif de traitement au plasma - Google Patents

Dispositif de traitement au plasma Download PDF

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Publication number
WO2011118408A1
WO2011118408A1 PCT/JP2011/055669 JP2011055669W WO2011118408A1 WO 2011118408 A1 WO2011118408 A1 WO 2011118408A1 JP 2011055669 W JP2011055669 W JP 2011055669W WO 2011118408 A1 WO2011118408 A1 WO 2011118408A1
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WO
WIPO (PCT)
Prior art keywords
flow path
temperature
nozzle
liquid
path
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PCT/JP2011/055669
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English (en)
Japanese (ja)
Inventor
真一 川崎
光秀 野上
良憲 中野
崇 佐藤
Original Assignee
積水化学工業株式会社
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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 CN201180015135.XA priority Critical patent/CN102884223B/zh
Priority to KR1020127027561A priority patent/KR101473547B1/ko
Priority to JP2012506932A priority patent/JP5503733B2/ja
Publication of WO2011118408A1 publication Critical patent/WO2011118408A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45563—Gas nozzles
    • C23C16/45578—Elongated nozzles, tubes with holes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45563—Gas nozzles
    • C23C16/4557—Heated nozzles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/3244—Gas supply means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32532—Electrodes
    • H01J37/32541—Shape
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32733—Means for moving the material to be treated
    • H01J37/32752—Means for moving the material to be treated for moving the material across the discharge
    • H01J37/32761—Continuous moving
    • H01J37/3277—Continuous moving of continuous material

Definitions

  • the present invention relates to a plasma processing apparatus for converting a reactive gas into plasma and bringing it into contact with an object to be processed, and particularly to a temperature control structure of a reactive gas supply nozzle in the plasma processing apparatus.
  • an electric heater is embedded in a reactive gas supply nozzle.
  • the supply nozzle is heated with an electric heater, and the temperature of the reaction gas is maintained at a high temperature. According to the electric heater, the heating time is short and the response is fast.
  • Wiring for power feeding is simple and ancillary equipment such as a controller is simple.
  • the tip of the reactive gas supply nozzle faces the gap between the pair of electrodes. Plasma treatment is performed by applying an electric field to the gap.
  • the supply nozzle is made of, for example, an insulating resin.
  • JP 2004-124238 A (0032, FIG. 4) JP 2009-035724 A International Publication WO 2009/008284 (Fig. 5)
  • the reactive gas supply nozzle is arranged in such a manner that the tip portion is arranged in the vicinity of the electrodes or faces the discharge space between the electrodes. Even in such a case, if the electric heater is disposed in a portion far from the tip of the nozzle, the possibility that the electric heater and the electrode are short-circuited is small. However, it is conceivable that the tip of the nozzle cannot be heated sufficiently. If the electrode is cooled by the cooling means, even the tip of the nozzle may be cooled.
  • the reaction component in the reaction gas is condensable, that is, when the reaction component is a liquid at room temperature and is vaporized to generate a reaction gas
  • the above-mentioned reaction component is generated particularly in the inside of the tip of the nozzle. May condense (condensate).
  • the electric heater is disposed near the tip of the nozzle, the insulation distance between the electric heater and the electrode is shortened, and there is a risk of short circuit.
  • a temperature sensor such as a thermocouple breaks down, the electric heater may be ignited due to overheating. In order to prevent this, if the sensor is duplicated, the cost increases.
  • the present invention has been made in view of the above circumstances, and provides a plasma processing apparatus that can prevent condensation inside the nozzle and avoid problems such as short circuits even when the reaction components of the reaction gas tend to condense.
  • the main purpose is to provide.
  • the present invention is a plasma processing apparatus for bringing a reaction gas containing a condensable reaction component into contact with an object to be processed and irradiating with plasma.
  • a pair of electrodes forming a discharge space near atmospheric pressure for plasma irradiation between each other;
  • a tip portion having a blow-out port is made of an insulator, and the tip portion is arranged in the vicinity of at least one of the pair of electrodes or the discharge space, and the reaction gas is passed from the blow-out port to the object to be processed.
  • a nozzle to spray, Nozzle temperature adjusting means for adjusting the temperature of the nozzle is disposed at a temperature adjusting path formed in the nozzle and through which the temperature adjusting liquid is passed, and is disposed away from the electrode and the nozzle, and the temperature of the temperature adjusting liquid is reacted in the reaction gas.
  • the liquid temperature control part which adjusts so that it may become higher than the condensation temperature of a component, and the pipe line which connects the said liquid temperature control part and the said temperature control path are characterized by the above-mentioned.
  • the temperature adjustment liquid whose temperature is adjusted by the liquid temperature adjustment unit is passed through the temperature adjustment path in the nozzle.
  • the temperature of the nozzle can be adjusted to be higher than the condensation temperature of the reaction components in the reaction gas.
  • a temperature control path can also be formed at the nozzle tip disposed near the electrode or the discharge space. Therefore, the reaction component can be reliably blown out from the nozzle in a gaseous state.
  • the surface treatment of the workpiece can be performed satisfactorily, and the treatment effect can be enhanced. It is not necessary to provide an electric heater and an electric system associated therewith in the nozzle, and it is easy to deal with leakage from the electrodes.
  • the temperature adjusting liquid is preferably insulating.
  • the electrical conductivity of the temperature adjusting liquid is preferably 50 ⁇ S / cm or less, more preferably 30 ⁇ S / cm or less, and still more preferably 10 ⁇ S / cm or less.
  • the object to be processed is a continuous film
  • at least one of the pair of electrodes is a cylindrical electrode around which the object to be processed is wound and rotated, and the nozzle is close to the cylindrical electrode You may do it.
  • the nozzle may face the discharge space.
  • the plasma processing apparatus may further include a film temperature adjusting means for adjusting the temperature of the cylindrical electrode and thus the temperature of the object to be processed to be lower than the condensation temperature.
  • the nozzle Although the nozzle is deprived of heat by the cylindrical electrode in the vicinity thereof, the nozzle can be reliably maintained at a high temperature by passing the temperature adjusting liquid through the temperature adjusting path.
  • the outer peripheral portion of the cylindrical electrode near the nozzle is heated by taking heat away from the nozzle, but since it is separated from the nozzle by rotation, the heating is temporary. Therefore, the electrode can be maintained at a low temperature, and thus the workpiece can be maintained at a low temperature. Therefore, the reaction components can be reliably condensed and adhered on the object to be processed, and the processing reaction can be reliably caused.
  • the temperature adjustment path extends from one end (first end) of the nozzle in the processing width direction to the other end. It is preferable to be provided over (second end). Thereby, the temperature of the nozzle can be uniformly controlled over almost the entire length.
  • the first end portion includes a first end surface in the longitudinal direction of the nozzle and the vicinity thereof.
  • the second end portion includes a second end surface opposite to the first end surface in the longitudinal direction of the nozzle and a vicinity thereof.
  • the entrance / exit port of the temperature control path may be provided on the first and second end faces of the nozzle, or may be provided on a side surface in the vicinity of the first and second end faces of the nozzle.
  • the nozzle is preferably provided with a dispersion path for uniformly dispersing the reaction gas in the processing width direction.
  • the electrode extends in the processing width direction.
  • the axial line of the cylindrical electrode faces the processing width direction.
  • the temperature adjustment path is a temperature adjustment forward path (upper flow path) through which the temperature adjustment liquid flows in one direction in the longitudinal direction (processing width direction) of the nozzle, and the temperature adjustment liquid is opposite to the one direction.
  • a downstream end of the temperature adjustment forward path and an upstream end of the temperature adjustment return path may be connected by a return path (connection path).
  • the temperature adjustment liquid heats the nozzle while flowing in the longitudinal direction of the nozzle in the temperature adjustment path, and then folds back in the return path and adds the nozzle while flowing in the temperature adjustment path in the direction opposite to the temperature adjustment path. Warm up. As the temperature adjusting liquid flows, the temperature gradually decreases due to heat exchange with the nozzle. Therefore, heating can be performed almost evenly regardless of the position in the longitudinal direction of the nozzle. Therefore, even if the length of the nozzle is large, the temperature of the entire nozzle can be controlled almost uniformly.
  • An upper flow path including first and second upper flow path portions that are arranged at the same height and flow part of the temperature adjustment liquid respectively, and a downstream position that is disposed higher than the upper flow path.
  • a connection path that extends vertically and has a lower end connected to the upper flow path and an upper end connected to the lower flow path, and the temperature adjusting liquid flows in the order of the upper flow path, the connection path, and the lower flow path. It is preferable.
  • the temperature adjustment liquid is first introduced into the lower upper flow path among the lower upper flow path and the high lower flow path. Therefore, after the temperature adjustment liquid has spread over the entire first upper flow path portion and the second upper flow path portion of the upper flow path, the temperature adjustment liquid ascends the connection path and is introduced into the lower lower flow path. As a result, it is possible to prevent the temperature control path from flowing biased to one of the first and second upper flow path portions. As a result, the temperature inside the nozzle can be reliably controlled over a wide range.
  • the upper flow path includes a branch portion that branches into the first upper flow path portion and the second upper flow path portion. Since the upper flow path is in a low place, the temperature adjusting liquid can be surely diverted from the branch part to both the first and second upper flow path portions, and both the first and second upper flow path portions are heated. It can be surely filled with the preparation.
  • the lower flow path includes first and second lower flow path portions that are arranged at the same height and flow a part of the temperature adjusting liquid.
  • the temperature adjusting liquid that has flowed through the first upstream portion is sent to the first lower flow path portion through the first connection path portion.
  • the temperature adjusting liquid that has flowed through the second upstream portion is sent to the second lower flow path portion through the second connection path portion.
  • the temperature adjustment liquid can surely flow in both the first upper flow path portion and the second upper flow path portion, the temperature adjustment liquid can be reliably supplied to both the first lower flow path portion and the second lower flow path portion. Can be shed. As a result, the temperature inside the nozzle can be controlled over a wider range.
  • the lower flow path includes a merging portion where the first lower flow path portion and the second lower flow path portion merge.
  • the temperature control liquid that has flowed through the first lower flow path portion and the temperature control path that has flowed through the second lower flow path portion merge at the junction.
  • the downstream ends of the first and second upper flow path portions may join together and continue to the lower end portion (upstream end) of the connection path, and the first and second ends from the upper end portion (downstream end) of the connection path. 2
  • the lower flow path portion may be branched.
  • the first and second upper flow path portions are aligned with each other in the alignment direction orthogonal to the processing width direction.
  • Each preferably extends in the direction. More preferably, the first and second upper flow path portions extend from the first end portion of the nozzle in the processing width direction to the second end portion.
  • the temperature of the nozzle can be controlled over a wide range.
  • the processing width direction and the arrangement direction are horizontally oriented.
  • the branch portion includes a branch path extending in the arrangement direction. It is preferable that the branch portion is provided at a first end portion or a second end portion of the nozzle.
  • first and second lower flow path portions are aligned with each other in the arrangement direction and extend in the processing width direction. More preferably, the first and second lower flow path portions extend from a first end portion of the nozzle in the processing width direction to a second end portion. It is preferable that the merging portion includes a merging channel extending in the arrangement direction. It is preferable that the junction is provided at the first end or the second end of the nozzle.
  • 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 present invention it is possible to prevent the reaction components in the reaction gas from condensing in the nozzle. Even if the nozzle is disposed in the electric field between the electrodes, it is possible to avoid an electrical failure such as a short circuit.
  • FIG. 1 is a perspective view schematically showing a plasma processing apparatus according to a first embodiment of the present invention. It is a perspective view which shows roughly the plasma processing apparatus which concerns on 2nd Embodiment of this invention. It is side surface sectional drawing of the nozzle which concerns on 3rd Embodiment of this invention. It is a perspective view which shows roughly the plasma processing apparatus which concerns on 4th Embodiment of this invention. It is a perspective view which shows roughly the plasma processing apparatus which concerns on 5th Embodiment of this invention.
  • FIG. 1 shows a first embodiment of the present invention.
  • the to-be-processed object 9 of this embodiment is comprised with the continuous resin film.
  • the to-be-processed film 9 is a protective film of a polarizing plate, for example.
  • the protective film 9 contains triacetate cellulose (TAC) as a main component.
  • TAC triacetate cellulose
  • the component of the film 9 is 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.
  • the thickness of the film 9 is, for example, about 100 ⁇ m.
  • the protective film 9 and a polarizing film made of a PVA film are bonded together with an adhesive to constitute a polarizing plate.
  • an aqueous adhesive such as an aqueous PVA solution is used.
  • the protective film 9 is surface-treated by the plasma processing apparatus 1 to improve the adhesion of the protective film 9.
  • the plasma processing apparatus 1 includes electrodes 11 and 12 and a nozzle 20.
  • the electrodes 11 and 12 are both constituted by cylindrical roll electrodes. Roll electrodes 11 and 12 are arranged in parallel to each other.
  • a direction along the axis of the electrodes 11 and 12 is appropriately referred to as a “processing width direction”.
  • a direction in which the electrodes 11 and 12 are arranged (a direction orthogonal to the processing width direction) is referred to as an “alignment direction”.
  • the processing width direction and the alignment direction are both horizontal, but the present invention is not limited to this.
  • a narrow gap 13 is formed between the roll electrodes 11 and 12.
  • One of the pair of electrodes 11 and 12 is connected to a power source (not shown). The other electrode is electrically grounded.
  • the power source supplies, for example, pulsed power to the electrodes 11 and 12. As a result, an electric field is applied between the pair of electrodes 11 and 12, plasma is generated in the gap 13 near atmospheric pressure, and the gap 13 becomes a discharge space near atmospheric pressure
  • a continuous sheet-like film 9 to be processed is wound around the circumference of the upper side of the roll electrodes 11 and 12 about a half turn with the width direction thereof being in the axial direction of the electrodes 11 and 12 (process width direction).
  • the film 9 to be treated is passed through the discharge space 13 along the peripheral surfaces of the roll electrodes 11, 12, suspended below the discharge space 13, and folded back by the guide roll 14.
  • the roll electrodes 11 and 12 are rotated in the same direction (clockwise in FIG. 1) around their own axes and in synchronization with each other. Thereby, the to-be-processed film 9 is conveyed from the roll electrode 11 to the roll electrode 12.
  • Film temperature adjusting means 3 is incorporated in the roll electrodes 11 and 12.
  • the film temperature adjusting means 3 includes, for example, an in-electrode temperature adjusting path 3 a formed inside the roll electrodes 11 and 12.
  • a temperature control medium such as temperature-controlled water is passed through the temperature control path 3a. Accordingly, the temperature of the electrodes 11 and 12 and the temperature of the film 9 to be processed in contact with the electrodes 11 and 12 are adjusted to be lower than the condensation temperature of the reaction components in the reaction gas described later.
  • the nozzle 20 is arranged above the discharge space 13 between the roll electrodes 11 and 12. At least the lower part (tip part in the blowing direction) of the nozzle 20 is made of resin and has an insulating property.
  • the nozzle 20 has a long shape extending long in the processing width direction. The length along the processing width direction of the nozzle 20 is substantially equal to or larger than the axial length of the roll electrodes 11 and 12. Both end portions of the nozzle 20 are disposed at substantially the same position in the processing width direction as the end portions on the same side of the roll electrodes 11 and 12, respectively.
  • the cross section orthogonal to the extension direction is tapering downward.
  • the lower end portion (tip portion) of the nozzle 20 is inserted into a gradually narrowing portion between the roll electrodes 11 and 12 and faces the upper end portion of the discharge space 13.
  • a blowout path 21 is formed inside the nozzle 20.
  • the upstream end of the blow-out path 21 is connected to the reactive gas source 2 through the supply path 2a.
  • the blow-out path 21 includes a dispersion path 22 that uniformly disperses the reaction gas from the supply path 2a in the processing width direction.
  • the tip of the blow-out path 21 reaches the lower end surface (tip surface) of the nozzle 20 to form a blow-out port 23.
  • the tip of the nozzle 20 has an outlet 23.
  • the reaction gas contains reaction components that are liquid at room temperature (about 15 ° C to 25 ° C).
  • reaction components include polymerizable monomers.
  • acrylic acid AA is used as a reaction component composed of a polymerizable monomer.
  • Acrylic acid vapor is flammable (explosive).
  • the reactive gas is generated in the reactive gas source 2.
  • the reactive gas source 2 is constituted by a vaporizer.
  • acrylic acid as a reaction component is stored in a liquid state.
  • the vaporizer 2 is provided with a heater (not shown), and the temperature of the liquid acrylic acid is adjusted by this heater.
  • 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 liquid acrylic acid and the distribution ratio between the part and the remainder of the carrier gas.
  • the reactive gas source 2 and the nozzle 20 are connected by a reactive gas supply path 2a.
  • the supply path 2a is formed of a resin tube.
  • a ribbon heater (supply path temperature adjusting means) is wound around the resin tube. The ribbon heater is provided over the entire length of the supply path 2a. A part or the whole of the supply path 2a may be constituted by a metal pipe instead of the resin tube.
  • the plasma processing apparatus 1 is provided with nozzle temperature adjusting means 30.
  • the nozzle temperature adjusting means 30 includes a liquid temperature adjusting unit 31, a nozzle internal temperature adjusting path 32 formed in the nozzle 20, and pipe lines 33 and 34 connecting the liquid temperature adjusting unit 31 and the temperature adjusting path 32.
  • the temperature adjusting liquid is circulated in the order of the liquid temperature adjusting unit 31, the outgoing line 33, the temperature adjusting path 32, and the return line 34.
  • the liquid temperature adjusting unit 31 is arranged away from the roll electrodes 11 and 12 and the nozzle 20.
  • the liquid temperature adjustment unit 31 adjusts the temperature of the temperature adjustment liquid.
  • the liquid temperature adjustment unit 31 includes a liquid temperature setting unit 31a, a liquid storage unit 31b, a liquid temperature sensor 31c, a liquid heating unit 31d, and a control unit 31e.
  • the liquid temperature setting unit 31a is configured by a touch panel, a dial, or the like, and a desired set temperature of the temperature adjustment liquid is input.
  • the set temperature of the temperature adjusting liquid is higher than the condensation temperature of the reaction components in the reaction gas.
  • the liquid storage part 31b is a space for storing the temperature control liquid, and may be a tank or a tube.
  • the liquid temperature sensor 31c detects the temperature of the temperature adjusting liquid in the liquid container 31b.
  • the liquid temperature sensor 31c may detect the temperature of the temperature adjustment liquid in the forward line 33 or the return line 34 instead of the temperature adjustment liquid in the liquid storage unit 31b. Alternatively, the liquid temperature sensor 31c may detect the temperature adjustment liquid in the temperature adjustment path 32, and may further detect the temperature of the nozzle 20 itself.
  • the liquid heating unit 31d includes a heat exchanger, an electric heater, and the like, and warms the temperature adjustment liquid in the liquid storage unit 31b.
  • the control unit 31e includes a microcomputer, an input signal conversion processing unit from the liquid temperature sensor 31c, a drive circuit for the liquid heating unit, and the like, and the temperature of the temperature adjustment liquid is determined based on a temperature detection value by the liquid temperature sensor 31c. The liquid heating unit 31d is controlled to reach the temperature set by the liquid temperature setting unit 31a.
  • the outgoing line 33 is connected to the outlet port of the liquid container 31d.
  • the outgoing line 33 extends to one end of the nozzle 20 in the longitudinal direction (first end, lower left in FIG. 1). It is preferable that at least a part of the outgoing line 33 is made of resin (insulating material). Preferably, a portion near the nozzle 20 of the outgoing line 33, and thus a portion near the electrodes 11 and 12, are made of resin (insulating material).
  • a liquid feed pump 37 is provided in the outgoing line 33.
  • the liquid feed pump 37 may be provided in the return pipe 34 or may be provided in the liquid temperature adjusting unit 31.
  • a distribution unit 35 is provided near the first end of the nozzle 20. In the distribution unit 35, the forward duct 33 is branched into a plurality (two in the figure).
  • a plurality (two in the figure) of temperature control paths 32 are formed inside the nozzle 20. At least one temperature control path 32 is disposed as low as possible (front end side) of the nozzle 20. Each temperature control path 32 extends over the entire length of the nozzle 20 in the longitudinal direction (process width direction). One end portion (first end portion, lower left portion in FIG. 1) of each temperature control path 32 reaches one end face (first end face) of the nozzle 20 and is connected to one of the branched outgoing pipes 33. .
  • each temperature control path 32 reaches the other end (second end) of the nozzle 20.
  • Return pipes 34 are respectively connected to the second ends of the temperature control paths 32. It is preferable that at least a portion close to the nozzle 20 of the return pipe 34, and hence a portion close to the electrodes 11 and 12, be made of resin (insulating material). Near the second end of the nozzle 20, a merging portion 36 is provided. A plurality of return pipelines 34 are joined at the junction 36. One return pipe 34 after joining extends from the joining part 36 to the liquid temperature adjusting part 31. The tip of the return pipe 34 is connected to the inlet port of the liquid storage part 31d. Although detailed illustration is omitted, the blow-out path 21 passes between the two temperature control paths 32 and 32 arranged in the alignment direction.
  • Water is used as the temperature control solution.
  • insulating pure water or ion-exchanged water is used as the temperature adjusting liquid.
  • the conductivity of the temperature adjusting liquid is sufficiently smaller than the conductivity of general tap water (about 100 ⁇ S / cm), preferably 50 ⁇ S / cm or less, more preferably 30 ⁇ S / cm or less, and even more preferably 10 ⁇ S. / Cm or less.
  • 0 ⁇ S / cm pure water or ion-exchanged water as measured with an electric conductivity measuring instrument on the order of ⁇ S / cm is used as the temperature adjusting liquid.
  • ion-exchanged water is used as a temperature control liquid, it is preferable to provide an ion-exchange filter 38 in the outgoing line 33 or the return line 34 to maintain electrical insulation.
  • the film 9 to be processed is wound around the roll electrodes 11 and 12 and the guide roll 14.
  • the roll electrodes 11 and 12 are rotated clockwise in FIG. 1, and the film 9 to be processed is conveyed substantially in the right direction.
  • Electric power is supplied to the electrodes 11 and 12 from a power source (not shown), an electric field is applied between the electrodes 11 and 12, and plasma discharge near atmospheric pressure is generated in the gap 13.
  • a carrier gas (N 2) to vaporize acrylic acid (AA), to produce a reaction gas (AA + N 2).
  • the temperature of the liquid acrylic acid in the vaporizer 2 is adjusted to 40 ° C. to 100 ° C., for example.
  • the reaction gas is sent from the vaporizer 2 to the gas supply path 2a.
  • the ribbon heater (supply path temperature adjusting means) provided in the gas supply path 2a maintains the temperature of the gas supply path 2a higher than the condensation temperature of acrylic acid in the reaction gas. For example, the temperature of the supply path 2a is adjusted to 40 ° C. to 200 ° C.
  • the reaction gas (AA + N 2 ) is introduced from the gas supply path 2 a into the blowing path 21 of the nozzle 20.
  • the reaction gas is uniformly dispersed in the longitudinal direction (process width direction) of the nozzle 20 by the dispersion path 22 of the blowing path 21 and then blown out from the blowing port 23 at the lower end of the nozzle 20 to the discharge space 13. 13 to the film 9 to be processed.
  • This blowing flow is a flow that is uniformly distributed in the processing width direction.
  • the film temperature adjusting means 3 lowers the temperature of the roll electrodes 11 and 12, and thus the temperature of the film 9 to be processed, lower than the condensation temperature of acrylic acid in the reaction gas.
  • the temperature of the film to be processed 9 is adjusted to 15 ° C. to 30 ° C.
  • acrylic acid in the reaction gas condenses and adheres to the film 9 to be processed.
  • This acrylic acid is activated by the plasma in the discharge space 13, and double bond cleavage, polymerization and the like occur.
  • Nitrogen in the reaction gas is turned into plasma (including excitation, activation, radicalization, ionization, etc.) in the discharge space 13.
  • 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. Thereby, an adhesion promoting layer is formed on the surface of the film 9 to be processed.
  • the nozzle temperature adjusting means 30 adjusts the temperature of the nozzle 20 to be higher than the condensation temperature of acrylic acid in the reaction gas. For example, the temperature of the nozzle 20 is adjusted to 40 ° C. to 200 ° C.
  • the set temperature of the nozzle 20 is input to the liquid temperature setting unit 31 a of the liquid temperature adjusting unit 31.
  • the liquid feed pump 37 is driven, and the temperature adjustment liquid (pure water or ion exchange water) of the nozzle temperature adjustment means 30 is circulated in the order of the liquid storage portion 31b, the forward conduit 33, the temperature adjustment passage 32, and the return conduit 34. .
  • the temperature of the temperature adjusting liquid is detected by the liquid temperature sensor 31c. Based on this temperature detection signal, the control unit 31e controls the liquid heating unit 31d to adjust the temperature adjustment liquid so that it becomes a set temperature.
  • the temperature-adjusted temperature adjustment liquid is introduced into each temperature adjustment path 32 of the nozzle 20 via the forward duct 33 and the distribution path 35.
  • This temperature adjustment liquid flows in the longitudinal direction of the nozzle 20 in the temperature adjustment path 32. Thereby, the nozzle 20 can be heated to be higher than the condensation temperature of the acrylic acid.
  • the upper limit of the temperature control liquid and thus the set temperature of the nozzle 20 is set below the explosion limit of acrylic acid.
  • the explosion point of acrylic acid changes depending on the oxygen concentration.
  • the tip of the nozzle 20 can be reliably heated to a temperature higher than the condensation temperature of the acrylic acid. Even when the roll electrodes 11 and 12 are cooled, the tip of the nozzle 20 in the vicinity thereof can be reliably maintained at a temperature higher than the condensation temperature of the acrylic acid. Therefore, it is possible to prevent the acrylic acid (reaction component) in the reaction gas from condensing, particularly at the tip portion in the nozzle 20. Thereby, acrylic acid can be reliably blown out from the blow-out port 23 at the tip of the nozzle 20 in a gaseous state, and can be sprayed uniformly on the film 9 to be processed. Therefore, processing uniformity can be ensured and processing quality can be improved. Moreover, clogging of the blowout path 21 can be prevented or suppressed.
  • the temperature adjustment path 32 is disposed near the roll electrodes 11 and 12, since the temperature adjustment liquid is insulative, there is no possibility that the temperature adjustment liquid and the electrodes 11 and 12 are electrically short-circuited. Therefore, it is possible to avoid the destruction of the control unit 31e and the liquid temperature sensor 31c of the liquid temperature adjusting unit 31 due to electricity traveling through the temperature adjustment liquid. Even if the reaction gas contains a combustible component such as acrylic acid, it is possible to avoid the occurrence of abnormality such as ignition due to electric leakage. Since the temperature of the nozzle 20 can be measured and controlled remotely, it is not necessary to provide the nozzle 20 with a temperature sensor such as a thermocouple.
  • the nozzle 20 can hardly be heated to the boiling point (100 ° C.) or higher of the temperature adjusting liquid (water). Therefore, it is not necessary to double the control system for safety, and an increase in equipment cost can be suppressed. Since the temperature adjustment liquid is water (pure water or ion exchange water or the like), the equipment cost of the nozzle temperature adjustment means 30 can be surely kept low. In order to maintain the electrical insulation of the temperature adjustment liquid, it is preferable to periodically exchange the temperature adjustment liquid.
  • a polarizing plate is produced by bonding the treated film 9 after treatment with a polarizing film made of a PVA film or the like.
  • An aqueous adhesive such as an aqueous PVA solution is used as the adhesive. Since the adhesiveness of the film to be treated 9 is enhanced in advance by the surface treatment, a polarizing plate having sufficient adhesive strength can be obtained.
  • FIG. 2 shows a plasma processing apparatus 1A according to the second embodiment of the present invention.
  • the apparatus 1A is for processing a film to be processed 9 wider than the apparatus 1 (FIG. 1) of the first embodiment, and the roll electrodes 11, 12 and the nozzle 20 are longer in the processing width direction than the first embodiment.
  • a plurality of temperature control paths 32 ⁇ / b> A of the temperature control means 30 are formed apart from each other in the vertical direction.
  • Each temperature adjustment path 32 ⁇ / b> A includes a temperature adjustment forward path 321 (upper flow path) and a temperature adjustment return path (lower flow path) 322. Both the temperature adjustment forward path 321 and the temperature adjustment return path 322 extend over the entire length of the nozzle 20.
  • the temperature adjustment forward path 321 and the temperature adjustment return path 322 of each temperature adjustment path 32 ⁇ / b> A are arranged at the same height in the nozzle 20 in the alignment direction.
  • the temperature adjustment forward path 321 is connected to the forward conduit 33 via a junction 36 (not shown).
  • the temperature adjustment path 321 and the temperature adjustment return path 322 are connected by a return path 323 (connection path).
  • the downstream end of the temperature adjustment return passage 322 is connected to the return conduit 34 via a junction portion 36 (not shown).
  • the blow-out path 21 passes between the temperature adjustment forward path 321 and the temperature adjustment return path 322.
  • the temperature adjusting liquid is sequentially introduced from the liquid temperature adjusting unit 31 through the outgoing pipe 33 to the temperature adjusting outgoing path 321 in the nozzle 20, and from the first end along the longitudinal direction (processing width direction) of the nozzle 20. It flows in one direction (upper right in FIG. 2) to the two ends. In this process, the nozzle 20 is heated. Thereafter, the temperature adjustment liquid is sent to the temperature adjustment return path 322 via the return path 323, and the one direction is from the second end to the first end along the longitudinal direction (process width direction) of the nozzle 20. It flows in the reverse direction (lower left in FIG. 2). In this process, the nozzle 20 is further heated. As the temperature adjusting liquid flows, the temperature gradually decreases due to heat exchange with the nozzle 20.
  • the nozzle 20 can be heated almost evenly regardless of the position in the longitudinal direction of the nozzle 20. Therefore, even if the length of the nozzle 20 is large, the temperature of the entire nozzle 20 can be adjusted almost uniformly in the longitudinal direction (process width direction). Thereafter, the temperature adjusting liquid is returned to the liquid temperature adjusting unit 31 via the return pipe 34.
  • FIG. 3 shows a third embodiment of the present invention.
  • This embodiment relates to a specific aspect of the nozzle 20.
  • a portion 24 on the upper side (base end side in the blowing direction) of the nozzle 20 is made of metal, and a portion 25 on the lower side (tip side in the blowing direction) is made of an insulating resin.
  • the nozzle base end portion 24 is relatively far from the discharge space 13 and hardly receives the electric field between the electrodes 11 and 12.
  • the nozzle base end portion 24 is connected to and supported by the mount 5.
  • the tip portion 25 including the outlet 23 of the nozzle 20 is inserted into the gradually narrowing portion between the electrodes 11 and 12 and faces the discharge space 13.
  • the side surface of the tapered portion of the nozzle tip portion 25 is a partial cylindrical concave surface along the peripheral surface of the corresponding roll electrode 11, 12.
  • a plurality of temperature control paths 32 are arranged side by side with the blowout path 21 interposed therebetween so as to form a pair in the opposing direction of the electrodes 11, 12 at intervals in the vertical direction.
  • FIG. 4 shows a plasma processing apparatus 1B according to the fourth embodiment of the present invention.
  • the reaction gas nozzle 20B that blows out the reaction gas is disposed away from the discharge space 13 on the upstream side in the rotation direction of the roll electrode 11.
  • the front end surface (lower surface) of the nozzle 20 faces the upper peripheral surface of the roll electrode 11 and is disposed close to the roll electrode 11.
  • the cross section orthogonal to the processing width direction of the nozzle 20B is substantially rectangular.
  • the point that the temperature adjustment path 32 of the nozzle temperature adjustment means 30 is formed in the nozzle 20B is the same as in the first embodiment.
  • a discharge generation gas nozzle 41 is disposed on the upper side and a discharge generation gas nozzle 42 is disposed on the lower side with the discharge space 13 interposed therebetween.
  • the discharge generation gas nozzles 41 and 42 have a structure that is inverted up and down. Each discharge generated gas nozzle 41 and 42 extends in the processing width direction. The tips of the discharge generation gas nozzles 41 and 42 face the discharge space 13.
  • a discharge generation gas supply path 43 is connected to the discharge generation gas nozzles 41 and 42, respectively.
  • Nitrogen (N 2 ) is used as the discharge product gas.
  • the discharge product gas does not contain a polymerizable monomer.
  • the discharge generated gas is not limited to nitrogen, and a rare gas such as argon or helium may be used.
  • the reactive gas (acrylic acid + N 2 ) is sprayed from the outlet 23 on the lower surface of the nozzle 20B to the film 9 to be processed on the upper peripheral surface of the roll electrode 11.
  • the temperature adjustment liquid of the nozzle temperature adjustment means 30 is circulated to adjust the temperature of the nozzle 20B.
  • the temperature of the nozzle 20B can be set higher than the condensation temperature of acrylic acid in the reaction gas.
  • the tip portion (lower portion) of the nozzle 20B in the vicinity of the roll electrode 11 can be reliably maintained at a high temperature. Therefore, acrylic acid can be blown out without condensing in the nozzle 20B. After the acrylic acid is blown out from the nozzle 20, it condenses on the low-temperature processed film 9 and adheres to the surface of the processed film 9.
  • the discharge product gas (N 2 ) is supplied from at least one of the discharge product gas nozzles 41 and 42 to the discharge space 13 to be converted into plasma.
  • the acrylic acid adhering portion of the film to be processed 9 eventually enters the discharge space 13 and receives plasma irradiation. Thereby, the plasma polymerization reaction of acrylic acid occurs on the surface of the film 9 to be processed in the discharge space 13, and the adhesion promoting layer is formed in the same manner as in the first embodiment.
  • the temperature adjustment liquid is less likely to conduct electricity, even if the nozzle 20B is disposed close to the electrode 11, the leakage from the electrode 11 to the temperature adjustment means 30 can be prevented, as in the first embodiment. .
  • FIG. 5 shows a fifth embodiment of the present invention.
  • the temperature adjustment path 32 in the reaction gas nozzle 20 includes a lower upper flow path 51, a middle flow path 52, and an upper lower flow path 53.
  • the upper flow path 51 is disposed at a relatively low position in the reaction gas nozzle 20.
  • the middle channel 52 is disposed at a higher position than the upper channel 51.
  • the lower flow path 53 is disposed higher than the middle flow path 52 (a relatively high position in the reaction gas nozzle 20).
  • the upper flow path 51 and the middle flow path 52 are connected via a connection path 54 extending vertically.
  • the middle stage flow path 52 and the lower flow path 53 are connected via a connection path 55 extending vertically.
  • the temperature adjusting liquid flows in the order of the upper flow path 51, the connection path 54, the middle flow path 52, the connection path 55, and the lower flow path 53.
  • the temperature control path structure of the fifth embodiment will be described in more detail.
  • the upper flow path 51 includes a first upper flow path portion 51a and a second upper flow path portion 51b.
  • Each flow path part 51a, 51b extends horizontally from the first end (lower left in FIG. 5) to the second end (upper right in FIG. 5) in the longitudinal direction (process width direction) of the reactive gas nozzle 20.
  • the first upper flow path portion 51a and the second upper flow path portion 51b are arranged in parallel in the alignment direction at the same horizontal height.
  • the first upper flow path portion 51 a is arranged so as to be biased toward the first roll electrode 11 from the vertical center line of the reaction gas nozzle 20.
  • the second upper flow path portion 51b is arranged so as to be biased toward the second roll electrode 12 from the center line.
  • An inlet port 50 is provided on the first end face (lower left in FIG. 5) of the reactive gas nozzle 20.
  • An outgoing line 33 from the liquid temperature adjusting unit 31 (see FIG. 1) is connected to the inlet port 50.
  • a first end (upstream end) of the upper flow path 51 is connected to the inlet port 50.
  • a branch path 51c (branch portion) is provided near the upstream end of the upper flow path 51.
  • the branch path 51c extends in the arrangement direction.
  • Upper flow path portions 51a and 51b branch from the branch path 51c.
  • the first upper flow path portion 51a branches from the end (upstream end) of the branch path 51c on the first roll electrode 11 side, and is aligned with the upper flow path 51 from the inlet port 50 to the branch path 51c.
  • the second upper flow path portion 51b is continuous with the end (downstream end) of the branch path 51c on the second roll electrode 12 side.
  • the middle stage flow path 52 includes a first flow path portion 52a and a second flow path portion 52b.
  • Each flow path portion 52a, 52b extends horizontally from the second end portion (upper right in FIG. 5) in the longitudinal direction of the reaction gas nozzle 20 to the first end portion (lower left in FIG. 5).
  • the first flow path portion 52a and the second flow path portion 52b are arranged in parallel in the alignment direction at the same horizontal height.
  • the first flow path portion 52a is disposed so as to be biased toward the first roll electrode 11 from the vertical center line of the reaction gas nozzle 20, and the second flow path portion 52b is biased toward the second roll electrode 12 from the center line. Has been placed.
  • the first flow path portion 52a is disposed in parallel with the first upper flow path portion 51a immediately above the first upper flow path portion 51a.
  • the second flow path portion 52b is disposed in parallel with the second upper flow path portion 51b immediately above the second upper flow path portion 51b.
  • connection path 54 is disposed at the second end of the reactive gas nozzle 20 (the end opposite to the branching portion 51c).
  • the connection path 54 includes a first connection path portion 54a and a second connection path portion 54b.
  • the first connection path portion 54 a is arranged so as to be biased toward the first roll electrode 11 from the vertical center line of the reaction gas nozzle 20.
  • the first connection path portion 54a extends vertically, and a lower end portion (upstream end) thereof is continuous with a second end portion (downstream end) of the first upper flow path portion 51a.
  • the upper end portion (downstream end) of the first connection path portion 54a is continuous with the second end portion (upstream end) of the first flow path portion 52a.
  • the second connection path portion 54b is arranged so as to be biased toward the second roll electrode 12 from the center line.
  • the second connection path portion 54b extends vertically, and a lower end portion (upstream end) thereof is connected to a second end portion (downstream end) of the second upper flow path portion 51b.
  • the upper end portion (downstream end) of the second connection path portion 54b is continuous with the second end portion (upstream end) of the second flow path portion 52b.
  • the middle channel 52 constitutes a “lower channel” with respect to the upper channel 51.
  • the first flow path portion 52a constitutes a “first lower flow path portion”
  • the second flow path portion 52b constitutes a “second lower flow path portion”.
  • the upper flow path 53 of the upper stage of the reaction gas nozzle 20 includes a first lower flow path portion 53a and a second lower flow path portion 53b.
  • Each flow path part 53a, 53b extends horizontally from a first end (lower left in FIG. 5) in the longitudinal direction of the reaction gas nozzle 20 to a second end (upper right in FIG. 5).
  • the first lower flow path portion 53a and the second lower flow path portion 53b are arranged in parallel in the alignment direction at the same horizontal height.
  • the first lower flow path portion 53a is arranged so as to be biased toward the first roll electrode 11 from the vertical center line of the reaction gas nozzle 20, and the second lower flow path portion 53b is biased toward the second roll electrode 12 side from the center line.
  • the first lower flow path portion 53a is disposed in parallel with the first flow path portion 52a immediately above the first flow path portion 52a.
  • the second lower flow path portion 53b is disposed in parallel with the second flow path portion 52b immediately above the second flow path portion 52b.
  • connection path 55 is disposed at the first end of the reactive gas nozzle 20 (the end opposite to the connection path 54).
  • the connection path 55 includes a first connection path portion 55a and a second connection path portion 55b.
  • the first connection path portion 55a is arranged so as to be biased toward the first roll electrode 11 from the center line.
  • the first connection path portion 55a extends vertically, and a lower end portion (upstream end) thereof is continuous with a first end portion (downstream end) of the first flow path portion 52a.
  • the upper end portion (downstream end) of the first connection path portion 55a is continuous with the first end portion (upstream end) of the first lower flow path portion 53a.
  • the second connection path portion 55b is disposed so as to be biased toward the second roll electrode 12 from the center line.
  • the second connection path portion 55b extends vertically, and a lower end portion (upstream end) thereof is continuous with a first end portion (downstream end) of the second flow path portion 52b.
  • the upper end portion (downstream end) of the second flow path portion 52b is continuous with the first end portion (upstream end) of the second lower flow path portion 53b.
  • the middle channel 52 constitutes an “upper channel” with respect to the lower channel 53.
  • the first flow path portion 52a constitutes a “first upper flow path portion”
  • the second flow path portion 52b constitutes a “second upper flow path portion”.
  • the lower flow path 53 is provided with a merge flow path 53c (merging portion).
  • the combined flow path 53c extends in the arrangement direction.
  • the second ends (downstream ends) of the first lower flow path portion 53a and the second lower flow path portion 53b are joined together via the combined flow path 53c.
  • the first lower flow path portion 53a continues to the end of the combined flow path 53c on the first roll electrode 11 side.
  • the second lower flow path portion 53b is connected to the end of the combined flow path 53c on the second roll electrode 12 side, and is aligned with the lower flow path 53 on the second end side (downstream side) from the combined flow path 53c.
  • An outlet port 56 is provided on the second end face of the reactive gas nozzle 20.
  • a second end (downstream end) of the lower flow path 53 is connected to the outlet port 56.
  • a return pipe 34 extends from the outlet port 56 to the liquid temperature adjusting unit 31 (see FIG. 1).
  • a slit-like gas flow path 21 (see FIG. 1) is provided in the nozzle 20 in a direction (vertical direction in FIG. 5) perpendicular to the processing width direction and the alignment direction. ing.
  • the gas flow path 21 passes between the first lower flow path portion 53a and the second lower flow path portion 53b, further passes between the first flow path portion 52a and the second flow path portion 52b, and further, the first upstream. It passes between the path portion 51a and the second upper flow path portion 51b.
  • the lower end portion (downstream end) of the gas flow path 21 is connected to the blowout port 23 (see FIG. 1) at the lower end of the nozzle 20.
  • One end of the gas flow path 21 in the processing width direction is on the center side in the processing width direction from the branch part 51c, and the other end of the gas flow path 21 in the processing width direction is on the center side in the processing width direction from the junction part 53c.
  • the temperature adjusting liquid from the liquid temperature adjusting unit 31 is introduced into the upper flow path 51 from the forward duct 33 through the inlet port 50.
  • a part Lq1 of the temperature adjusting liquid is diverted from the branch part 51c to the first upper flow path part 51a.
  • the remaining part (other part) Lq2 of the temperature adjusting liquid is diverted from the branch part 51c to the second upper flow path part 51b.
  • part of the temperature control liquid Lq1, Lq2 flows through the first and second upper flow path portions 51a, 51b from the first end side to the second end side.
  • the temperature adjusting liquid is diverted to one of the flow path portions 51a and 51b, for example, the first upper flow path portion 51a. That is, it is assumed that most of the temperature adjustment liquid goes to the part Lq1 and the flow rate of the remaining part Lq2 is almost zero. Even in such a case, after the temperature adjustment liquid fills the entire first upper flow path portion 51a, it becomes easier to flow to the other second upper flow path portion 51b than to rise the first connection path portion 54a. Therefore, the temperature adjusting liquid can be distributed to the second upper flow path portion 51b. As a result, the temperature adjustment liquid can flow through both the flow path portions 51a and 51b.
  • the temperature adjusting liquid Lq1 that has passed through the first upper flow path portion 51a rises in the first connection path portion 54a and is introduced into the first flow path portion 52a.
  • the temperature adjustment liquid Lq2 that has passed through the second upper flow path portion 52a moves up the second connection path portion 54b and is introduced into the second flow path portion 52b. Thereby, a part of each of the temperature control liquids Lq1 and Lq2 flows from the second end portion side to the first end portion side through the first and second flow path portions 52a and 52b.
  • the temperature adjustment liquid Lq1 that has passed through the first flow path portion 52a rises in the first connection path portion 55a and is introduced into the first lower flow path portion 53a.
  • the temperature adjustment liquid Lq2 that has passed through the second flow path portion 52b rises in the second connection path portion 55b and is introduced into the second lower flow path portion 53b.
  • a part of each of the temperature control liquids Lq1 and Lq2 flows from the first end portion side to the second end portion side through the first and second lower flow path portions 53a and 53b.
  • these temperature control liquid Lq1, Lq2 joins in the junction part 53c.
  • the temperature adjusting liquid after joining is returned to the liquid temperature adjusting unit 31 from the return pipe line 34 through the outlet port 56.
  • the reaction gas nozzle 20 can be temperature-controlled in a wide range.
  • the temperature adjustment liquid is not limited to water such as pure water or ion-exchanged water, and preferably has insulating properties.
  • a fluorine-based inert liquid such as Fluorinert (registered trademark) may be used.
  • the boiling point of the temperature adjustment liquid is preferably low from the viewpoint of safety.
  • Only one temperature control path 32 may be provided in the nozzles 20 and 20B. In this case, it is preferable that one temperature control path 32 is arranged at the tip of the nozzles 20 and 20B in the blowing direction as much as possible.
  • the nozzles 20 and 20B only have to be formed of an insulator at least at the tip including the outlet 23, and the base end of the nozzles 20 and 20B opposite to the outlet 23 is a conductor such as metal. It may be configured.
  • a water leakage sensor may be provided below the nozzles 20 and 20B so that the leakage of the temperature adjusting liquid can be detected.
  • the upper flow path 51 may be branched into three or more upper flow path portions.
  • one of the three or more upper flow path portions constitutes a “first upper flow path portion”, and the other one constitutes a “second upper flow path portion”.
  • the middle stage flow path 52 may have three or more flow path portions.
  • the lower flow path 53 may have three or more lower flow path portions.
  • the inlet port 50 may be connected to an intermediate portion in the extending direction of the branch path 51c.
  • the outlet port 56 may be connected to an intermediate portion in the extending direction of the combined flow path 53c.
  • the downstream ends of the upper flow path portions 51 a and 51 b of the upper flow path 51 may be merged, and the upper flow path 51 downstream from the merge portion may be continuous with the lower end portion of one connection path 54.
  • the first and second flow path portions 52 a and 52 b of the middle stage path 52 may be branched from the upper end portion of one connection path 54.
  • the downstream ends of the first and second flow path portions 52 a and 52 b of the intermediate stage 52 may join together, and the intermediate stage 52 downstream from the junction may be connected to the lower end of one connection path 55.
  • the first and second flow path portions 53a and 53b of the lower flow path 53 may be branched from the upper end portion of one connection path 55.
  • the branch portion 51c may be provided in an intermediate portion in the longitudinal direction (process width direction) of the reactive gas nozzle 20, and the two flow path portions 51a and 51b are opposite to each other in the longitudinal direction of the reactive gas nozzle 20 from the branched portion 51c. It may extend to.
  • the merging portion 53c may be provided at an intermediate portion in the longitudinal direction (processing width direction) of the reactive gas nozzle 20, and the two flow path portions 53a and 53b are arranged in the longitudinal direction of the reactive gas nozzle 20 with the merging portion 53 interposed therebetween. They may extend from opposite sides toward the merging portion 53c and merge with each other.
  • the electrode structure of the plasma processing apparatus 1 is not limited to the pair of roll electrodes 11 and 12.
  • it may be a parallel plate electrode, a pair of roll electrode and plate electrode, or a pair of roll electrode and partial cylindrical concave electrode.
  • the nozzles 20 and 20 ⁇ / b> B are disposed near at least one of the electrodes, or are disposed so as to face the discharge space 13.
  • the one electrode may be a flat plate electrode or a partial cylindrical concave electrode.
  • the present invention is not limited to the surface treatment of the protective film for a polarizing plate, but can be applied to the surface treatment of various resin films.
  • the workpiece 9 is not limited to a resin film, and may be a glass substrate, a semiconductor wafer, or the like.
  • the processing content is not limited to the formation of the plasma polymerized film, but may be plasma CVD, and is not limited to the film formation, and can be applied to various processes such as cleaning, surface modification, and etching.
  • the reaction gas component is appropriately selected according to the processing content. For example, in plasma CVD, TMOS, TEOS, etc. are mentioned as a reactive component of the reactive gas.
  • the present invention is applicable, for example, to the manufacture of flat panel display (FPD) polarizing plates and semiconductor wafers.
  • FPD flat panel display

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Analytical Chemistry (AREA)
  • Plasma Technology (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

La présente invention se rapporte à un dispositif de traitement au plasma qui peut empêcher la condensation à l'intérieur d'une buse, évite des mauvais fonctionnements, tels que des courts-circuits, même si les composants réactifs du gaz de réaction ont tendance à se condenser. Un espace de décharge (13) est formé entre les électrodes d'une paire d'électrodes (11, 12) d'un dispositif de traitement au plasma (1), et un corps traité (9) est exposé au plasma. Une buse (20) est disposée près d'au moins une électrode de la paire d'électrodes (11, 12) ou près de l'espace de décharge (13). Un gaz de réaction contenant un composant réactif de condensation est pulvérisé par la buse (20) sur l'objet traité (9). La température de la buse (20) est réglée au moyen d'un moyen de réglage de température de buse (30). Un trajet de réglage de température (32) est formé à l'intérieur de la buse (20) et sert de moyen de réglage de température (30), et un fluide de régulation de température est amené à circuler à travers ledit trajet de réglage de température (32). Au moyen d'une unité de réglage de température de liquide (31), le fluide de régulation de température est régulé de manière à être à une température supérieure à la température de condensation du composant réactif.
PCT/JP2011/055669 2010-03-24 2011-03-10 Dispositif de traitement au plasma WO2011118408A1 (fr)

Priority Applications (3)

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CN201180015135.XA CN102884223B (zh) 2010-03-24 2011-03-10 等离子处理装置
KR1020127027561A KR101473547B1 (ko) 2010-03-24 2011-03-10 플라즈마 처리 장치
JP2012506932A JP5503733B2 (ja) 2010-03-24 2011-03-10 プラズマ処理装置

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JP2010-068746 2010-03-24
JP2010068746 2010-03-24

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KR (1) KR101473547B1 (fr)
CN (1) CN102884223B (fr)
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WO (1) WO2011118408A1 (fr)

Citations (4)

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JPH11329117A (ja) * 1998-05-13 1999-11-30 Fujikura Ltd Ｃｖｄ反応装置
JP2003268553A (ja) * 2002-03-13 2003-09-25 Konica Corp 薄膜形成方法
JP2005256160A (ja) * 2004-02-13 2005-09-22 Fujikura Ltd 成膜装置及び吐出手段並びに酸化物超電導導体の製造方法
WO2008029622A1 (fr) * 2006-08-29 2008-03-13 Konica Minolta Holdings, Inc. Appareil de formation de films minces et procédé de formation de films minces

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KR20050103251A (ko) * 2002-10-07 2005-10-27 세키스이가가쿠 고교가부시키가이샤 플라즈마 표면 처리 장치
US8608900B2 (en) * 2005-10-20 2013-12-17 B/E Aerospace, Inc. Plasma reactor with feed forward thermal control system using a thermal model for accommodating RF power changes or wafer temperature changes
US8110815B2 (en) * 2006-06-12 2012-02-07 Semequip, Inc. Vapor delivery to devices under vacuum
KR101153585B1 (ko) * 2007-07-09 2012-06-12 세키스이가가쿠 고교가부시키가이샤 필름 표면 처리 방법 및 편광판의 제조 방법 및 표면 처리 장치
JP4897742B2 (ja) * 2007-07-12 2012-03-14 積水化学工業株式会社 プラズマ処理方法及び装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11329117A (ja) * 1998-05-13 1999-11-30 Fujikura Ltd Ｃｖｄ反応装置
JP2003268553A (ja) * 2002-03-13 2003-09-25 Konica Corp 薄膜形成方法
JP2005256160A (ja) * 2004-02-13 2005-09-22 Fujikura Ltd 成膜装置及び吐出手段並びに酸化物超電導導体の製造方法
WO2008029622A1 (fr) * 2006-08-29 2008-03-13 Konica Minolta Holdings, Inc. Appareil de formation de films minces et procédé de formation de films minces

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JP5503733B2 (ja) 2014-05-28
KR101473547B1 (ko) 2014-12-16
CN102884223B (zh) 2015-01-07
CN102884223A (zh) 2013-01-16
TW201138559A (en) 2011-11-01
KR20130005293A (ko) 2013-01-15
JPWO2011118408A1 (ja) 2013-07-04

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