TW201224026A - Film surface treatment method and device - Google Patents

Abstract

To improve the adhesive durability of a resin film, oxygen- and nitrogen-containing electrical-discharge gas for pretreatment is fed between electrodes (12, 13), formed into a plasma under near-atmospheric pressure, and brought into contact with a film (9) to be treated (plasma pretreatment step). At this time, the supply of energy is adjusted. The supply of energy, which is based on the power supplied from a power source (3), is preferably 0.5-7.5 Wsec/cm2 per unit area of the film (9) to be treated. Subsequently, reaction gas containing a polymerizable monomer is brought into contact with the film to be treated after the plasma pretreatment step (reaction gas blowing step). Electrical discharge gas for polymerizing treatment is then formed into a plasma at near-atmospheric pressure and is brought into contact with the film to be treated (plasma polymerization treatment step).

Description

201224026 VI. Description of the Invention: [Technical Field] The present invention relates to a method and apparatus for surface treatment of a resin-treated film, and relates to an adhesive property suitable for a protective film such as a polarizing plate, or even A film surface treatment method and apparatus for improving durability and the like. [Prior Art] For example, a polarizing plate is incorporated 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, polyvinyl alcohol) as a main component. The protective film contains a TAC film containing triacetate 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. The adhesion between the PVA film and the above-mentioned adhesive is good, but the adhesion of the TAC film is not good. Therefore, alkalizing treatment is performed in order to improve the adhesion of the TAC film. The alkalization treatment is a method in which a TAC film is immersed in a high-temperature, high-concentration lye. Therefore, it is pointed out that there is a problem of handling 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. [Prior Art Document] [Patent Document 1] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-25604 [Abstract] [Problems to be Solved by the Invention] 158970.doc

S 201224026 Usually, a lower aliphatic alcohol or a plasticizer is added to a resin film such as a TAC film. When these added components are precipitated (out) on the surface of the resin film, the penetration of the polymerizable monomer into the resin film is hindered or the polymerization is inhibited. Factor (oxygen source, etc.). If so, the durability at high temperatures or under high humidity is unstable. [Means for Solving the Problems] In order to solve the above problems, the method of the present invention is characterized in that it is a surface treatment method for surface treatment of a resin-treated film, and includes: a plasma pretreatment step, which is a discharge gas for pretreatment containing oxygen and nitrogen is pulverized (including excitation, activation, radicalization, ionization, etc.) in the vicinity of atmospheric pressure and brought into contact with the film to be treated; a reaction gas spraying step The reaction gas containing the polymerizable monomer is brought into contact with the treated film after the plasma pretreatment step; and the plasma polymerization treatment step is performed after the reaction gas spraying step or the reaction gas spraying step. The discharge gas for the polymerization treatment is plasma-treated near the atmospheric pressure and brought into contact with the film to be treated; and is adjusted so that the supply energy in the plasma pretreatment step is within a specific range. When the surface of the film to be treated is added with a lower aliphatic alcohol or a plasticizer, etc., the nitrogen and oxygen plasma which are subjected to the electric (four) treatment step can be decomposed and reduced, or can be removed. Therefore, by carrying out the reaction gas spraying step, the polymerizable monomer can be surely adhered to the resin film' and can be infiltrated into the inside of the resin film. By reducing or dividing in advance

S 158970.doc 201224026 The above-mentioned precipitation component prevents the precipitation component from becoming an obstacle to adhesion and penetration of the polymerizable monomer. By polymerizing the polymerizable monomer, the adhesion promoting layer can be formed not only on the surface of the resin film but also inside, and the adhesion promoting layer can be surely fixed to the resin film. Further, since the polymerization inhibitor (e.g., oxygen) in the above-mentioned precipitation component can be removed in advance, the polymerization reaction in the plasma polymerization treatment step can be promoted, and the polymerization degree of the polymerizable monomer can be improved. As a result, even when the temperature is high or wet, the decrease in the adhesion force can be suppressed, and the adhesion durability can be improved. The apparatus of the present invention is characterized in that it is a surface treatment apparatus for surface treatment of a resin-treated film; the method comprising: a plasma pretreatment section comprising a pair of pretreatment electrodes, and the pretreatment electrodes are mutually The pretreatment pretreatment discharge gas containing oxygen and nitrogen is plasma-pulverized near the atmospheric pressure and brought into contact with the treated film; the reaction gas supply portion 'containing the plasma after contacting the pretreatment discharge gas a reaction gas nozzle facing the film to be treated, and a reaction gas containing a polymerizable monomer is ejected from the reaction gas nozzle and brought into contact with the film to be processed; and a plasma polymerization treatment unit including a pair of polymerization processing electrodes, and After the discharge of the reaction gas or simultaneously with the discharge, the discharge gas for the polymerization treatment is electrically electrified near the atmospheric pressure and brought into contact with the treated film between the polymerization treatment electrodes; The supply energy in the plasma pretreatment section is set within a specific range. In the above film surface treatment apparatus, the film to be processed is first treated by a plasma pretreatment section. Nitrogen and oxygen plasma are generated in the plasma pretreatment section, and 158970.doc -6-201224026 is irradiated to the film to be treated. When an additive component such as a lower aliphatic alcohol or a plasticizer is precipitated on the surface of the film to be treated, the precipitated additive component can be reduced or removed by electropolymerization of nitrogen and oxygen. Thereafter, the reaction gas is brought into contact with the film to be treated in the reaction gas supply unit. Thereby, the polymerizable monomer of the reaction gas towel can be surely adhered to the resin film and further penetrated into the interior of the resin crucible. By pre-treating or removing the above-mentioned precipitated component', it is possible to prevent the precipitated component from becoming an obstacle to adhesion and penetration of the polymerizable soap body. The polymerizable monomer is plasma-polymerized by plasma irradiation of the plasma polymerization treatment portion. Thereby, the adhesion promoting layer can be formed not only on the surface of the resin film but also inside, and the adhesion promoting layer can be surely fixed to the resin film. Further, since the polymerization inhibitor (for example, oxygen) in the precipitation component can be reduced or removed in advance, the polymerization reaction in the plasma polymerization treatment unit can be accelerated, and the polymerization degree of the polymerizable monomer can be increased, and even at a high temperature The adhesion force drop can also be suppressed under the lower or more wet conditions and the durability of the adhesion can be improved. Here, the above-mentioned specific range refers to a range of supply energy which exhibits the effect of reducing or removing the above-mentioned precipitation component and exhibiting the penetration of the above-mentioned polymerizable monomer into the above-mentioned resin film. If the above-mentioned supply energy is too small, the above-mentioned precipitation component cannot be sufficiently reduced or removed. If the supply energy is too large, the polymerizable monomer cannot be sufficiently permeated into the resin film. In the adjustment of the supply energy, it is preferable that the supply energy of the electric power supplied by the electric power supply for the electropolymerization in the electric pretreatment step is 〇5 to 7 5 W sec per unit area of the film to be treated. W. The power source is connected to the pretreatment electrode, and the supply energy based on the supply power of the power source is preferably 0.5 to 7.5 W.sec/cm 2 per unit area of the film to be processed 158970.doc 201224026. By setting the above-mentioned supply energy to 〇 5 W-Sec/cm 2 or more, the decomposition action of the above-mentioned precipitation component can be surely exhibited. By setting the above-mentioned supply energy to 7 5 w.sec/cm 2 or less, the surface state of the eucalyptus membrane can be maintained in a state in which the polymerizable monomer can be sufficiently infiltrated. Thereby, the adhesion promoting layer can be surely fixed to the resin film. Here, the supply energy may be adjusted by the area of the discharge surface of the pretreatment electrode (the size of the discharge space), the relative movement speed of the film to be processed, and the like in addition to the power supplied from the power source. Usually, the above-mentioned power source converts the commercial parent power into DC power, and the DC power is converted to a high frequency and output to the pre-processing electrode. The above supplied electric power can be specified by the above-described direct current electric power. The volume content of oxygen in the discharge gas for pretreatment is preferably 〇····. Thus, the precipitated component can be reliably reduced or removed. The plasma of the discharge gas by pretreatment is ' When an oxygen atom active species and a nitrogen molecule are produced, the life of the oxygen atom active species is shorter, and the active species of the nitrogen molecule are longer. The oxygen atom active species are repeatedly excited and attenuated among the nitrogen molecular active species. At this time, if the oxygen content of the pretreatment pretreatment gas is excessive (more than 50%), the excited oxygen atom active species easily collides with the oxygen molecules and is attenuated. Therefore, the reduction efficiency or the removal efficiency of the precipitation component is lowered. When the discharge gas for pretreatment is completely free of oxygen or oxygen (less than 0'1%), the components cannot be separated and analyzed, and it is difficult to reduce and further remove the precipitated components. The film to be treated is continuously continuous and continuously It is preferable to transfer the above-mentioned film surface treatment apparatus film transfer mechanism, preferably the above-mentioned 158970.doc 201224026 to the pretreatment electric #, the above reaction. The gas nozzle, & The transfer path of the processed electrode to the processed film is sequentially arranged from the upstream side along the transport mechanism, whereby the processed film can be transported along the transport path, and plasma pretreatment, reaction gas supply, and plasma are performed. The polymerization process is continuously processed. Therefore, the processing time can be shortened and the processing efficiency can be improved. Here, the vicinity of the atmospheric pressure refers to the range, and it is preferable to consider the ease of pressure adjustment or the simplification of the device configuration. 1.33X 104~l〇.664xl〇4 pa, more preferably 9 331χ1〇4~ l〇.397xl〇4 pa 〇 The present invention is suitable for the treatment of a difficult-adhesive optical resin film for the difficult-to-contact optical resin When the film is attached to the easy-adhesive optical resin film, it is suitable for improving the adhesion of the difficult-to-adhere optical resin film. The main component of the above-mentioned difficult-to-adhere optical resin film may, for example, be a cellulose (TAC) or a polypropylene. Dilute (pp, p〇iypr〇pyiene), polyethylene (PE, p〇lyethylene), cycloolefin polymer (c〇p, cycl〇〇lefin polymer) 'c〇c 'cycloolefin copolymer, Gather PET, polyethylene terephthalate, polymethylmethacrylate, polyimide, or the like. The main component of the above-mentioned easy-to-adhere optical resin film is exemplified. For example, polyvinyl alcohol (PVA), ethylene-vinyl acetate copolymer (EVA), etc. Examples of the polymerizable monomer include monomers having an unsaturated bond and a specific functional group. The specific functional group is preferably selected from the group consisting of a hydroxyl group, a carboxyl group, and an ethyl group.

S 158970.doc 201224026 A glycidyl group, an epoxy group, an ester group of a carbon number hiO, a sulfone group or an aldehyde group, particularly preferably a hydrophilic group such as a slow group or a trans group. Examples of the monomer containing an unsaturated bond and a hydroxyl group include ethylene glycol decyl acrylate, allyl alcohol, and hydroxyethyl methacrylate. Examples of the monomer containing an unsaturated bond and a carboxyl group include acrylic acid, mercaptoacrylic acid, itaconic acid, maleic acid, and 2-mercaptopropene propionic acid. Examples of the monomer containing an unsaturated bond and an ethyl oxime group include vinyl acetate and the like. Examples of the monomer containing an unsaturated bond and a glycidyl group include mercapto acrylate glycidol. Examples of the monomer containing an unsaturated bond and an ester group include ruthenium acrylate, ethyl acrylate, butyl acrylate, tert-butyl acrylate, 2-ethyl hexyl acrylate, octyl acrylate, and ruthenium methacrylate. Ester, ethyl mercaptoacetate, butyl methacrylate, tert-butyl methacrylate, isopropyl methacrylate, 2-ethyl methacrylate, and the like. Examples of the monomer containing an unsaturated bond and an aldehyde group include acrylic aldehyde and crotonaldehyde. Preferably, the polymerizable monomer is a monomer containing an ethylenically unsaturated double bond and a slow group. Examples of such a monomer include acrylic acid (ch2=CHC00H) and methacrylic acid (ch2=c(ch3)cooh). The above polymerizable monomer is preferably acrylic acid or methacrylic acid. Thereby, the adhesion of the difficult resin film can be surely improved. The above polymerizable monomer is more preferably acrylic acid. In the case where the film to be treated is a polymer film of an olefin monomer such as COP, COC, PP or PE, it is preferred that the above reaction gas contains a polymerizable monomer 158970.doc

S •10- 201224026 Water-soluble monomer and dilute hydrocarbon monomer. The volume concentration of the dilute hydrocarbon monomer in the reaction gas is preferably more than u times the volume concentration of the water-soluble monomer. The dilute hydrocarbon monomer is an unsaturated group having a double bond and having no polar functional group, and may be a linear village (4), and (4) may have a number of (10) or more. Preferably, as a lean furnace, the system is used in a liquid near the room temperature and is easily gasified. The number of carbon atoms of the olefinic monomer is preferably from $8 to more than s. Specific examples of the straight-chain thin-pore-type monomer include decene, hexene, i-heptene, and octyl. It is preferable that the double-bonded end is at the end of the straight chain, but is not particularly limited thereto. Examples of the cyclic olefinic monomer include, in addition to 1-cyclopentene, 1-cyclohexan, b-cycloheptene, and cyclooctene, cyclopentene and monopentamethylene hydride (DCPD). A cyclic diene such as dicycl〇pentadiene). The above olefin-based monomer is preferably a cyclic diene, particularly preferably cyclopentadiene or dicyclopentadiene. Thereby, the compatibility of the liquefied layer and even the promoting layer with the olefin-based monomer polymerized film can be improved, and in particular, the compatibility with the film containing the cycloolefin polymer (COP) can be improved. Further, the cyclic dioxime is a *Dieis· alder reaction, etc., and has high polymerizability and is easily copolymerized with a water-soluble monomer. The above water-soluble monomer is preferably a monomer comprising an aldehyde group, a carboxyl group, or a hydroxyl group. This can improve the compatibility with the adhering member such as a binder containing a component having a polarity such as PVA or a polarizing element. Specifically, examples of the water-soluble monomer include acetaldehyde, vinyl alcohol, acrylic acid (AA), mercaptoacrylic acid, styrenesulfonic acid, acrylamide, mercaptopropenylamine, and quinone dimethylamine. Acrylamide, hydrazine, hydrazine-dimethyl decylamine, and the like. Particularly, as the water-soluble monomer, acetaldehyde or acrylic acid is preferred. The acetaldehyde constitutes a compound in which vinyl alcohol and ketone-enol tautomer are present and coexist 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 selected from inert gases such as nitrogen, argon and helium. From the viewpoint of economy, it is preferred to use nitrogen as a carrier gas. ° Most polymerizable monomers such as acrylic acid or mercaptoacrylic acid are in the liquid phase at normal temperature and pressure. Such a polymerizable monomer may be vaporized in a carrier gas such as an inert gas. The method of vaporizing a polymerizable monomer in a carrier gas is a method of extruding a carrier gas in a polymerizable monomer liquid by a method of extruding a saturated vapor on a liquid surface of a polymerizable monomer liquid by a carrier gas. A method of heating a polymerizable monomer liquid to promote evaporation thereof, and the like. Extrusion and heating, or foaming and heating may also be used in combination. In the case where the polymerizable monomer is heated and vaporized, the polymerizable monomer is preferably selected to have a boiling point of 3 〇〇 t > c or less in consideration of the burden on the heater. Further, the polymerizable monomer is preferably selected so as not to be decomposed by heating (chemical change). The second discharge gas for the polymerization treatment may, for example, be an inert gas of nitrogen (10) or a rare gas (Ar, Ne, He, etc.). [Effect of the Invention] According to the present invention, the adhesion durability of the resin film can be improved. [Embodiment] Hereinafter, embodiments of the present invention will be described with reference to the drawings. As shown in Fig. 1, the treated film ^ M is in the form of a continuous sheet. The film to be treated 9 in this embodiment is a canthraquinone film for a polarizing plate. The film is made by, for example, Sanyi I58970.doc •i2·

S 201224026 Cellulose (TAC) is a main component of TAC film. The thickness of the film 9 is, for example, about 100 μm. The polarizing film including the PVA film and the TAC film 9 are bonded by a bonding agent to constitute a polarizing plate. As the adhesive, a water-based adhesive such as a PVA aqueous solution can be used. Prior to the subsequent step, the TAC film 9 is surface-treated by the film surface treating device 1, thereby increasing the bonding strength of the TAC film 9, thereby improving the bonding time. 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), cycloolefin copolymer (COC), and poly-pair. A film of various resins such as phthalic acid ethyl ester (PET), polydecyl methacrylate (PMMA), and polyimine (PI). As shown in Fig. 1, the film surface treatment apparatus 1 of the first embodiment includes a film surface treatment unit 10' gas supply sources 2a to 2c and a power source 3. As shown in FIGS. 1 and 2, the film surface treatment unit 10 includes a plurality of (here, three) light electrodes 11, 12, 13, one or a plurality of (here, two) reaction gas nozzles 21, 22 And the discharge gas nozzle 30. The electrodes 12, 13' gas supply source 2a, the power source 3, and the discharge gas nozzle 3' constitute a plasma pretreatment portion A. The reaction gas nozzles 21 and 22 and the gas supply source 2b constitute a reaction gas supply unit B. The electrodes 12 and 13, the gas supply source 2c, the power source 3, and the discharge gas nozzle 3' constitute a plasma polymerization processing unit c. The electrodes 12 and 13, the power source 3, and the discharge gas nozzle 3〇 have both the components of the plasma pretreatment unit A and the components of the plasma polymerization treatment unit c. Each of the roller electrodes 11 to 13 is formed to have a processing width orthogonal to the axis of the drawing.

S 158970.doc 201224026 The cylindrical shape of the W direction. The three roller electrodes 11 to 13 are arranged in parallel to each other in Fig. 1 . The roller electrode 11 on the left side and the roller electrode 12 on the center are disposed apart from each other. The center roller electrode 12 is disposed adjacent to the right roller electrode 13. The roller electrode 11 on the left side and the roller electrode 12 on the center are electrically grounded. A power source 3 is connected to the electrode 13 on the right side. The power source 3 converts, for example, DC power into a pulse wave of the frequency power, and supplies the pulse wave high frequency power to the roller electrode 13. Thereby, a plasma discharge is generated between the electrodes 12 and 13 at a pressure near atmospheric pressure. The space 19 between the mutually opposing portions of the roller electrodes 12, 13 becomes a discharge space near atmospheric pressure. Specifically, the narrowest portion between the roller electrodes ^, U and the space in the vicinity thereof become the discharge space Η. The roller electrodes 12 and 13 also function as one of the plasma pretreatment sections 8 as an electrode for pretreatment, and as an electrode for polymerization treatment as one of the plasma polymerization treatment sections c. The TAC film 9 to be treated is wound around the circumference of the upper side of the three roll electrodes "~^ for about half a week. A portion between the roller electrode 左侧 on the left side of the TAC film 9 and the roller electrode in the center is pulled out from the roller electrodes 11, 12 to the lower side, and folded back by one or a plurality of (two in the figure) guide rolls 41. . A portion between the roller electrode 12 at the center of the TAC film 9 and the roller electrode 13 on the right side is pulled out from the roller electrodes 12, 13 to the lower side, and folded back by one or a plurality of (two in the drawing) guide rolls 42. Although not shown in the drawings, a rotation mechanism is connected to each of the roller electrodes u to 13. The rotation mechanism includes a drive unit such as a motor, and a transmission mechanism that transmits the drive force of the drive unit to the axes of the roller electrodes 11 to 13. The communication mechanism is constituted by, for example, a pulley mechanism or a gear row. The roller electrodes 11 to 13 are rotated by the respective rotation axes of the respective axes and synchronized with each other. The roller electrodes Η~13 can be rotated in both directions of the positive and negative I58970.doc 201224026. Roll electrodes 11 to 13 are due to the figure! The middle direction is turned clockwise, and the film 9 can be transported to the forward direction (right in Fig. i). The transport speed of the film 9 is, for example, about 2 to 60 m/min. The roller electrodes 11 to 13 are retracted in the counterclockwise direction in Fig. 1, and the TAC film 9 can be wound back to the return direction (left in the figure). The roller electrodes 11, 12, 13 have a function as a support mechanism and a transport mechanism of the film 9. A temperature adjustment mechanism (not shown) is provided in each of the roller electrodes 11, 12, and 13. For example, a temperature adjustment path is formed in each of the roller electrodes 11 to 13, and the temperature adjustment medium is passed through a temperature control medium such as temperature-regulating water. Thereby, the roller electrodes u to n can be tempered. Further, it is possible to adjust the temperature of the film 9 on the circumferential surface of the roller electrodes n to 13. The set temperature of the film 9 is preferably about 25 〇 c 5 (circle rc), and the top of the roller electrode 11 on the left side is disposed. The reaction gas nozzle 21 is disposed above the center roller electrode 12. The reaction gas nozzle 22 is disposed. The supply path 4 extends from the supply source 2b of the reaction gas, and the supply path 4 is branched and connected to each of the reaction gas nozzles 21 and 22. The reaction gas nozzles 21 extend in the processing width direction w (the direction perpendicular to the plane of the paper in FIG. i) to have substantially the same length as the roller electrode U, and have a certain degree in the circumferential direction of the roller electrode 11 (left and right in FIG. 1). Although the detailed illustration is omitted, the rectifying portion is provided in the reaction gas nozzle 21. The rectifying portion includes a chamber or a slit extending in the processing width direction w, and a plurality of small holes arranged in the processing width direction w. The reaction gas from the supply path 4 is homogenized in the treatment width direction W. The discharge port 2ia is formed on the lower surface of the reaction gas nozzle 21 so as to be distributed in the processing width direction and the electrode circumferential direction. The lower side of the reaction gas nozzle 21 is disposed below. There is a shielding member 23. The cross section of the shielding member 23 orthogonal to the processing width direction w is curved in an arc shape, and I58970.doc, 201224026 is extended by the same length as the roller electrode 11 in the processing width direction w. The both ends of the arcuate direction (left and right in Fig. 1) of the shielding member 23 extend further toward the circumferential direction of the roller electrode 11 than the reaction gas nozzle 21. The shielding member 23 is along the upper side of the roller electrode 11. The peripheral surface of the shielding member 23 separates the reaction gas spraying space 17 between the shielding member 23 and the roller electrode 11. The ejection port 21a penetrates the shielding member 23 in the thickness direction (up and down) and faces the reaction gas entanglement space 17. The reaction gas in the inner rectifying portion is ejected from the ejection port 21a to the ejection space 17 while maintaining the uniform state. By the shielding member 22, the reaction gas can be temporarily left in the ejection space 17, and the external airflow can be suppressed or prevented. The central reaction gas nozzle 22 extends in the processing width direction w to have substantially the same length as the roller electrode 12, and has a certain degree in the circumferential direction of the electrode 12 (about the left and right in FIG. 1). Although the detailed drawing is omitted, a rectifying portion is provided in the reaction gas nozzle 2 2. The rectifying portion includes a chamber or a slit extending in the processing width direction w, and a plurality of small holes arranged in the processing width direction w. The reaction gas from the supply path 4 is homogenized in the treatment width direction w. The discharge port 22a is formed on the lower surface of the reaction gas nozzle 22 so as to be distributed in the processing width direction and the electrode circumferential direction. The central reaction gas nozzle 22 A shielding member 24 is disposed under the shielding member 24. The cross section orthogonal to the processing width direction w of the shielding member 24 is curved in an arc shape, and a curved plate extending in substantially the same length as the roller electrode 2 in the processing width direction w And constitute. Both end portions of the shielding member 24 in the arc direction (left and right in Fig. 1) extend further toward the circumferential direction of the roller electrode 12 than the reaction gas nozzle 22. The shielding member 24 is along the circumferential surface of the upper side of the roller electrode 12. A reaction gas spray space 18 is drawn between the shield member 24 and the reticle 12 of the 158970.doc • 16 - 201224026. The discharge port 22a penetrates the shield member 24 in the thickness direction (up and down), and sprays the space 18 toward the reaction gas. The reaction gas passing through the rectifying portion in the nozzle 22 is ejected from the ejection port 22& to the ejection space 18 while maintaining the uniform state. The reaction gas is temporarily left in the spray space 18 by the shield member 24', and the outside airflow can be suppressed or prevented from entering the spray space 丨8. The reaction gas contains a polymerizable monomer as a reaction component. Here, acrylic acid AA is used as the polymerizable monomer. Further, the reaction gas contains a carrier gas. Nitrogen (N2) is used as a carrier gas. The polymerizable monomer is not limited to acrylic acid, and may be methyl acrylic acid, itaconic acid, maleic acid or the like. The carrier gas is not limited to nitrogen (n2), and may be a rare gas such as Ar or He or another inert gas. Although the detailed drawings are omitted, the reaction gas supply source 2b is constituted by a vaporizer. In the gasifier, acrylic acid AA (polymerizable monomer) is accumulated in a liquid state. The carrier gas (N2) is introduced into the gasifier. The acrylic acid AA is vaporized and mixed in the carrier gas (N2) to form a reaction gas (AA + N2). The carrier gas can be introduced into the upper side from the liquid surface of the liquid acrylic acid in the vaporized state, or can be introduced into the interior of the liquid acrylic acid to cause foaming. The vaporization of acrylic acid can be adjusted according to the temperature of the gasifier 1: even the concentration of acrylic acid in the reaction gas can be adjusted. Alternatively, a portion of the carrier gas may be introduced to the gasifier and the remainder may be bypassed within the gasifier to adjust the flow ratio of the portion to the remainder to thereby adjust the concentration of acrylic acid in the reaction gas. A temperature control mechanism (not shown) such as a heating belt is provided in the piping constituting the reaction gas supply path 4. Each of the reaction gas nozzles 21 and 22 is provided with a temperature adjustment mechanism (not shown) such as a temperature adjustment path through which 158970.doc 5 •17·201224026 warm water passes. With these temperature control mechanisms, the discharge temperature of the reaction gas can be adjusted. The discharge temperature of the reaction gas is preferably higher than the condensation temperature of acrylic acid. The discharge temperature of the reaction gas is preferably from about 50 ° C to about 100 ° C. A discharge gas nozzle 30 and a closing member 39 are provided between the center roller electrode 12 and the right roller electrode 13. The blocking member 39 is disposed above the discharge space 19. The discharge gas nozzle 30 is disposed below the discharge space 19. The blocking member 39 and the discharge gas nozzle 30 sandwich the discharge space 19 to face each other. The cross section of the upper blocking member 39 orthogonal to the processing width direction w is tapered toward the lower end and extends in the processing width direction w for a long time. The lower end (front end) of the closing member 39 faces the discharge space 19. The occluding member 39 occludes the upper end portion of the discharge space 19 to some extent. The discharge gas nozzle 30 is disposed inside the folded portion of the TAC film 9 between the roller electrodes 12 and 13. The cross section of the discharge gas nozzle 30 orthogonal to the processing width direction w is tapered toward the upper end, and extends in the processing width direction w. The discharge port of the upper end (front end) of the discharge gas nozzle 30 faces the discharge space 19. The discharge gas nozzle 3 闭 occludes the lower end of the discharge space 19 to some extent. The supply path 5a from the pretreatment discharge gas supply source 2a and the supply path 5c from the polysilicon treatment discharge gas supply source 2c are connected to a switching mechanism 5e such as a three-way valve. The switching mechanism 56 supplies two discharge gas sources. The middle portion is selectively connected to the discharge gas nozzle 30 via the common path 5. Although the detailed drawings are omitted, a rectifying portion is provided in the discharge gas nozzle 3A. The rectifying portion includes a chamber or slit extending in the processing width direction w, a plurality of small holes arranged in the processing width direction W of 158970.doc 201224026, and the discharge gas from the supply path 5 is uniformized in the processing width direction W. . The discharge gas passing through the rectifying portion is ejected from the discharge port at the upper end of the nozzle 30 while maintaining a uniform state. A pretreatment discharge gas is accumulated in the supply source 2a. The discharge gas for pretreatment contains nitrogen (N2) and oxygen (〇2). The volume fraction of oxygen in the discharge gas for pretreatment is preferably from 0.1 vol% to 50 vol%. The discharge gas for pretreatment is preferably clean dry air (CDA, Clean Dry Air). This can reduce operating costs. The clean and dry air has an oxygen content of 21 v〇1% & right. A discharge gas for polymerization treatment is accumulated in the supply source 2c. The radioactive system for polymerization treatment is composed of nitrogen (N2) gas. The discharge gas for polymerization treatment is not limited to nitrogen (NO, and may be a rare gas such as Ar or He or another inert gas. The gas supply sources 2b and 2c are supplied by a supply unit of nitrogen and a supply unit containing oxygen. The gas supply mechanism may be operated by selecting either one of a pretreatment mode in which nitrogen and oxygen are mixed and supplied to the discharge gas nozzle 3, and a polymerization processing mode in which only nitrogen is supplied to the discharge gas nozzle 30. A method of surface-treating the film to be processed 9 by the film surface treatment apparatus 上述 having the above configuration will be described. The surface treatment is performed in the order of the plasma pretreatment step, the reaction gas spraying step, and the plasma polymerization treatment step. [Plastic Pretreatment Step] The TAC film 9 to be treated is wound around the roll electrodes 11, 12, 13 and the guide rolls 15897 〇.d〇c 201224026 41, 42. Then the 'roll electrodes u, 12, 13 are shown in the figure. In the first clockwise rotation, the TAC film 9 is conveyed to the substantially right direction in the order of the roller electrodes 1A, 12, and 13. The discharge gas nozzle 30 is connected to the discharge gas supply source for pretreatment in the two supply sources 2a and 2c. 2a Further, the reaction gas supply is not performed from the supply source 2b. Then, the pretreatment discharge gas (N2 + 〇2) is supplied from the supply source 2a to the nozzle 30' and ejected from the nozzle 30 into the interelectrode space 19. The power source 3 supplies electric power to the roller electrode 丨3, and an electric field is applied between the electrodes 丨2 and 丨3. Thereby, an atmospheric piezoelectric slurry discharge is generated in the interelectrode space 19, thereby plasma-discharging the pre-treatment discharge gas. In the case of generating a nitrogen molecule active species, an oxygen atom active species, etc., the active species contact the surface of the TAC film 9, thereby decomposing components such as a lower aliphatic alcohol or a plasticizer deposited on the surface of the TAC film 9. In this case, the above-mentioned precipitation component can be reduced and removed. In this case, the energy supplied for the plasmaization (for example, the energy supplied from the DC power supply for the AC conversion in the power source 3) (the power source for the plasmaization) The supply energy of the power supply is adjusted so as to be 0.5 to 7.5 W.sec/cm 2 per unit area of the TAC film 9. The energy can be reliably decomposed by setting the supply energy to 〇5 W.sec/cm2 or more. The above precipitated components, and can be confirmed The effect of reducing or removing the precipitation component is exhibited in the field. By setting the supply energy to 7.5 W.seeW or less, the surface state of the film 9 can be maintained in a state in which the monomer is allowed to permeate. In addition to the power supply, it can be adjusted by the size of the transfer rate discharge space 19 of the TAC film 9, etc. Further, by setting the content of oxygen in the discharge gas for pretreatment to 158970.doc -20- 201224026 vol% ～50 v〇l%, the component can be further reliably analyzed. By setting the oxygen content to 0.1 vol% or more, the effect of reducing the precipitation component or the removal effect can be surely exhibited. By setting the oxygen content to 50% or less, it is possible to suppress the attenuation caused by the collision of the oxygen species active species with the oxygen molecules, and it is possible to prevent the decrease in the precipitation component or the decrease in the removal action. The TAC film 9 passes through the discharge space 19 in a state of contacting the roller electrode 12, and is folded back by the guide roller 42 to pass through the discharge space 19 in the state of the contact roller electrode 13. Therefore, the TAC film 9 is connected to the discharge space 19. Perform 2 treatments. [Rewinding step] After the completion of the plasma pretreatment step, the supply of the pretreatment discharge gas from the supply source 2a is stopped. Then, the roller electrodes 11, 12, 13 are reversed to be wound back into the TAC film 9. [Reaction gas spraying step] Next, the roller electrodes 11, 12, and 13 are rotated forward again, and the TAC film 9 is again transported in the forward direction in the order of the electrodes 11, 12, and 13. At the same time, the reaction gas (AA + N2) is distributed from the supply source 2b to the two nozzles 21, 22, and is ejected from the discharge ports 21a, 22a to the reaction gas injection spaces 17, 18, respectively. The TAC film 9 is in contact with the reaction gas in the reaction gas spraying space 17, and is further in contact with the reaction gas in the reaction gas spraying space 18. Thereby, the acrylic acid (reaction component) in the reaction gas is condensed and contracted on the surface of the TAC film 9, and adhered to the TAC film 9 and further penetrates into the inside of the TAC film 9. By reducing or removing the above-mentioned precipitation component in advance in the pretreatment step, it is possible to prevent the precipitation component from becoming an obstacle to adhesion and penetration of acrylic acid. Moreover, by preprocessing

S 158970.doc -21 - 201224026 The setting of the energy supply, while maintaining the surface of the TAC film 9 in a state of allowing monomer permeation, so that acrylic acid can be surely infiltrated into the interior of the TAC film 9 by two sprays In the spaces 17 and 18, the reaction gas is brought into contact with the TAC film 9 twice, and even if the transport speed of the TAC film 9 is large, the amount of adhesion of acrylic acid or even the amount of penetration can be surely ensured. [Purpose polymerization treatment step] The discharge gas for polymerization treatment is sent from the supply source 2c to the nozzle 3〇 at the same time as the start of the spraying of the reaction gas or before the ejection, and is ejected from the nozzle 30 into the interelectrode space 19. . At the same time, electric power is supplied from the power source 3 to the roller electrode 13' and an electric field is applied between the roller electrodes 12, 13. Thereby, the atmospheric piezoelectric slurry discharge is generated in the interelectrode space 19, and the polymerization process is plasma-plasmaized. The TAC film 9 subjected to the above-described reaction gas spraying step is introduced into the discharge space 19. The acrylic acid adhering to and permeating the TAC film 9 is activated by the discharge gas plasma in the discharge space 19, thereby causing the double bond to be broken, aggregated, or the like. Further, bonds such as c_c, c 〇, and C H of the surface molecules of the TAC film 9 are cut. In the bond cutting portion, a polymer bond of acrylic acid (graft polymerization) or a COOH group decomposed from acrylic acid or the like is bonded. Since the above-mentioned precipitation component is reduced or removed in advance, generation of a polymerization inhibitor such as oxygen from the precipitation components can be suppressed, and the degree of polymerization of acrylic acid can be sufficiently increased. Thereby, an adhesion promoting layer of a polymer containing acrylic acid can be formed on the surface of the TAC film 9. Since acrylic acid is sufficiently adhered to the diced: film 9 and sufficiently penetrates into the inside, not only the surface of the TAC film 9 but also an adhesion promoting layer can be formed inside. Thereby, the adhesion promoting layer can be surely fixed to the tac film 9° 158970.doc -22-201224026 The surface-treated TAC film 9 is adhered to the hidden polarizing film via a water-based adhesive such as a pVA aqueous solution to prepare a polarizing plate. . Since the adhesion promoting layer is sufficiently fixed to the TAC film 9, it is possible to maintain good adhesion strength for a long period of time and to stably exhibit durability at high temperatures or under wet conditions. Thereby, the quality of the polarizing plate can be sufficiently ensured, and reliability can be improved. Other embodiments of the present invention will be described. In the following embodiments, the same configurations as those of the above-described embodiments are denoted by the same reference numerals, and their description is omitted. 3 and 4 show the second embodiment of the present invention. The film surface treatment apparatus according to the second embodiment includes the electropolymer pretreatment unit A and the plasma polymerization treatment unit C, respectively. The components of the electric power pretreatment unit A include a roller electrode on the left side and a hot electrode 15 for pretreatment. The electrodes u, 15 constitute a pair of pretreatment electrodes. The pretreatment heat electrode 15 is formed in a flat plate shape and extends in parallel with the roller in the processing width direction w. The pretreatment hot electrode 15 is used with a roller electrode. On the left side. P is configured in a phased manner. For the pretreatment hot electrode. A pretreatment space 16 is formed with the roller electrode 11. The supply path 5 for the pretreatment discharge gas is arbitrarily extended from the supply source 2a and connected to the pretreatment space 16. The pretreatment hot electrode 15 is connected to the pretreatment power source 3a. The pre-processing power source 3& supplies, for example, a pulse-wave power to the roller electrode. Thereby, an electric field is applied between the electrodes 15 and 11, and an electro-convergence discharge is generated under a pressure near atmospheric pressure. The pre-treatment space 16 becomes near atmospheric pressure. Discharge space. 7 The components of the plasma polymerization treatment unit C include a central roller (four) and electrodes (12) 13 on the right side (fourth) m.

S 158970.doc •23· 201224026 Extreme. The roller electrode 13 is connected to the polymerization processing power source 3 c for the plasma polymerization processing unit C. The c-polymerization processing power source 3 c supplies the pulsed electric power to the roller electrode 13, for example. Thereby, an electric field is applied between the electrodes 13 and 12, and a plasma discharge is generated under a pressure in the vicinity of the atmospheric pressure. The discharge space 19 serves as a polymerization processing space dedicated to the plasma polymerization processing unit C. The discharge gas nozzle 30 constitutes a nozzle dedicated to the plasma polymerization treatment unit C. The supply path 5c for the polymerization treatment discharge gas extends from the supply source 2c and is connected to the nozzle 30. In the film surface treatment apparatus 1A, the pair of pretreatment electrodes 11 and 15, the reaction gas nozzles 21 and 22, and the pair of polymerization processing electrodes I2 and 13 are arranged in this order along the upstream side of the transport path of the tac film 9. According to the second embodiment, the plasma pretreatment step, the reaction gas spraying step, and the plasma polymerization treatment step are continuously performed while sequentially transporting the TAC film 9 in the forward direction. When it is described in detail, the roller electrodes 11, 12, and 13 are rotated forward in the clockwise direction in Fig. 3, and the TAC film 9 is conveyed to the substantially right direction in the order of the roller electrodes 11, 12, and 13 (transporting step). Simultaneously with the above-described transfer, electric power is supplied from the power source 3a to the electrode 15, and the pre-treatment discharge gas is supplied from the supply source 2a to the pre-treatment space plasma pretreatment step). Thereby, the atmospheric piezoelectric discharge is generated in the pretreatment space 16 and the pretreatment discharge gas is plasmaized, and the TAC film is contacted at 9° to reduce or remove the lower aliphatic alcohol or plasticizer. ingredient. At this time, as in the first embodiment, the supply energy for plasma formation (for example, the DC power supply before the AC conversion in the power source 3a is calculated 158970.doc)

The energy supply of S - 24 · 201224026 is adjusted so that the unit area of the TAC film 9 is 0.5 to 7.5 W.sec/cm 2 . The supply energy can be adjusted by the supply power from the pretreatment power source 3a, the transfer speed of the TAC film 9, the size of the pretreatment space 16, and the like. Then, the TAC film 9 is sprayed into the space 17 through the reaction gas, and is further sprayed into the space 18 by the reaction gas. In the reaction gas spraying spaces 丨7 and 丨8, the reaction gas is sprayed from the nozzles 21 and 22 to the TAC film 9, and the acrylic acid in the reaction gas adheres to the TAC film 9, and further penetrates into the TAC film 9. (Reaction gas spraying step). Then, the TAC film 9 is introduced into the polymerization treatment space μ. At the same time, the power is supplied from the polymerization power source 3c to the roller electrode 13, and the polymerization process discharge gas is supplied from the nozzle 30 to the polymerization processing space i9 (electropolymerization processing step). Thereby, the atmospheric piezoelectric slurry is discharged in the polymerization processing space 19, and the polymerization gas for the polymerization treatment is plasma-treated and brought into contact with the TAC film 9. Thereby, the acrylic monomer adhered and infiltrated into the TAC film 9 can be plasma-polymerized to form an adhesion promoting layer. In the second embodiment, since the plasma pretreatment, the reaction gas supply, and the electrification polymerization treatment can be continuously performed, the processing time can be shortened and the processing efficiency can be 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, the carrier gas (N2 or the like) in the reaction gas may also have a discharge gas for polymerization treatment. A gas mixture of a polymerizable monomer such as acrylic acid and a discharge gas for a carrier gas polymerization treatment such as A may be supplied from the nozzle 30 to the discharge space 19, 158970.doc • 25·

S 201224026 Simultaneously, the spraying of the polymerizable monomer to be treated (reaction gas spraying step) and the plasma irradiation for plasma polymerization treatment (plasma polymerization processing step) are performed. In this case, the nozzles 21 and 22 for the reaction gas may be omitted. In the first embodiment (Fig. 1), the roller electrode 11 and the reaction gas nozzle 21 may be omitted. In the second embodiment (Fig. 3), the roller electrode 丨丨 and the reaction gas nozzle 21' may be omitted, and the pretreatment hot electrode 15 may be disposed to face the left side portion of the roller electrode 12, and the electrodes 15 and 12 are arranged. A pair of pretreatment electrodes are formed. The shielding members 23, 24 may also be omitted. The occluding member 39 can also be omitted. The discharge gas nozzle 3 〇 may be disposed at a position above the discharge space 丨 9 at the position of the closing member 39. 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. [Embodiment 1] Although the embodiment will be described, the present invention is not limited to the following embodiment. The surface treatment of the film to be processed 9 is performed using the film surface treatment apparatus 1 shown in Figs. 1 and 2 . The film to be treated 9 is a TAC film. The width width w of the TAC film 9 is 330 mm. The size of the device 1 is as follows. The axial length of the processing width direction w of the roller electrodes 11, 12, 13 is: 350 mm The thickness of the discharge space 19 (the distance between the roller electrodes 12, 13): 〇.7 mm The upper and lower sides of the discharge space 19: about 30 mm 158970.doc -26- 201224026 Processing width direction of reaction gas nozzles 21, 22... 325 mm Discharge width of treatment width direction w of discharge gas nozzle 30: 325 mm [plasma pretreatment step] First, for TAC film 9 Performing plasma pretreatment - The TAC film 9 is wound around the roller electrodes 11, 12, 13 and conveyed in the forward direction (substantially right direction in the drawing), and a voltage is applied between the electrodes 12 and 13 to generate an atmospheric piezoelectric slurry. Discharge. At the same time, the pretreatment discharge gas is supplied from the nozzle 30 to the discharge space 19 to be electrically incinerated and brought into contact with the film 9. The processing conditions are as follows. Transfer speed of film 9 k) m/min Set temperature of film 9: 4 〇.放电Pretreatment discharge gas ^2 : 20 slm 〇2 : 5 slm (content rate 20 vol%) Plasma condition power supply: 1408 W (AC conversion of DC 440 Vx3.2 A) Application between electrodes 12 and 13 Voltage: Vpp = 16.7 kV Supply energy per unit area of the film 9: 1.6 W. SeC/cm 2 The above-mentioned supply energy was calculated by the following formula. Supply this amount = (plasma irradiation time X supply power) / discharge area (Formula 1) The plasma irradiation time is caused by the time when the dots on the film 9 pass through the discharge space 19, and the dots on the film 9 pass twice. In the discharge space 19, it becomes the electric glory: the irradiation time = (the length above the discharge space / the film transport speed) χ 2 (Expression s 158970.doc • 27·201224026 The discharge area is the upper length of the discharge space 19 and the roller electrodes 12, 13 The product of the axial length in the width direction w is processed. After the plasma pretreatment step is completed, the roller electrodes 11, 12, 13 are reversed to be wound back into the TAC film 9. [Reaction gas spraying step] Thereafter, the roller electrode is again applied 11, 12, 13 are rotated forward, and the TAC film 9 is transported in the forward direction, and the reaction gas spraying step and the plasma polymerization processing step are carried out. In the reaction gas spraying step, the gas is supplied to the gasifier of the reaction gas supply source 2b. The polymerizable monomer is vaporized in a carrier gas to obtain a reaction gas, and the reaction gas is equally distributed to the two nozzles 21 and 22, and is discharged to the spray spaces 17, 18, respectively, to be in contact with the membrane 9. The processing conditions of the gas spraying step are as follows. : 30 m / min Setting temperature of membrane 9 : 4 〇. Setting temperature of 〇 gasifier: 14 〇 ° C Reaction gas polymerizable monomer: acrylic acid (aa) 15 g / min carrier gas. N2 80 slm nozzle 21 Setting temperature of 22: 75. 〇 [plasma polymerization treatment step] In the subsequent plasma polymerization treatment step, a voltage is applied between the electrodes 12 and 13 to generate an atmospheric piezoelectric slurry discharge. At the same time, a discharge gas for polymerization treatment is used from the nozzle 30. It is supplied to the discharge space 19 to be plasmalized and brought into contact with the film 9. The processing conditions of the plasma polymerization treatment step are as follows. Further, the plasma polymerization treatment step 158970.doc

S -28- 201224026 The film transport speed and film set temperature are the same as the reaction gas spray step. Discharge gas for polymerization treatment: N2 20 slm Nozzle 30 set temperature: 40 °C Plasma condition Power supply: 1833 W (AC conversion of DC 470 Vx3.9 A)

Applied voltage between the electrodes 12 and 13: Vpp = 17.5 kV The treated TAC film 9 was bonded to the PVA film. As the adhesive, an aqueous solution obtained by mixing (A) a PVA 5 wt% aqueous solution having a polymerization degree of 500 and (B) a sodium carboxymethylcellulose sodium 2 wt% aqueous solution was used. The mixing ratio of (A) and (B) is set to (A): (B) = 20:1. The drying conditions of the adhesive were set to 8 (TC, 5 minutes). A sample of 25 mm width was cut out from the film 9 after the filming. The tensile strength of the initial stage (soon after hardening of the adhesive) was measured for 5 samples. It is a floating roll method (JIS K 6854). The initial tensile strength is 10.3 N/25 mm on average. Further, the remaining samples are investigated for durability after exposure to high temperature and high humidity under warm conditions. The sample was kept at 60 ° C and 95% RH. The sample was kept in the test chamber under the warm conditions for 1 hour, and then, after cooling for 3 minutes, the tensile strength was measured. The measurement method was set to be the same as the measurement of the initial tensile strength. Roll method (JIS K 6854). The measurement result was an average of 6.2 N/25 mm for 5 samples, so that sufficient adhesion durability was obtained. [Embodiment 2] In Example 2, the same apparatus as in Example 1 was used. The film transport speed in the plasma pretreatment step was changed to 10 m/min with respect to Example 1. Therefore, the supply energy per unit area of the film 9 became 4.8 158 970.doc -29 · 201224026 W.secW. Other than this, the Korean order and processing conditions except the plasma pretreatment step 'The reaction gas timing and the electric t polymerization treatment step are the same as in the first embodiment. The subsequent procedure after the surface treatment and the tensile strength measurement procedure also include the warm heat treatment, which is the same as in the example i. The measurement result is the initial stretching. The tensile strength (following durability) after the heat treatment of 10.4 N/25 mm' was 5.6 N/25 mm. A sufficient adhesive durability was obtained. [Example 3] In Example 3, the use and the implementation were The same apparatus was used, and the surface treatment was performed under the same conditions as in Example i except that the composition of the discharge gas for pretreatment was N2 12.5 sIm and 〇2 125 - (content ratio 50). The supply energy per unit area is Μ Wwc/cm2»The subsequent procedure of the surface treatment and the tensile strength measurement procedure including the warm heat treatment are the same as in the example 。. The initial tensile strength is 9.8 N/25 mm. The tensile strength (following durability) after the heat treatment was 5.8 N/25 mm, and sufficient adhesion durability was obtained. [Example 4] In Example 4, the apparatus 1A of Fig. 3 and Fig. 4 was used. The electrodes 11 and 15 of the pretreatment unit a are placed The length of the upper portion of the space 17 is about 3 mm. The other dimensions of the device 1A are the same as those of the device i of the embodiment. The material and width of the film 9 are also the same as those of the first embodiment. In the order of 12, 13, the plasma pretreatment step of the plasma pretreatment unit A is continuously performed in sequence, and the reaction gas spraying step using the reaction gas supply unit B and the plasma polymerization processing unit c are used. The plasma polymerization treatment step. Of course, there is no rewinding step between the plasma pretreatment step and the reaction gas spraying step 15897 〇.d〇c • 30· 201224026. The transport speed of the film 9 was set to 3 〇 m/min °. The plasma conditions of the electrolysis pretreatment step were as follows. Power supply: m〇w (AC conversion of DC 350 Vx3.6A) Voltage applied between electrodes 11 and 15: Vpp=14 〇kv Supply energy per unit area of film 9: 0.7 W.sec/cm2 at device 1A In this case, the film 9 passes through the discharge space of the plasma pretreatment portion a, and the number of times is one. Therefore, the plasma irradiation time is calculated by substituting the following formula for Equation 2. 3) Electron irradiation time = (upper length of discharge space / film conveyance speed) (Processing conditions of the method) The reaction gas addition step and the money polymerization treatment step are the same as those of the embodiment i except for the plasma pretreatment step. The procedure for determining the adhesion procedure at the surface and the tensile strength also includes warm heat treatment, which is the same as in Example 1. The initial tensile strength is 10.1 N/25 mm, and the heat treatment is as follows. The properties are 6.2 N/25 mm. A sufficient adhesive durability can be obtained. The processing conditions and evaluation results of Examples 1 to 4 are shown in Table 158970.doc -31. 201224026 [Table i] Example 1 Example 2 Example 3 Example 4 Apparatus 1 1 1 ΙΑ n2 slm 20 20 12.5 20 〇 2 slm 5 5 12.5 5 Film temperature °C 40 40 40 40 Pre-film speed m/min 30 10 30 30 Supply DC voltage V 440 440 440 350 Step-up supply of DC current A 3.2 3.2 3.2 3.6 Supply of power W 1408 1408 1408 1260 Applied voltage Vpp kV 16.7 16.7 16.7 14 Supply energy W.sec/cm2 1.6 4.8 1.6 0.7 Anti-carrier gas N2 slm 80 80 80 80 Monomer AA g/min 15 15 15 15 gas Body gasifier temperature °c 140 140 140 140 Spray reaction gas ejection temperature °C 75 75 75 75 Attachment film temperature °c 40 40 40 40 Step or film speed m/min 30 30 30 30 & Electric discharge gas n2 Slm 20 20 20 20 Slurry discharge gas temperature °c 40 40 40 40 Supply DC voltage V 470 470 470 470 Process supply DC current A 3.9 3.9 3.9 3.9 Step supply power W 1833 1833 1833 1833 Voltage application Vpp kV 17.5 17.5 17.5 17.5 Evaluation of initial tensile strength N/25 mm 10.3 10.4 9.8 10.1 Durable tensile strength N/25 mm 6.2 5.6 5.8 6.2 [Example 5] In Example 5, the same apparatus 1 as in Example 1 was used, and relative to the examples (1) The film transport speed in the plasma pretreatment step was changed to 8 m/min. Therefore, the supply energy per unit area of the film 9 was 6.0 W_sec/cm2. Other processing procedures and processing conditions In addition to the plasma pretreatment step, the reaction gas spraying step and the plasma polymerization processing step are also the same as in the first embodiment. The procedure for determining the adhesion procedure after the surface treatment and the tensile strength also includes the heat treatment of 158970.doc -32-201224026, which is the same as in the first embodiment. The initial tensile strength was 9.3 N/25 mm, and the tensile strength (following durability) after the heat treatment was 47 N/25 mm. A sufficient adhesion durability can be obtained. [Example 6] In Example 6, the same apparatus 1 as in Example 1 was used, and the film transport speed in the plasma pretreatment step was changed to 65 m/min with respect to Example 1. Therefore, the supply energy per unit area of the film 9 becomes 7 4 W.sec/cm2. Other processing procedures and processing conditions In addition to the plasma pretreatment step, the reaction gas spraying step and the plasma polymerization processing step are also the same as in the first embodiment. The subsequent procedure after the surface treatment and the measurement of the tensile strength also included the warm heat treatment' as in the first embodiment. The initial tensile strength was 8.5 N/25 mm, and the tensile strength (and subsequent durability) after heat treatment was 3.6 N/25 mm. A sufficient adhesion durability can be obtained. The treatment conditions and evaluation results of Examples 5 and 6 are shown in Table 2.

C 158970.doc .33* 201224026 [Table 2] Example 5 Example 6 Apparatus 1 1 Plasma pretreatment step N2 slm 20 20 〇2 slm 5 5 Membrane temperature °C 40 40 Membrane speed m/min 8 6.5 Supply DC Voltage V 440 440 Supply DC current A 3.2 3.2 Supply power w 1408 1408 Applied voltage Vpp kV 16.7 16.7 Supply energy. W^sec/cm2 6.0 7.4 Reaction gas spray step & Plasma polymerization treatment step Carrier gas N2 slm 80 80 Single Volume AA g/min 15 15 Gasifier temperature _ °C 140 140 Reaction gas ejection temperature °C 75 75 Film temperature °C 40 40 Film speed m/min 30 30 Discharge gas N2 slm 20 20 Discharge gas temperature °C 40 40 Supply DC voltage V 470 470 Supply DC current A 3.9 3.9 Supply power w 1833 1833 Applied voltage Vpp kV 17.5 17.5 Evaluation Initial tensile strength N/25 mm 9.3 8.5 Long-term tensile strength N/25 mm 4.7 3.6 [Comparative Example 1] In Comparative Example 1, the same apparatus 1 as in Example 1 was used, and the plasma pretreatment step was omitted, and only the reaction gas spraying step and the plasma polymerization treatment step were performed. Therefore, the plasma pretreatment supply energy per unit area of the film 9 is zero. 158970.doc -34·201224026 The treatment conditions of the reaction gas spraying step and the plasma polymerization treatment step are the same as in the first embodiment. The subsequent procedure after the surface treatment and the measurement procedure of the tensile strength also included a warm heat treatment, which was the same as in Example 1. The measurement results showed that the initial tensile strength was 6·2 N/25 mm. The tensile strength (following durability) after the heat treatment was 0·7 N/25 mm. Then, the durability was drastically lowered as compared with the examples. From the results of Examples 1 to 4 and Comparative Example 1, it was confirmed that the post-treatment durability can be greatly improved by performing the plasma pretreatment step before the reaction gas spraying step and the plasma polymerization treatment step. [Comparative Example 2] In Comparative Example 2, the same apparatus 1 as in Example 1 was used, and the film transport speed in the plasma pretreatment step was changed to 5 m/min with respect to Example 1. Therefore, the supply energy per unit area of the film 9 becomes 9.7 w.sec/cm2. Other processing procedures and processing conditions In addition to the plasma pretreatment step, the reaction gas spraying step and the plasma polymerization processing step are also the same as in the first embodiment. The subsequent procedure after the surface treatment and the measurement procedure of the tensile strength also include the warm heat treatment' as in the first embodiment. The initial tensile strength was 7·6 N/25 mm, and the tensile strength (following durability) after the heat treatment was 0.4 N/2 5 mm. Then, the durability was drastically lowered as compared with Examples 1 to 4. [Comparative Example 3] In Comparative Example 3, the same apparatus 1 as in Example 1 was used, and the film transport speed in the plasma pretreatment step was changed to 3 m/min with respect to Example 1. Therefore, the supply energy per unit area of the film 9 becomes 16" w.sec/cm2. Other processing procedures and processing conditions In addition to the plasma pretreatment step, the reaction gas spraying step and the plasma polymerization processing step are also the same as those in Embodiment 1 158970.doc -35 - 201224026. The post-surface pick-up procedure and the tensile strength measurement procedure also include warm heat treatment, and examples! The initial tensile strength of the phase is 5.6 N/25 mm, and the tensile strength (following durability) after heat treatment is N /2 5 m. Then, the durability was drastically lowered as compared with Examples 1 to 4. Fig. 5 is a graph showing the results of Examples 1 to 6 and Comparative Examples 1 to 3. As is clear from Fig. 5, "II" is adjusted to a suitable size by adjusting the supply energy in the plasma pretreatment step, and it is found that the adhesion durability can be sufficiently improved. If the supply energy is too small, or the supply energy is 0 (comparative example), the effect of improving the durability can not be obtained. On the other hand, if the supply energy is too large (Comparative Examples 2 and 3), the durability is lowered. It is considered that the surface of the film 9 is not excessively penetrated into the inside of the film 9 due to the excessively flattened polystyrene monomer, and thus the adhesion of the adhesion promoting layer is lowered, specifically, based on the power source 3, "the DC supply" When the supply energy calculated by electric power is about 0.5 to 7.5 W'sec/cm2 per unit area of the film 9, the adhesion durability can be surely improved. If the supply energy exceeds the unit area of the film 9 by about 7 5 w_sec/cm 2 Then, the durability was remarkably lowered. [Comparative Example 4] In Comparative Example 4, the same apparatus 1 as in Example 1 was used, and the composition of the pretreatment discharge gas in the plasma pretreatment step was changed with respect to Example 1. It is only 2 25 slm (oxygen content rate 100%). The other treatment procedures and processing conditions are the same as in the first embodiment except for the plasma pretreatment step, and the reaction gas spraying step and the plasma polymerization treatment step. The procedure followed by the surface treatment and the tensile strength measurement procedure also included a warm heat treatment, which was the same as in Example 1. The initial tensile strength was 9.6 N/25 mm, and the warming was 158970.doc • 36 - 201224026 Post pull The strength (following durability) was 3.1 N/25 mm. Then, the durability was lowered as compared with Examples 1 to 4. [Comparative Example 5] In Comparative Example 4, the same apparatus 1 as in Example 1 was used, and the operation was carried out. Example 1 The composition of the pretreatment discharge gas in the plasma pretreatment step was changed to only N2 25 slm (oxygen content rate 〇%). Other processing procedures and processing conditions except the electrolysis pretreatment step, the reaction gas The spraying step and the plasma polymerization treatment step are also the same as in the first embodiment. The subsequent procedure of the surface treatment and the tensile strength measurement procedure also include a warm heat treatment, which is the same as that of the first embodiment, and the temperature is the same. The tensile strength (following durability) after the initial tensile strength of 2.2 N/25 was 0·4 N/25 mm, and the durability was drastically decreased as compared with Examples 1 to 4. From Examples 1 to 6 and As a result of the comparison of the examples 4 and 5, it was found that the oxygen content of the discharge gas for pretreatment was sufficient, and it was found that the oxygen content of the discharge gas for pretreatment was too large (Comparative Example 4). Oxygen atom active species produced by electropolymerization discharge On the other hand, it is considered that if the pre-treatment discharge gas does not contain oxygen (Comparative Example 5), the components cannot be separated and analyzed. The processing conditions and evaluation results of Comparative Examples 1 to 5 are shown in table 3.

S 158970.doc -37- 201224026 [Table 3] Comparative Example Comparative Example Comparative Example Comparative Example 1 2 3 4 5 Device 1 1 1 1 1 n2 slm / 20 20 0 25 〇2 slm / 5 5 25 0 Electric film Temperature °C / 40 40 40 40 Slurry film speed m / min / 5 3 30 30 J only processing step supply DC voltage V / 440 440 440 440 Supply DC current A / 3.2 3.2 3.2 3.2 Supply power W / 1408 1408 1408 1408 Applied voltage Vpp kV / 16.7 16.7 16.7 16.7 Supply energy W_sec/cm2 0 9.7 16.1 1.6 1.6 Carrier gas n2 slm 80 80 80 80 80 Reaction gas spray monomer AA g/min 15 15 15 15 15 Gasifier temperature °c 140 140 140 140 140 Reaction gas ejection temperature °C 75 75 75 75 75 Attachment & Film temperature °c 40 40 40 40 40 Film speed m/min 30 30 30 30 30 Discharge gas n2 slm 20 20 20 20 20 Pulp Poly discharge gas temperature °C 40 40 40 40 40 Combined processing steps to supply DC voltage V 470 470 470 470 470 Supply DC current A 3.9 3.9 3.9 3.9 3.9 Supply power W 1833 1833 1833 1833 1833 Applied voltage Vpp kV 17.5 17.5 17.5 17.5 17.5 Evaluation Strong initial tensile strength Degree N/25 mm 6.2 7.6 5.6 9.6 2.2 Long-term tensile strength N/25 mm 0.7 0.4 0.5 3.1 0.4 [Industrial Applicability] The present invention can be applied to a polarizing plate such as a flat panel display (FPD) Manufacturing. [Brief Description of the Drawings] FIG. 1 is a side view showing a film surface treatment apparatus according to a first 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 side view showing the film surface treatment apparatus according to the second embodiment of the present invention in an illustrated manner. Fig. 4 is a perspective view showing a treatment portion of the film surface treatment apparatus according to the second embodiment. Fig. 5 is a graph showing the results of Examples 1 to 4 and Comparative Examples 1 to 3. [Description of main component symbols] 2a Pretreatment discharge gas supply source 2b Reaction gas supply source 2c Polymerization treatment discharge gas supply source 3 Power supply 3a Pretreatment power supply 3c Polymerization processing power supply 4 Reaction gas supply path 5 Discharge gas common supply path 5a Pretreatment discharge gas supply path 5b Polymerization process discharge gas supply path 5e Switching mechanism 9 TAC film (processed film) 10 Film surface treatment portion 11 Roll electrode 12 Roll electrode 158970.doc

S 201224026 13 Roll electrode 15 Preheating electrode for pretreatment 16 Pretreatment space 17 Reaction gas spray space 18 Reaction gas spray space 19 Discharge space, polymerization treatment space 21 Reaction gas nozzle 21a Ejection port 22 Reaction gas nozzle 22a Ejection port 23 Masking Member 24 Masking member 30 Discharge gas nozzle 39 Closing member 41 Guide roller 42 Guide roller A Plasma pretreatment portion B Reaction gas supply portion C Plasma polymerization processing portion 158970.doc -40-

Claims (1)

201224026 VII. Patent application scope: κ-film surface treatment method, which is characterized in that it is surface-treated for a resin-treated film; the method comprises the following steps: an electric pre-treatment step, which will contain oxygen and nitrogen The pretreatment is performed. The electric gas is plasmatized near atmospheric pressure and brought into contact with the film to be treated; and the reaction gas spraying step is performed by contacting the reaction gas containing the polymerizable monomer with the plasma pretreatment step. a post-processed film; and a plasma polymerization treatment step of slurrying the discharge gas for polymerization treatment at a temperature near atmospheric pressure after the reaction gas spraying step or simultaneously with the reaction gas spraying step It contacts the above-mentioned treated film; and is adjusted in such a manner that the supplied energy in the plasma pretreatment step is within a specific range. 2. The film surface treatment method according to claim 1, wherein the supply energy of the power supply based on the power source for the plasmaization in the plasma pretreatment step is set to be 〇5~ per unit area of the film to be treated. 75 W-sec/cm2 〇3. The film surface treatment method according to claim 1 or 2, wherein the volume ratio of oxygen occupied by the above-mentioned pretreatment electric discharge gas is 〇10/〇~5〇0/〇 . A film surface treatment apparatus characterized by being surface-treated with a resin-treated film; comprising: a plasma pretreatment section comprising a pair of pretreatment electrodes, and the pretreatment electrodes Between each other, the pretreatment discharge gas 158970.doc 201224026 containing oxygen and nitrogen is pulverized near the atmospheric pressure and brought into contact with the treated film; and the reaction gas supply portion includes and contacts the discharge for the pretreatment. a reaction gas nozzle facing the film to be treated after the plasma of the gas, and a reaction gas containing the polymerizable monomer is ejected from the reaction gas nozzle and brought into contact with the film to be processed; and a plasma polymerization treatment unit includes a pair of polymerization treatment electrodes, and after the reaction gas is ejected or simultaneously with the ejection, the discharge gas for polymerization treatment is plasma-pulped near the atmospheric pressure between the polymerization treatment electrodes and is brought into contact with the above-mentioned The film is processed; and the supply energy in the plasma pretreatment section is set within a specific range. The film surface treatment apparatus according to claim 4, wherein the pretreatment electrode is connected to a power source, and the supply energy based on the supply power of the power source is 05 to 7 5 w.sec/cm 2 per unit area of the film to be processed. 6. The film surface treatment apparatus according to claim 4, wherein the film to be processed is in a continuous sheet shape, and further wherein the film surface treatment device includes a conveying mechanism that continuously conveys the film to be processed, and the pair of pretreatment electrodes The reaction gas nozzle and the pair of polymerization processing electrodes are disposed in order from the upstream side of the transport path of the processed film along the transport mechanism. 158970.doc