TW201319637A - Method for starting surface treatment of film and surface-treatment device - Google Patents

Abstract

In the present invention, loss of a film to be treated is minimized or prevented, when a surface treatment on a film to be treated is started using a reaction gas containing a polymerizable monomer. Delivery of the reaction gas from a supply source (31) is started, and the delivered reaction gas is discharged without being sent to a supply nozzle (33). After a required amount of time (T1) has elapsed following the start of delivery, transfer of a film (9) to be treated is started. Also started is the bringing of discharge gas that has been transformed into plasma into contact with the film (9) to be treated. The discharging of the reaction gas is stopped, and blowing out of the reaction gas from the supply nozzle (33) is started.

Description

Film surface treatment starting method and surface treatment device

The present invention relates to a method and a surface treatment apparatus for starting a surface treatment of a resin-treated film, for example, a film surface treatment for an adhesion improving treatment of a protective film suitable for a polarizing plate, etc. Method and surface treatment device.

For example, a polarizing plate is mounted in a liquid crystal display device. The polarizing plate includes a polarizing film and a protective film. Usually, the polarizing film contains a PVA film containing polyvinyl alcohol (PVA) as a main component. The protective film contains a TAC film containing triacetyl cellulose (TAC) as a main component. A water-based adhesive such as a polyvinyl alcohol-based or polyether-based adhesive is used as an adhesive for the film. Although the adhesion between the PVA film and the above-mentioned adhesive is good, the adhesion of the TAC film is not good. Therefore, the saponification treatment is performed in order to improve the adhesion of the TAC film. The saponification treatment immerses the TAC film in a high-temperature, high-concentration alkali solution. Therefore, it is pointed out that there is a problem of workability or waste disposal.

As an alternative technique, in Patent Document 1, a film of a polymerizable monomer is formed on the surface of the protective film before the subsequent step, and then the atmospheric piezoelectric slurry is irradiated. The polymerizable monomer is vaporized from the state of the solution, for example, and is sent to the protective film in a vapor state, and is condensed on the surface of the protective film. Further, a plasma polymerization reaction of a polymerizable monomer is caused by irradiation of the above-mentioned atmospheric piezoelectric slurry, and a plasma polymerization film of a polymerizable monomer is formed on the surface of the protective film.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-25604

When the surface treatment of the film to be processed such as a protective film for a polarizing plate (including restarting after the temporary stop) is started, it takes a certain amount of time (stabilization period) until the supply concentration of the polymerizable monomer is stabilized. Therefore, the processing state of the length portion transported in the above-described stabilization period in the front end portion of the processed film in the transport direction becomes unstable. Therefore, it is necessary to discard the above-mentioned length portion of the film to be processed, and the loss is large.

In order to solve the above problems, the method of the present invention is a surface treatment starting method characterized in that a reaction gas containing a polymerizable monomer and a plasma (including excitation, activation, radicalization, ionization, etc.) are used. When the discharge gas is brought into contact with the resin-treated film to surface-treat the film to be treated, the surface treatment start method of the surface treatment is started; and the reaction gas is sent from the reaction gas supply source without being sent out. The reaction gas is sent to the discharge port of the supply nozzle facing the film to be processed, and is discharged after the elapse of a predetermined period of time from the start of the discharge, and the discharge of the plasma to be treated is started. The film to be treated further stops the discharge and starts to eject the reaction gas from the discharge port.

Usually, the concentration of the polymerizable monomer in the reaction gas is temporarily unstable after the reaction gas is sent from the supply source. Do not spray the reaction gas on the side The film is discharged on the film, and the concentration of the polymerizable monomer is stabilized. Thereafter, the surface of the film to be processed is transferred, and the surface treatment is started. Thereby, it is possible to suppress or prevent the treatment state of the end portion in the conveyance direction of the film to be processed from becoming unstable, and it is possible to reduce the length of the film portion which is unstable in such a treatment state, or to form a film portion which is unstable in the above-described treatment state. Thereby, the loss of the film to be treated can be suppressed or prevented. That is, it is also possible to suppress or prevent the loss of the film to be treated by using the method of the present invention when it is convenient to start again after a temporary stop due to some malfunction or the like.

The above-mentioned required time is preferably a stabilization period corresponding to the stabilization of the concentration of the polymerizable monomer in the reaction gas. Thereby, the concentration of the polymerizable monomer can be reliably stabilized at the start of the conveyance of the film to be processed and at the start of the surface treatment. Therefore, the treatment state can be surely stabilized from the beginning of the surface treatment of the film to be treated. Therefore, the loss of the treated film can be further suppressed or prevented.

It is preferable to start the conveyance of the film to be processed, and then start to bring the plasma discharge gas into contact with the film to be processed. Thereby, it is possible to prevent a specific portion of the film to be treated from being subjected to a large heat damage due to continuous plasma irradiation, and further, it is possible to prevent the film to be processed from being broken at the specific portion.

Preferably, the discharge of the plasma-discharged gas is started to contact the film to be treated, and then the reaction gas is discharged from the supply nozzle. Thereby, the plasma polymerization reaction of the polymerizable monomer can be surely generated from the start of the discharge of the reaction gas from the supply nozzle, and the plasma polymerization film of the polymerizable monomer can be surely formed on the surface of the film to be treated. Therefore, it is possible to prevent the polymerizable monomer from remaining directly on the film to be treated in the form of a monomer. Therefore, it can be prevented The residual monomer is transferred to the device member or the peripheral member on the transport path of the film to be treated. Alternatively, the above residual monomer can be prevented from being transferred to the equipment used in the subsequent step of the surface treatment. As a result, it is possible to prevent a decrease in the yield due to the above transfer (transfer).

The apparatus of the present invention is a film surface treatment apparatus characterized in that the surface of the film to be treated is surface-contacted by bringing a reaction gas containing a polymerizable monomer and a plasma discharge gas into contact with a resin-made film to be treated. a processor; the reaction gas supply system comprising: a supply passage extending from a supply source of the reaction gas; and a supply nozzle connected to a downstream end of the supply passage; and a support transport mechanism opposite to the supply nozzle Supporting the processed film, and transporting the processed film along the transport path; the plasma generating unit plasma-dissolving the discharge gas downstream of the supply nozzle on the transport path; and the discharge path is connected to the above a middle portion of the reaction gas supply system; and a control unit that discharges the reaction gas sent from the supply source from the discharge passage when the surface treatment is started, and starts the transfer after a lapse of a lapse of time from the start of the delivery And the above-mentioned plasma formation, and stopping the discharge and starting to eject the reaction from the supply nozzle Body.

By the control of the above-described control means, the reaction gas is not sprayed onto the film to be processed and discharged from the start of the reaction of the reaction gas until the elapse of the required time. Therefore, it can be avoided that the concentration of the polymerizable monomer is unstable. The surface of the treated film is treated. Then, the surface treatment is started by the conveyance of the film to be processed, etc., thereby suppressing or preventing the treatment state of the end portion in the conveyance direction of the film to be processed from being unstable, and the film having such an unstable treatment state can be reduced. The length of the portion may not form a portion of the film which is unstable in the above treatment state. Thereby, the loss of the film to be treated can be suppressed or prevented.

The above plasma formation and surface treatment are preferably carried out in the vicinity of atmospheric pressure. Here, the vicinity of the atmospheric pressure means a range of 1.013 × 10 ⁴ to 50.663 × 10 ⁴ Pa, and in consideration of ease of pressure adjustment or simplification of the device configuration, it is preferably 1.333 × 10 ⁴ to 10.664 × 10 ⁴ Pa. More preferably, it is 9.331 × 10 ⁴ ~ 10.397 × 10 ⁴ Pa.

The present invention is preferably used for the treatment of an optical resin film which is difficult to bond, and is preferably used for an optical resin film which is difficult to adhere when the optical resin film which is difficult to adhere is attached to an optical resin film which is easy to adhere. Continuity.

Examples of the main component of the above-mentioned difficult-to-adhere optical resin film include triacetyl cellulose (TAC), polypropylene (PP), polyethylene (PE), and cycloolefin polymer (COP, cycloolefin). Polymer), cycloolefin copolymer (COC), polyethylene terephthalate (PET), polymethyl methacrylate (PMMA, polymethyl methacrylate), polyimine (PI, polyimide) )Wait.

The main component of the above-mentioned easy-to-adhere optical resin film is, for example, polyvinyl alcohol (PVA) or ethylene-vinyl acetate copolymer (EVA).

Examples of the above polymerizable monomer include an unsaturated bond and a specific official. The monomer of the energy base. The specific functional group is preferably selected from the group consisting of a hydroxyl group, a carboxyl group, an ethyl fluorenyl group, a glycidyl group, an epoxy group, an ester group having a carbon number of 1 to 10, a mercapto group, an aldehyde group, and particularly preferably a carboxyl group or a hydroxyl group. Hydrophilic group.

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, and 2-methylpropenylpropionic acid.

Examples of the monomer having an unsaturated bond and an acetyl group include vinyl acetate and the like.

Examples of the monomer having an unsaturated bond and a glycidyl group include glycidyl methacrylate and the like.

Examples of the monomer having an unsaturated bond and an ester group include methyl acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, and methyl methacrylate. Ethyl methacrylate, butyl methacrylate, butyl methacrylate, isopropyl methacrylate, 2-ethyl methacrylate, and the like.

Examples of the monomer having an unsaturated bond and an aldehyde group include acrolein and crotonaldehyde.

The polymerizable monomer is preferably a monomer having an ethylenically unsaturated double bond and a carboxyl group. Examples of such a monomer include acrylic acid (CH ₂ =CHCOOH) and methacrylic acid (CH ₂ =C(CH ₃ )COOH). The above polymerizable monomer is preferably acrylic acid or methacrylic acid. Thereby, the adhesion of the difficult-to-adhere resin film can be surely improved. The above polymerizable monomer is more preferably acrylic acid.

The film to be treated is an olefin monomer such as COP, COC, PP or PE. In the case of a film, the reaction gas preferably contains a water-soluble monomer and an olefin-based monomer as a polymerizable monomer. The volume concentration of the olefin monomer in the reaction gas is preferably 1.1 times or more the volume concentration of the water-soluble monomer.

The olefin-based monomer is an unsaturated hydrocarbon having a double bond and having no polar functional group, and may be linear or cyclic, and the number of double bonds may be one or two or more. It is preferably used as a liquid in the vicinity of room temperature, and is easily vaporized as an olefin type monomer. The carbon number of the olefin monomer is preferably 5 or more and 8 or less. Specifically, examples of the linear olefin-based monomer include 1-pentene, 1-hexene, 1-heptene, and 1-octene. It is preferred to have a double bond at the end of the linear chain, but it is not particularly limited thereto. Examples of the cyclic olefin-based monomer include 1-cyclopentene, 1-cyclohexene, 1-cycloheptene, and 1-cyclooctene, and examples thereof include cyclopentadiene and dicyclopentadiene (DCPD). , dicyclopentadiene) and other cyclic diene. The above olefin-based monomer is preferably a cyclic diene, and particularly preferably cyclopentadiene or dicyclopentadiene. Thereby, the compatibility of the liquefied layer and the subsequent promoting layer with the olefin-based monomer polymerized film can be improved, and in particular, the compatibility with the film containing the cyclic olefin polymer (COP) can be improved. Further, the cyclic diene is easily polymerized by a Diels-alder reaction or the like, and is easily copolymerized with a water-soluble monomer.

The water-soluble monomer is preferably a monomer having an aldehyde group, a carboxyl group, or a hydroxyl group. Thereby, compatibility with an adhering member such as an adhesive containing a polar component such as PVA or a polarizing element can be improved. Specifically, examples of the water-soluble monomer include acetaldehyde, vinyl alcohol, acrylic acid (AA), methacrylic acid, styrenesulfonic acid, acrylamide, methacrylamide, and N,N- Dimethylaminopropyl acrylamide, N,N-dimethyl decylamine, and the like. As the water-soluble monomer, acetaldehyde or acrylic acid is particularly preferable. Acetaldehyde is a compound which constitutes a vinyl alcohol and a keto-enol tautomer and which coexists with vinyl alcohol. Therefore, compatibility with a vinyl alcohol-based adhesive or a polarizing element can be improved.

The reaction gas may also include a carrier gas for transporting the polymerizable monomer. The carrier gas is preferably an inert gas selected from the group consisting of nitrogen, argon, and helium. From the viewpoint of economy, it is preferred to use nitrogen as a carrier gas.

Most of the polymerizable monomers such as acrylic acid or methacrylic acid are in a liquid phase at normal temperature and normal pressure. Such a polymerizable monomer can be vaporized in a carrier gas such as an inert gas. As a method of vaporizing a polymerizable monomer in a carrier gas, a method of extruding a saturated vapor on a liquid surface of a polymerizable monomer solution with a carrier gas; and bubbling a carrier gas in a polymerizable monomer solution is exemplified. Method; a method of heating a polymerizable monomer solution to promote evaporation, and the like. Squeeze and heat, or foaming and heating may also be used in combination. These vaporization methods are preferably carried out using a vaporizer. In any of the vaporization methods, it takes time from the start of vaporization until the concentration of the polymerizable monomer in the reaction gas is stabilized. Further, it takes time to stabilize the concentration in the reaction gas supply path connecting the vaporizer and the supply nozzle. That is, when the polymerizable monomer is vaporized, it is necessary to vaporize latent heat. Therefore, the temperature in the vaporizer is temporarily lowered immediately after the vaporization operation. Thereafter, the temperature of the vaporizer is slowly recovered to the set temperature by the operation of the temperature adjustment mechanism or the like. During the temperature fluctuation of the vaporizer, the concentration of the polymerizable monomer in the reaction gas is unstable. Further, in the reaction gas supply passage, the polymerizable monomer in the reaction gas is adsorbed to the inner wall of the tube constituting the reaction gas supply passage, or the condensed polymerizable monomer is vaporized, so that the self-reactive gas is supplied. The concentration of the polymerizable monomer of the reaction gas in the supply becomes unstable until the adsorption and vaporization are brought into an equilibrium state from the start. As a result, it takes a certain amount of time for the concentration of the polymerizable monomer in the reaction gas ejected from the supply nozzle to become stable. According to the present invention, even in the unstable period of the concentration of the polymerizable monomer, the treatment state of the end portion in the conveyance direction of the film to be treated can be suppressed or prevented from becoming unstable, and the loss of the film to be treated can be suppressed or prevented.

In the case where the polymerizable monomer is heated and vaporized, the polymerizable monomer is preferably selected to have a boiling point of 300 ° C or less in consideration of the burden of the heater. Further, it is preferred that the polymerizable monomer is selected so as not to be decomposed (chemically changed) by heating.

Examples of the discharge gas include a rare gas of nitrogen (N ₂ ) or a rare gas (Ar, Ne, He, etc.).

According to the present invention, when the surface treatment of the film grease to be treated is started, the treatment state of the end portion before the conveyance direction of the film to be treated can be suppressed or prevented from becoming unstable, and the length of the unstable film portion can be reduced, or The formation of the above unstable film portion is prevented. Therefore, the loss of the treated film can be suppressed or prevented.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.

Fig. 1 and Fig. 2 show a film surface treatment apparatus 1 according to an embodiment of the present invention. The object to be treated 9 of the apparatus 1 is a resin film which is a protective film of a polarizing plate (film laminate). The film to be treated 9 is composed of a TAC film containing triacetyl cellulose (TAC) as a main component, and is formed into a continuous sheet shape. The thickness of the film 9 is, for example, About 100 μm.

Further, the film to be treated 9 is not limited to the TAC film, and may be composed of polypropylene (PP), polyethylene (PE), cycloolefin polymer (COP), cyclic olefin copolymer (COC), polyparaphenylene. A film of various resins such as ethylene formate (PET), polymethyl methacrylate (PMMA), and polyimine (PI).

As shown in FIG. 1, the film surface treatment apparatus 1 includes a treatment tank C, a discharge gas supply system 20, and a reaction gas supply system 30. A processing unit 10 that also supports the transport mechanism and the plasma generating unit is housed inside the processing tank C. As shown in FIGS. 1 and 2, the treatment unit 10 includes three main rolls 11, 12, and 13. The main rolls 11 to 13 are cylindrical bodies having the same diameter and the same axial length. The axes of the main rolls 11 to 13 are oriented in the width direction w orthogonal to the plane of the paper of Fig. 1 . The three main rolls 11 to 13 are juxtaposed in the horizontal direction (left and right in Fig. 1) orthogonal to the w direction.

In Fig. 1, a gap 4A is formed between the left main roller 11 and the center main roller 12. A gap 4B is formed between the center main roller 12 and the right main roller 13. The thickness of the narrowest portion of the gaps 4A and 4B is, for example, about 1 mm to several mm.

A pair of (plural) reversing rollers 14A, 14A are disposed below the main rolls 11, 12. A pair of (plural) reversing rollers 14B and 14B are disposed below the main rollers 12 and 13. The axes of the reversing rollers 14 are parallel to the main rollers 11 to 13.

A rotation mechanism 15 for rotating the main rollers 11 to 13 around the axis is connected to each of the main rollers 11 to 13 (in Fig. 1, only the connection of the main roller 13 and the rotation mechanism 15 is shown). The rotation mechanism 15 includes a drive unit such as a motor and a transmission mechanism that transmits the driving force of the drive unit to the axes of the main rollers 11 to 13. The communication mechanism is constituted, for example, by a belt-pulley mechanism or a gear train.

The main rollers 11 to 13 and the reverse roller 14 cooperate with each other to form a transport path 19 that sequentially reaches the main roller 11, the reverse roller 14A, the main roller 12, the reverse roller 14B, and the main roller 13. The continuous sheet-like processed film 9 is wound in the continuous direction along the transport path 19, and the width direction thereof is oriented in the w direction (the direction orthogonal to the plane of the paper of FIG. 1), and the continuous sheet-like processed film 9 is wound. On the rollers 11~14. Specifically, the film to be processed 9 is wound around the circumferential surface of the upper side of the main rolls 11, 12, and 13 for about half a week. The portion of the film to be processed 9 and the portion between the main roller 11 and the main roller 12 are dropped below the gap 4A through the gap 4A, and are wound around the reversing rollers 14A and 14A. The portion of the film to be processed 9 and the portion between the main roller 12 and the main roller 13 are dropped below the gap 4B through the gap 4B, and are wound around the reversing rollers 14B and 14B. By the rotation mechanism 15, the three main rollers 11 to 13 are synchronized with each other, and rotated clockwise in FIG. 1, whereby the main roller 11, the reverse roller 14A, the main roller 12, the reverse roller 14B, and the like, along the conveyance path 19, The main film 13 sequentially transports the film to be processed 9. The conveyance speed of the film to be processed 9 is set, for example, in the range of about 2 m/min to 60 m/min.

Although not shown in the drawings, a temperature control passage (membrane temperature adjustment mechanism) through which a temperature control medium such as water flows is provided inside each of the main rolls 11, 12, and 13. Thereby, the main rolls 11 to 13 can be tempered, and the temperature of the film 9 to be treated which is in contact with the main rolls 11 to 13 can be adjusted. The set temperatures of the main rolls 11 to 13 and the film to be treated 9 are preferably lower than the condensation temperature of the polymerizable monomer described below.

The main rolls 11 to 13 also serve as electrodes of the plasma generating unit 10. Hereinafter, the main rolls 11, 12, and 13 are also referred to as roll electrodes 11, 12, and 13, respectively. Specifically, at least the outer peripheral portion of each of the roller electrodes 11 to 13 is made of a metal, and a solid dielectric layer (not shown) is coated on the outer peripheral surface of the metal portion. Power supply 2 Connected to the central roller electrode 12. The roller electrodes 11, 13 on both sides are electrically grounded. The power source 2 supplies high frequency power to the roller electrode 12. The supplied electric power is, for example, a intermittent wave such as a pulse, but is not limited thereto, and may be a continuous wave such as a sine wave. By this electric power supply, an electric field is applied between the roller electrodes 11 and 12 to generate a plasma discharge, and an electric field is applied between the roller electrodes 12 and 13 to generate a plasma discharge. The gap 4A becomes the plasma processing space of the front stage. The gap 4B becomes the plasma processing space of the rear stage.

The gas supply systems 20, 30 respectively have a front line corresponding to the processing spaces 3A, 4A of the preceding stage and a rear line corresponding to the processing spaces 3B, 4B of the rear stage. In the following, when each of the components of the gas supply systems 20 and 30 is clearly indicated as belonging to the front-end pipeline and the rear-end pipeline, "A" is added to the components belonging to the preceding pipeline, and the constituent elements belonging to the downstream pipeline are added. Attach "B" to the symbol. Further, the same applies to the reaction gas discharge system 40 described below. In FIG. 1, with respect to all the components of the gas supply systems 20 and 30, "A" is added to the components of the preceding pipeline, and "B" is added to the components of the subsequent pipeline.

Each of the pipelines in the front stage and the rear stage of the discharge gas supply system 20 includes a discharge gas source 21, a discharge gas passage 22, and a discharge gas nozzle 23. At the discharge gas source 21, the discharge gas is compressed and stored. Nitrogen (N ₂ ) was used as the discharge gas. A rare gas such as Ar, He, or Ne may be used instead of N ₂ as a discharge gas. The discharge gas passage 22 extends from the discharge gas source 21. An electromagnetic on-off valve 54 is provided in the discharge gas passage 22. The downstream end of the discharge gas passage 22 is connected to the discharge gas nozzle 23.

Furthermore, the discharge gas of the front stage can be constituted by a single discharge gas source which is shared The discharge source 21B of the body source 21A and the subsequent stage, and the discharge gas passage 22 derived from the single discharge gas source 21 may be branched and connected to the discharge gas nozzles 23A and 23B.

The discharge gas nozzle 23A of the preceding stage is disposed on a portion of the lower side of the plasma processing space 4A of the front stage between the roller electrodes 11, 12. As shown in FIG. 2, the discharge gas nozzle 23A extends long in the w direction, and the cross section orthogonal to the w direction becomes tapered upward. The discharge port 23e of the upper end (front end) of the discharge gas nozzle 23A has a slit shape extending in the w direction and faces the plasma processing space 4A. N ₂ (discharge gas) from the discharge gas source 21A is sent to the discharge gas nozzle 23A via the discharge gas passage 22A, and is discharged from the discharge port 23e of the nozzle 23A to the plasma processing space 4A.

The discharge gas nozzle 23B of the latter stage is disposed on a portion of the lower side of the plasma processing space 4B of the later stage between the roller electrodes 12 and 13. The discharge gas nozzle 23B extends long in the w direction, and the cross section orthogonal to the w direction becomes tapered upward. The discharge port 23e of the upper end (tip) of the discharge gas nozzle 23B has a slit shape extending in the w direction and faces the plasma processing space 4B. N ₂ (discharge gas) from the discharge gas source 21B is sent to the discharge gas nozzle 23B via the discharge gas passage 22B, and is discharged from the discharge port 23e of the nozzle 23B to the plasma processing space 4B.

Although not shown in the drawings, a rectifying portion that uniformly disperses the discharge gas from the discharge gas passage 22 in the w direction is provided inside each of the discharge gas nozzles 23. Thereby, the discharge gas of the discharge gas becomes a gas flow uniformly distributed in the w direction. Further, a temperature control passage (discharge gas temperature adjustment mechanism) through which a temperature control medium such as water flows is provided inside each discharge gas nozzle 23. With this, you can put The electric gas nozzle 23 is tempered to adjust the temperature at which the discharge gas is ejected. The set temperature of the discharge gas nozzle 23 is preferably lower than the condensation temperature of the polymerizable monomer described below.

A blocking member 24A is provided on a portion of the upper side of the plasma processing space 4A between the roller electrodes 11 and 12. The upper end portion of the plasma processing space 4A is blocked to some extent by the blocking member 24A. The blocking member 24A and the discharge gas nozzle 23A are vertically opposed to each other via the plasma processing space 4A. Further, a blocking member 24B is provided on a portion of the upper side of the plasma processing space 4B between the roller electrodes 12 and 13. The upper end portion of the plasma processing space 4B is blocked to some extent by the blocking member 24B. The blocking member 24B and the discharge gas nozzle 23B are vertically opposed to each other via the plasma processing space 4B. A nozzle having the same configuration as that of the discharge gas nozzle 23 can be used as the closing members 24A and 24B, and the discharge gas nozzle 23 can be vertically inverted. The discharge gas can also be ejected from the nozzle 24 on the upper side of the occluding member 24. The discharge gas can be simultaneously ejected from the upper and lower nozzles 24, 23, or can be ejected from only one of them.

As shown in FIG. 1, each of the previous and subsequent stages of the reaction gas supply system 30 includes a reaction gas supply source 31, a reaction gas supply passage 32, and a reaction gas supply nozzle 33. The reaction gas supply source 31 is composed of a vaporizer that vaporizes the polymerizable monomer. Acrylic acid (AA) was used as a polymerizable monomer. Acrylic acid is stored in the vaporizer 31 in a liquid state. A temperature adjustment mechanism (not shown) such as a heater is incorporated in the vaporizer 31 to maintain acrylic acid at a set temperature. Further, a carrier gas source 34 is attached to the vaporizer 31. Nitrogen gas (N ₂ ) as a carrier gas is stored in the carrier gas source 34 by compression. The carrier gas introduction passage 35 extends from the carrier gas source 34, and the introduction passage 35 is connected to the vaporizer 31. An electromagnetic opening and closing valve 55 is provided in the introduction passage 35.

The carrier gas source 34 supplies a carrier gas containing nitrogen to the vaporizer 31 via the introduction passage 35. The vaporizer 31 vaporizes the acrylic acid in the above carrier gas (N ₂ ). The vaporization method of acrylic acid may be a foaming method in which a carrier gas is foamed in a solution of acrylic acid, or may be a method of extruding a saturated vapor on a liquid surface of acrylic acid in a vaporizer by using a carrier gas. A reaction gas (AA+N ₂ ) is formed by mixing vaporized acrylic acid with a carrier gas.

The supply passage 32 extends from the vaporizer 31. A heating belt (reaction gas temperature regulating mechanism) is wound around the tube constituting the supply passage 32. Thereby, the temperature of the reaction gas passing through the supply passage 32 can be adjusted so as to be equal to or higher than the condensation temperature of the acrylic acid, thereby preventing the acrylic acid from being condensed in the supply passage 32. A supply nozzle 33 is connected to the downstream end of the supply passage 32.

Further, the vaporizer 31A of the front stage and the vaporizer 31B of the subsequent stage may be constituted by a single vaporizer which is shared, and the supply passage 32 from the single vaporizer may be branched and connected to the respective supply nozzles 33A, 33B.

As shown in Fig. 2, the supply nozzle 33 has a container shape that extends long in the w direction. As shown in FIG. 1, a discharge port 33e is provided on the lower surface of the supply nozzle 33. Although the detailed illustration is omitted, the discharge port 33e is distributed over a wide range of the longitudinal direction and the short side direction of the lower surface of the supply nozzle 33.

The supply nozzle 33A of the preceding stage is disposed on the upstream side of the plasma processing space 4A of the preceding stage in the transport path 19. Specifically, the supply nozzle 33A is disposed above the main roller 11 . The lower surface of the supply nozzle 33A faces the peripheral surface of the upper side of the main roll 11, and is further opposed to the film 9 to be processed on the main roll 11. A surface is formed between the lower surface of the supply nozzle 33A and the outer surface of the upper side of the main roller 11. The front section is sprayed with the processing space 3A. The film to be processed 9 passes through the inside of the processing space 3A. A shielding member 36A is attached to the lower surface of the supply nozzle 33A. The shield member 36A has a circular arc-shaped cross section as viewed in the w direction, and has a curved plate shape extending in the w direction. By causing the shielding member 36A to extend on both sides of the circumferential direction of the main roller 11 from the supply nozzle 33A, the ejection processing space 3A is extended from the supply nozzle 33A on both sides in the circumferential direction of the main roller 11. The discharge port 33e of the supply nozzle 33A passes through the shield member 36A and is connected to the spray processing space 3A. The reaction gas from the vaporizer 31A is sent to the supply nozzle 33A via the supply passage 32A, and is discharged from the discharge port 33e of the nozzle 33A to the spray processing space 3A.

The supply nozzle 33B of the subsequent stage is disposed between the plasma processing space 4A of the previous stage in the transport path 19 and the plasma processing space 4B of the subsequent stage. Specifically, the supply nozzle 33B is disposed above the main roller 12. The lower surface of the supply nozzle 33B faces the peripheral surface of the upper side of the main roll 12, and is further opposed to the surface of the processed film 9 on the main roll 12. A subsequent processing space 3B is formed between the lower surface of the supply nozzle 33B and the peripheral surface of the upper side of the main roller 12. The film to be processed 9 passes through the inside of the processing space 3B. A shielding member 36B is attached to the lower surface of the supply nozzle 33B. The shield member 36B has a circular arc-shaped cross section as viewed in the w direction, and has a curved plate shape extending in the w direction. By causing the shielding member 36B to extend on both sides of the circumferential direction of the main roller 12 from the supply nozzle 33B, the ejection processing space 3B is extended from the supply nozzle 33B on both sides in the circumferential direction of the main roller 12. The discharge port 33e of the supply nozzle 33B passes through the shield member 36B and is connected to the spray processing space 3B. The reaction gas from the vaporizer 31B is sent to the supply nozzle 33B via the supply passage 32B, and is sprayed from the nozzle 33B. The outlet 33e is ejected to the spray processing space 3B.

Although not shown in the drawings, a rectifying portion that uniformly disperses the reaction gas from the supply passage 32 in the w direction is provided inside each of the supply nozzles 33. Thereby, the discharge gas of the reaction gas becomes a gas flow uniformly distributed in the w direction. Further, a temperature control passage (reaction gas temperature adjustment mechanism) through which the temperature control medium such as water flows is provided inside each supply nozzle 33. Thereby, the supply nozzle 33 can be tempered, and the temperature of the reaction gas passing through the supply nozzle 33 can be adjusted. The set temperature of the supply nozzle 33 is preferably equal to or higher than the condensation temperature of the acrylic acid in the reaction gas. Thereby, it is possible to prevent the acrylic acid from being condensed in the supply nozzle 33.

A reaction gas discharge system 40 is connected to the middle of the reaction gas supply system 30. The reaction gas discharge system 40 has two exhaust passages 42 corresponding to the respective lines of the front and rear sections of the supply system 30. The exhaust passage 42A in the front stage is connected to the supply passage 32A via the connection portion 41A on the supply passage 32A. The exhaust passage 42B in the subsequent stage is connected to the supply passage 32B via the connection portion 41B on the supply passage 32B.

In each of the supply passages 32 of the front stage and the rear stage, an opening and closing valve 51 is provided on the upstream side (the vaporizer 31 side) via the connection portion 41, and an opening and closing valve 52 is provided on the downstream side (the supply nozzle 33 side). An opening and closing valve 53 is provided in each of the exhaust passages 42 in the front and rear stages. Each of the opening and closing valves 51 to 53 is constituted by an electromagnetic opening and closing valve. By the opening and closing operations of the on-off valves 51 to 53, the operation mode of the film surface treatment apparatus 1 is switched to the reaction gas discharge mode and the exhaust mode. In the reaction gas discharge mode, the vaporizer 31 is connected to the supply nozzle 33, and the reaction gas is ejected from the supply nozzle 33 from the vaporizer 31 via the supply passage 32. In exhaust mode The vaporizer 31 is connected to the exhaust passage 42 and the reaction gas is introduced into the exhaust passage 42 from the vaporizer 31 via the supply passage 32 to the connection portion 41 and is discharged.

Further, the connecting portion 41 is preferably located on a portion of the reaction gas supply system 30 on the upstream side of the opening and closing valve 52. Preferably, the connecting portion 41 and the opening and closing valve 52 are provided in the vicinity of the supply nozzle 33.

Instead of the three opening and closing valves 51 to 53, a three-way valve may be provided in the connecting portion 41.

The two exhaust passages 42A and 42B are joined to each other and connected to the detoxification device 43. The detoxification device 43 is constituted, for example, by an alkali scrubber, and performs a decontamination operation such as removal of acrylic acid from the exhaust gas. The detoxification device 43 may be shared with the detoxification device of the exhaust system (not shown) that exhausts the internal environment of the treatment tank C. An acrylic acid recovery device may be disposed in the reaction gas discharge system 40 to recover the acrylic acid and return it to the vaporizer 31.

Further, the film surface treatment apparatus 1 includes a control mechanism 8. The control mechanism 8 includes a microcomputer, a drive circuit, a signal conversion circuit, and the like. The microcomputer controls the action of the film surface treatment apparatus 1. The drive circuit drives the power source 2, the rotating mechanism 15, the electromagnetic opening and closing valves 51 to 55, and the like based on an instruction from the microcomputer.

The method of surface-treating the film to be processed 9 by the film surface processing apparatus 1 is demonstrated based on the timing chart of FIG. 3 centering on the start operation of a surface process.

At present, it is assumed that the operation of the film surface treatment apparatus 1 is stopped (including temporary suspension due to some malfunction or the like). At this time, the power source 2 and the rotating mechanism 15 are stopped. Therefore, the plasma discharge in the plasma processing space 4 is not performed, and the plasma discharge is not performed. The handling of the film 9 is carried out. Further, the opening and closing valves 51 to 55 are closed. Therefore, the supply of gas to the processing spaces 3, 4 is not performed. When the operation of the membrane surface treatment apparatus 1 is started (including the restart after the recovery of the failure or the like), the reaction gas discharge step is first performed. Thereafter, the transfer step and the plasma irradiation step are sequentially started. The switching from the reaction gas discharge step to the reaction gas spray step is then carried out. The details are described below.

(1) Reaction gas discharge step

First, the opening and closing valve 51 of each of the lines of the supply system 30 and the exhaust system 40 in the front and rear stages is opened by the control unit 8, the opening and closing valve 52 is closed, and the opening and closing valve 53 is opened. Thereby, the supply system 30 and the exhaust system 40 are in the exhaust mode, the supply nozzle 33 is blocked from the vaporizer 31, and the exhaust passage 42 communicates with the vaporizer 31. Further, the on-off valve 55 is opened. Thereby, the carrier gas (N ₂ ) of a specific flow rate is introduced into the vaporizer 31 from the carrier gas source 34 via the introduction passage 35. The acrylic acid (AA) in the vaporizer 31 is vaporized and mixed with the carrier gas (N ₂ ) to form a reaction gas (AA+N ₂ ). This reaction gas is sent from the vaporizer 31 to the supply passage 32. After the reaction gas flows to the connection portion 41, it does not proceed to the supply nozzle 33 from here, but is guided to the exhaust passage 42 and discharged. Therefore, the reaction gas is not ejected from the supply nozzle 33, and the acrylic monomer does not adhere to the film to be processed 9.

At the beginning of the delivery of the reaction gas from the vaporizer 31, typically the concentration of acrylic acid in the reaction gas is unstable and deviates from the desired set concentration. In detail, when the acrylic acid in the vaporizer 31 is vaporized, it is necessary to vaporize latent heat. Therefore, the temperature in the vaporizer 31 is temporarily lowered immediately after the introduction of the carrier gas (N ₂ ) (initiation of vaporization). Then, by operating the temperature adjusting mechanism of the vaporizer 31, the temperature in the vaporizer 31 is slowly recovered to the set temperature. During the temperature fluctuation of the vaporizer 31, the vaporization amount of acrylic acid is unstable, and the acrylic acid concentration in the reaction gas is unstable. Further, in the reaction gas supply passage 32 (in the passage from the vaporizer 31 to the connection portion 41 in this stage), the adsorption and vaporization of the acrylic acid are also caused from the start of the supply of the reaction gas until the adsorption and vaporization become The acrylic acid concentration became unstable during the equilibrium state. As time passes, the concentration of acrylic acid in the reaction gas gradually stabilizes to approach the set concentration. The time (stabilization period) until the concentration of the acrylic acid is stabilized is, for example, about several minutes to several ten minutes. The reaction gas discharge step is continued until the time T ₁ corresponding to the stabilization period elapses. The time T ₁ is determined in advance within a range of several minutes to ten minutes and stored in the memory unit of the control unit 8. Specifically, the time T ₁ is usually preferably from 2 minutes to 15 minutes. Alternatively, the concentration of the acrylic acid in the reaction gas may be detected by a concentration sensor, and based on the detected concentration, whether or not the concentration of the acrylic acid is stable may be determined, thereby judging from the result whether or not the stabilization period (i.e., the required time T ₁ ) has elapsed.

The conveyance of the film 9 to be processed is not performed during the reaction gas discharge step. Therefore, the loss of the film to be processed 9 can be avoided.

(2) The beginning of the transfer step

After the time T _1, 12, 13 drive the rotation of the rotary mechanism 15 through the main roll, the film 9 is started to be processed conveyed.

(3) The beginning of the plasma irradiation step

Then, the opening and closing valve 54 of each line in the front stage and the rear stage of the discharge gas supply system 20 is opened, and the discharge gas (N ₂ ) of the discharge gas supply system 20 is supplied from the discharge gas nozzle 23 to the plasma processing space 4. Further, the power source 2 is driven to supply high-frequency power to the roller electrode 12 to generate a plasma discharge in the space 4. Thereby, the discharge gas (N ₂ ) is plasma (including excitation, decomposition, activation, radicalization, ionization), and the plasma discharge gas contacts the film 9 to be processed in the plasma processing space 4. That is, the film to be treated 9 is irradiated with nitrogen plasma. Before the start of the plasma irradiation, the conveyance of the film to be processed 9 is started in advance, whereby the continuous irradiation of the specific portion of the film to be processed 9 can be avoided. Therefore, it is possible to prevent the specific portion from being subjected to a large thermal damage, and it is possible to prevent the treated film 9 from being broken at the specific portion. The time T ₂ from the start of the transfer step to the start of the plasma irradiation step is, for example, a time until the transfer speed of the processed film 9 becomes a certain speed in the middle of the set speed increase. Further, the time T ₂ is not limited to the time until the certain speed is reached, and may be the time until the set speed is reached, or may be the time derived from the other index. The time T _{2 is} preferably set to, for example, several seconds. Specifically, the time T _{2 is} preferably set to about 2 to 5 seconds.

Further, the timing at which the opening and closing valve 54 is opened to start the supply of the discharge gas to the plasma processing space 4 can be set to be carried out before the plasma irradiation is started by starting the supply of electric power from the power source 2, and can also be set to be transported by the processed film 9. After the start, it may be set in the passage of the time T _{1 for} the stabilization of the reaction gas.

(4) The beginning of the reaction gas spraying step

Then, with respect to each of the lines in the front stage and the rear stage of the reaction gas supply system 30, the opening and closing valve 52 is opened in a state where the opening and closing valve 51 is opened, and the opening and closing valve 53 is closed. Thereby, the self-exhaust mode is switched to the reaction gas discharge mode, the exhaust passage 42 is closed, and the vaporizer 31 is in communication with the supply nozzle 33. Therefore, stop The reaction gas is discharged from the exhaust passage 42 (the end of the reaction gas discharge step). Then, the reaction gas from the vaporizer 31 is sent to the supply nozzle 33 through the supply passage 32, and is discharged from the discharge port 33e to the spray processing space 3. The acrylic acid in the reaction gas is condensed on the film to be treated 9 in the spray processing space 3 and adhered to the surface of the film to be processed 9 in a film form. With the conveyance of the film to be processed 9, the portion to which the acrylic acid adheres is introduced into the plasma processing space 4, and is irradiated with plasma. Thereby, a plasma polymerization reaction of acrylic acid is generated on the surface of the film 9 to be processed in the plasma processing space 4, and an adhesion promoting layer containing a plasma polymer film of acrylic acid can be formed on the surface of the film to be processed 9.

By stabilizing the concentration of the acrylic acid in the reaction gas by the reaction gas discharge step in advance, the plasma polymerization film of acrylic acid can be stably formed from the start of the reaction of the reaction gas on the film 9. Therefore, it is possible to prevent or suppress the treatment state of the end portion before the conveyance direction of the film to be treated from becoming unstable, to prevent the film portion which is unstable in such a treatment state from being formed, or to sufficiently shorten the film portion which is unstable in the above-described treatment state. length. Thereby, the loss of the film to be processed 9 can be prevented or suppressed. It is not limited to the normal start of the operation, and the resumption of the film to be processed 9 can be prevented or suppressed by using the above-described starting sequence when the operation is resumed after the temporary stop due to some failure or the like.

Further, before the start of spraying the reaction gas on the film to be processed 9, the plasma irradiation is started in advance, whereby the plasma polymerization reaction of acrylic acid can be surely generated from the beginning of the discharge of the reaction gas. Therefore, it is possible to prevent the acrylic acid from remaining directly on the film to be treated 9 as a monomer, and to prevent the residual monomer from being transferred to the device member or the peripheral member on the conveying path 19 downstream of the ejection processing space 3. Further, the above residual monomer can be prevented from being transferred to the table The device used in the subsequent steps of the surface processing. As a result, it is possible to prevent a decrease in the yield due to the above transition. In particular, it is possible to prevent the residual monomer from being transferred to the reversing roller 14 and adhering as dirt, and it is possible to surely prevent contamination of the film to be treated 9 when it comes into contact with the reversing roller 14, thereby reducing the yield.

The time T ₃ from the start of the plasma irradiation step to the start of the reaction gas spraying step is preferably as short as possible, for example, several seconds, more preferably within 5 seconds. Therefore, the time from the start of the conveyance of the film to be processed 9 to the start of the discharge from the supply nozzle 33 is several seconds to ten seconds. By shortening the time T ₃ , the loss of the film to be processed 9 can be further reliably prevented or suppressed.

In addition, it is preferable that the timing of opening the on-off valve 52 is the time T ₄ until the reaction gas is ejected from the connection portion 41 or the on-off valve 52 to the supply nozzle 33 (the supply nozzle 33 is replaced by the reaction gas from the connection portion 41 or the on-off valve 52). It is set in the supply passage 32 on the side and the replacement time of the gas in the supply nozzle 33). That is, the timing of opening the on-off valve 52 is preferably performed only at a time T ₄ earlier than the start of the reaction gas injection. The replacement time T ₄ depends on the length of the supply passage 32, etc., but is usually about several seconds and is about 10 seconds at the maximum. Therefore, as shown at T ₄ <T ₃ when the case, preferably the electric power is supplied from the power supply 2 to the beginning of opening and closing valve 523 is opened. In the case of T ₄ ≒T _{3 ,} it is preferable to open the on-off valve 52 substantially simultaneously with the supply of electric power from the power source 2 . In the case of T ₄ > T _{3 ,} it is preferable to open the on-off valve 52 before starting to supply electric power from the power source 2 . In order to prevent transfer, it is preferably T ₄ <T ₃ .

(5) fixed processing steps

Thereafter, the carrying step, the plasma irradiation step, and the reaction gas spraying step are continued. According to the film surface treatment apparatus 1, the conveyance is carried along the conveyance path 19 The membrane 9 is processed, and the reaction gas spray in the spray processing space 3A in the preceding stage, the plasma irradiation in the plasma processing space 4A in the preceding stage, the reaction gas spray in the spray processing space 3B in the subsequent stage, and The plasma in the plasma treatment space 4B of the latter stage is irradiated. The first adhesion promoting layer containing the acrylic plasma polymer film can be formed on the surface of the film to be processed 9 by the reaction gas spraying in the preceding stage and the plasma irradiation. Then, the second adhesion promoting layer containing the acrylic plasma polymerized film can be further laminated on the first adhesion promoting layer by the reaction gas spraying in the subsequent stage and the plasma irradiation. Thereby, the overall thickness of the adhesion promoting layer can be increased, and the adhesion of the film to be processed 9 can be further improved.

The present invention is not limited to the above embodiments, and various modifications can be made without departing from the spirit and scope of the invention.

For example, in the embodiment, the opening and closing valve 52A of the front stage and the opening and closing valve 52B of the subsequent stage are opened and closed at the same timing, but the opening and closing timing of the opening and closing valves 52A and 52B may be timed up and down. For example, in the reaction gas spraying step, the opening and closing valve 52A may be opened after the opening and closing valve 52A is opened. The other on-off valves 51 and 53 to 55 are also the same. In the embodiment, the opening and closing valves of the front stage and the opening and closing valves of the subsequent stage are opened and closed at the same timing. However, the timing can be made one after the other.

The timing of starting the irradiation of the plasma on the film to be processed 9 may be performed after the reaction gas discharge step is performed only for the duration T ₁ , and may be simultaneously with the transfer start timing of the film to be processed 9 , and if the intervals of the start timings are short, The plasma irradiation start timing may also precede the transfer start timing.

Can be treated with the film 9 of the conveyance start timing simultaneously or plasma irradiation start timing of the supply nozzle 33 is ejected from the timing of the reaction gas to the reaction gas only as long as the duration T ₁ discharge step, the timing of the beginning of the interval if such When it is short, the discharge timing of the reaction gas may be preceded by the transfer start timing or the plasma irradiation start timing.

As described above, the connection portion 41 of the reaction gas discharge system 40 is preferably located on the upstream side of the reaction gas supply system 30 with respect to the opening and closing valve 52, and the connection portion 41 and the opening and closing valve 52 are provided in the vicinity of the supply nozzle 33, but may not necessarily be provided. The connection portion 41 may be provided in a portion of the reaction gas supply system 30 from the vaporizer 31 to the discharge port 33e and on the upstream side of the opening and closing valve 52.

The exhaust passage 42 is not limited to being connected to the middle of the supply passage 32, and may be directly connected to the vaporizer 31 or branched from the reaction gas passage in the supply nozzle 33.

The number of the main rolls (roll electrodes) 11, 12, ... is not limited to three, and may be two or four or more.

The number of lines of the gas supply systems 20 and 30 is not limited to two in the front stage and the rear stage, and may be one or three or more.

The electrode structure of the plasma generating portion is not limited to a pair of roller electrode structures, and may be a parallel plate electrode.

The support transport mechanism of the film to be processed 9 may be provided separately from the electrode structure such as a parallel plate electrode. The support transport mechanism may also have a guide roller, a take-up roller, and a take-up roller that are separated from the electrodes. The support transport mechanism may also have an operator or a floating platform.

The reaction gas can also be directly supplied to the plasma processing space 4. In this case, the carrier gas of the reaction gas may also serve as a discharge gas.

The polymerizable monomer is not limited to acrylic acid, and may be methacrylic acid, itaconic acid, maleic acid or the like. The carrier gas is not limited to nitrogen (N ₂ ), and may be a rare gas such as Ar or He or another inert gas.

The present invention is not limited to the surface treatment of the protective film for a polarizing plate, and can be applied to a treatment of forming a polymer film of a polymerizable monomer on various resin films.

[Example 1]

Although the examples are described, the present invention is not limited to the following examples.

The surface treatment of the film to be processed 9 is performed using a device having substantially the same structure as that of the film surface treating apparatus 1 shown in Fig. 1. As the film to be processed 9, a TAC film was used. The width of the film 9 in the w direction is 330 mm.

1) Reaction gas discharge step

First, the respective lines of the reaction gas supply system 30 and the exhaust system 40 in the front stage and the rear stage are set to the exhaust mode, and the reaction gas of the vaporizer 31 is led to the exhaust passage 42 and discharged.

Acrylic acid (AA) was used as the polymerizable monomer in the reaction gas, and nitrogen (N ₂ ) was used as the carrier gas.

The carrier gas flow rate is 40 slm in both the front and rear pipelines.

The set temperatures of the vaporizers 31A, 31B were both 140 °C.

The set flow rate of the acrylic acid in the reaction gas was set to 7.5 g/min in both the front stage line and the rear stage line.

The time T ₁ for stabilizing the concentration of the acrylic acid in the reaction gas was set to T ₁ = 5 min. That is, the above reaction gas was discharged for 5 minutes. In the meantime, the rotation of the main rolls 11 to 13 is not performed, and the power supply from the power source 2 is not performed.

The vent gas system is detoxified using an alkali scrubber 43.

2) Transfer step

When the elapse of 5 minutes from the start of the discharge of the reaction gas, the rotation of the main rolls 11, 12, and 13 is started, and the conveyance of the film 9 to be processed is started. The set conveyance speed of the film to be processed 9 was set to 30 m/min.

The set temperatures of the main rolls 11 to 13 (the temperature of the film to be processed 9) were set to 40 °C.

3) Plasma irradiation step

After the conveyance of the film to be processed 9 is started, electric power is supplied from the power source 2 at the time when the conveyance speed reaches 10 m/min, and plasma irradiation in the plasma processing space 4 is performed. That is, the discharge gas is plasma-treated in the plasma processing space 4 and brought into contact with the treatment film 9.

The time T ₂ from the start of the conveyance of the film 9 to the start of the plasma irradiation is about 3 seconds.

The power supply is 3015 W (450 V × 6.7 A) for the DC before AC conversion.

The applied voltage between the roller electrodes was Vpp = 18.1 kV between the electrodes 11 and 12 in the front stage and the electrodes 12 and 13 in the rear stage.

Nitrogen (N ₂ ) was used as the discharge gas. The discharge gas (N ₂ ) flow rate is 20 slm in both the front line and the rear line.

The set temperatures of the discharge gas nozzles 23A and 23B were both 40 °C.

4) Reaction gas spraying step

Then, the respective lines in the front stage and the rear stage are switched from the exhaust mode to the reaction gas injection mode, and the reaction gas is discharged from the exhaust passage 42 to eject the reaction gas from the supply nozzle 33.

The time T ₃ from the start of the plasma irradiation to the start of the discharge of the reaction gas is about 5 seconds.

The set temperatures (discharge temperatures of the reaction gases) of the supply nozzles 33A and 33B were all set to 75 °C.

5) Evaluation 1

In the TAC film 9 after the surface treatment, the portion which is located in the spray processing space 3A at the start of the spraying of the reaction gas is used as the processing start portion, and the number of the processing starts from the processing start portion to the downstream side in the transport direction. The diaphragm is taken at a location separated by a certain distance. The above specific distances are 30 m, 60 m, 90 m, 120 m, 150 m, and 180 m6. The portion of 30 m is the portion of the film located in the spray processing space 3A at the point of 1 minute from the start of the spraying of the above reaction gas. The portion of 60 m is the portion of the film located in the spray processing space 3A at the point of 2 minutes from the start of the spraying of the above reaction gas. The portion of 90 m is the portion of the film located in the spray processing space 3A at the point of 3 minutes from the start of the spraying of the above reaction gas. The portion of 120 m is the portion of the film located in the spray processing space 3A at a point of time 4 minutes from the start of the spraying of the above reaction gas. The portion of 150 m is the portion of the film located in the spray processing space 3A at the point of 5 minutes from the start of the spraying of the above reaction gas. The portion of 180 m is the portion of the film located in the spray processing space 3A at the point of 6 minutes from the start of the spraying of the above reaction gas.

These collected TAC films were bonded to a PVA film to prepare a polarizing plate sample. An aqueous solution of a 5 wt% aqueous solution of (A) PVA having a degree of polymerization of 500 and a 2 wt% aqueous solution of (B) sodium carboxymethylcellulose was used as an adhesive. The mixing ratio of (A) and (B) is set to (A): (B) = 20:1. Dry the adhesive The drying condition was set to 80 ° C for 5 minutes. The polarizer sample has a width of 25 mm. The initial tensile strength of the polarizing plate sample (the subsequent strength when not exposed to the following warm conditions) was measured. The measurement method was set to a floating roll method (JIS K6854). The initial tensile strength of five polarizing plate samples was measured for each collected portion, and the average value was determined.

The results are shown in Table 1, which was 10.3 N/25 mm on the polarizing plate sample at a position of 30 m. The polarizing plate sample at 60 m was 10.4 N/25 mm. The polarizing plate sample at a position of 90 m was 10.1 N/25 mm. The polarizing plate sample at a position of 120 m was 10.9 N/25 mm. The polarizing plate sample at 150 m was 10.5 N/25 mm. The polarizing plate sample at 180 m is 10 N/25 mm.

It was confirmed that good processing performance was exhibited at least one minute from the start of the treatment (start of the spraying of the reaction gas).

Further, the durability bonding strength after exposure to a high temperature and a moist temperature condition was also measured. The warming conditions were set to 60 ° C and 95% RH. The polarizing plate sample was kept for 1 hour in the constant temperature and humidity chamber under the warm conditions. Thereafter, the polarizing plate sample was taken out from the constant temperature and humidity chamber, and cooled for 1.5 minutes, and thereafter, the tensile strength was measured. The measurement method was set to the floating roll method (JIS K6854) which is the same as the initial tensile strength.

The results are shown in Table 1. The polarizing plate sample at a position of 30 m was 6.2 N/25 mm. The polarizing plate sample at 60 m is 6.3 N/25 mm. The polarizing plate sample at a position of 90 m was 6.1 N/25 mm. The polarizing plate sample at a position of 120 m was 6.1 N/25 mm. The polarizing plate sample at 150 m is 6.5 N/25 mm. Polarized plate sample at 180 m The upper is 6.1 N/25 mm.

The durability adhesive strength can also be confirmed to be sufficiently large at least one minute after the start of the treatment (start of the spraying of the reaction gas).

Therefore, the loss of the film to be processed 9 can be set to less than 30 m.

6) Evaluation 2

Further, after the surface treatment described above, the presence or absence of the transfer of the acrylic monomer to the reverse roller 14 was investigated. Specifically, the reverse roll 14 was wiped with an ethanol impregnated rag, extracted with 50 ml of ethanol, and the presence or absence of acrylic acid was investigated by gas chromatography. As a result, acrylic acid was not detected, and it was confirmed that the acrylic monomer was not transferred to the reversing roll 14. Therefore, it is speculated that acrylic acid is sufficiently plasma-polymerized.

[Comparative Example 1]

In Comparative Example 1, the reaction gas discharge step was omitted. Except for this aspect, the same treatment as in Example 1 was carried out. That is, using the same apparatus as in Example 1, the operation was started in the order of the transport step, the plasma irradiation step, and the reaction gas spraying step without performing the reaction gas discharge. The processing conditions of the respective steps and the switching timing of the next step are the same as those of the first embodiment (except the reaction gas discharging step). The evaluation method after the treatment was also the same as in the first embodiment.

The results are shown in Table 1. The polarizing plate sample having an initial adhesion strength of 30 m was 3.2 N/25 mm. The polarizing plate sample at 60 m was 3.9 N/25 mm. The polarizing plate sample at a position of 90 m was 5.6 N/25 mm. The polarizing plate sample at a position of 120 m was 7.6 N/25 mm. The polarizing plate sample at 150 m is 9.2 N/25 mm. The polarizing plate sample at a position of 180 m was 10.3 N/25 mm.

Further, the polarizing plate sample having a durability of 30 m was 0.7 N/25 mm. The polarizing plate sample at 60 m was 0.8 N/25 mm. The polarizing plate sample at a position of 90 m was 1.1 N/25 mm. The polarizing plate sample at 120 m is 1 N/25 mm. The polarizing plate sample at a position of 150 m was 3.3 N/25 mm. The polarizing plate sample at 180 m is 6.5 N/25 mm.

The treatment performance could not reach the level of Example 1 from about 4 to 5 minutes from the start of the treatment, and reached the level of Example 1 after 5 minutes to 6 minutes from the start of the treatment. The loss of the film to be processed 9 is about 180 m.

According to the result of Comparative Example 1, when the apparatus of Example 1 was confirmed, the time T _{1 of the} reaction gas discharge step was preferably about T ₁ = 5 minutes.

Further, in Comparative Example 1, the presence or absence of the transfer of the acrylic monomer to the reverse roller 14 was also examined in the same manner as in the evaluation 2 of Example 1, and as a result, no change was observed in the acrylic acid.

[Comparative Example 2]

In Comparative Example 2, the apparatus for omitting the reaction gas discharge system 40 in Fig. 1 was used. Therefore, the reaction gas discharge step is not performed. Further, the order of the plasma irradiation step and the reaction gas spraying step was reversed to that of Comparative Example 1. That is, the operation is performed in the order of the transport step, the reaction gas spraying step, and the plasma irradiation step. Specifically, the conveyance of the film to be processed 9 is started, and the supply of the reaction gas from the vaporizer 31 is started at a time point when the conveyance speed is 10 m/min or more. After the supply of the reaction gas was started, the nitrogen plasma irradiation was started after 30 seconds. The treatment conditions of each step and the evaluation method after the treatment were the same as in Example 1 (except the reaction gas discharge step).

The results are shown in Table 1. The polarizing plate sample having an initial adhesion strength of 30 m was 3.3 N/25 mm. The polarizing plate sample at 60 m is 4 N/25 mm. The polarizing plate sample at a position of 90 m was 5.4 N/25 mm. The polarizing plate sample at a position of 120 m was 7.8 N/25 mm. The polarizing plate sample at 150 m was 8.8 N/25 mm. The polarizing plate sample at a position of 180 m was 10.8 N/25 mm.

Further, the polarizing plate sample having a durability of 30 m was 0.7 N/25 mm. The polarizing plate sample at 60 m was 0.8 N/25 mm. The polarizing plate sample at a position of 90 m was 1.3 N/25 mm. The polarizing plate sample at 120 m is 1.2 N/25 mm. The polarizing plate sample at 150 m is 3.6 N/25 mm. The polarizing plate sample at 180 m is 6.2 N/25 mm.

Therefore, the tendency of the processing performance was substantially the same as that of Comparative Example 1.

Further, the presence or absence of the transfer of the acrylic monomer to the reverse roller 14 was examined in the same manner as in the evaluation 2 of the first embodiment. As a result, acrylic acid was detected, and the transfer was confirmed.

According to the results of Example 1 and Comparative Examples 1 and 2, it was confirmed that the surface of the film to be processed 9 was first treated, and the reaction gas discharge step was first performed, whereby the loss of the film to be processed 9 was greatly reduced. Further, it was confirmed that the transfer of the acrylic acid monomer can be prevented by starting the spraying of the reaction gas after the start of the plasma irradiation.

[Industrial availability]

The present invention can be applied, for example, to the manufacture of a polarizing plate of a flat panel display (FPD).

1‧‧‧ Film surface treatment device

2‧‧‧Power supply

3‧‧‧Spray processing space

4‧‧‧Discharge gap (plasma processing space)

8‧‧‧Control agency

9‧‧‧Processed film

10‧‧‧Processing Department (supporting transport mechanism, plasma generation department)

11, 12, 13‧‧‧ Roll electrode

14‧‧‧Reverse Roller

15‧‧‧Rotating mechanism

19‧‧‧Transfer path

20‧‧‧Discharge gas supply system

21‧‧‧Discharge gas source

22‧‧‧Discharge gas path

23‧‧‧Discharge gas nozzle

23e‧‧‧Spray outlet

24‧‧‧ occlusion components

30‧‧‧Reactive gas supply system

31‧‧‧Vaporizer (reactive gas supply source)

32‧‧‧Reactive gas supply path

33‧‧‧Reactive gas supply nozzle

33e‧‧‧Spray outlet

34‧‧‧ Carrier gas source

35‧‧‧Carrier gas introduction pathway

36‧‧‧Shielding members

40‧‧‧Reactive gas discharge system

41‧‧‧Connecting Department

42‧‧‧Exhaust passage

43‧‧‧Injury device

51, 52, 53‧ ‧ electromagnetic opening and closing valve

54, 55‧‧‧Electromagnetic opening and closing valve

C‧‧‧Processing tank

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a circuit diagram of a film surface treatment apparatus according to an embodiment of the present invention.

Fig. 2 is a perspective view of a processing unit of the film surface treatment apparatus.

Fig. 3 is a timing chart showing the operation at the start of the operation of the film surface treatment apparatus.

1‧‧‧ Film surface treatment device

2‧‧‧Power supply

3A, 3B‧‧‧spray processing space

4A, 4B‧‧‧ discharge gap (plasma processing space)

8‧‧‧Control agency

9‧‧‧Processed film

10‧‧‧Processing Department (supporting transport mechanism, plasma generation department)

11, 12, 13‧‧‧ Roll electrode

14A, 14B‧‧‧Reverse Roller

15‧‧‧Rotating mechanism

19‧‧‧Transfer path

20‧‧‧Discharge gas supply system

21A, 21B‧‧‧discharge gas source

22A, 22B‧‧‧discharge gas path

23A, 23B‧‧‧discharge gas nozzle

23e‧‧‧Spray outlet

24A, 24B‧‧‧ occlusion components

30‧‧‧Reactive gas supply system

31A, 31B‧‧‧Vaporizer (reaction gas supply source)

32A, 32B‧‧‧Reactive gas supply path

33A, 33B‧‧‧Reactive gas supply nozzle

33e‧‧‧Spray outlet

34A, 34B‧‧‧ carrier gas source

35A, 35B‧‧‧ carrier gas introduction pathway

36A, 36B‧‧‧ Shielding members

40‧‧‧Reactive gas discharge system

41A, 41B‧‧‧ Connections

42A, 42B‧‧‧ exhaust passage

43‧‧‧Injury device

51A, 51B, 52A, 52B, 53A, 53B‧‧‧ electromagnetic opening and closing valves

54A, 54B, 55A, 55B‧‧‧ electromagnetic opening and closing valve

C‧‧‧Processing tank

Claims (5)

A method of starting a surface treatment by subjecting a reaction gas containing a polymerizable monomer and a plasma discharge plasma to a surface of the film to be treated by contacting a film to be treated with a resin, and starting The surface treatment start method of the surface treatment; and the reaction gas is sent from the reaction gas supply source while the reaction gas is not sent to the discharge port of the supply nozzle facing the film to be processed; After the elapse of the elapse of the elapse of the start of the ejecting, the film to be processed is started to be transported, and the plasma-discharged discharge gas is brought into contact with the film to be treated, and the discharge is stopped to start the discharge of the reaction gas from the discharge port. The surface treatment start method of claim 1, wherein the required time corresponds to a stabilization period until a concentration of the polymerizable monomer in the reaction gas is stabilized. The surface treatment start method according to claim 1 or 2, wherein the transfer of the film to be processed is started, and then the discharge plasma of the plasma is started to contact the film to be processed. A surface treatment starting method according to claim 1 or 2, wherein the discharge of the plasma-discharged gas is started to contact the film to be treated, and then the reaction gas is ejected from the supply nozzle. A film surface treatment apparatus which is characterized in that a surface of a treated film is treated by bringing a reaction gas containing a polymerizable monomer and a plasma discharge gas into contact with a resin-made treated film; its The present invention includes a reaction gas supply system including a supply passage extending from a supply source of the reaction gas, and a supply nozzle connected to a downstream end of the supply passage, and a support transport mechanism that supports the surface opposite to the supply nozzle The processed film transports the processed film along the transport path; the plasma generating unit plasma-discharges the discharge gas downstream of the supply nozzle on the transport path; and the discharge path is connected to the reactive gas supply system And a control unit that discharges the reaction gas sent from the supply source from the discharge passage when the surface treatment is started, and starts the conveyance and the plasma formation after a lapse of a lapse of time from the start of the delivery. And stopping the discharge and starting to eject the reaction gas from the supply nozzle.